JPH06271414A - Antifungal powder and production thereof - Google Patents

Abstract

PURPOSE:To provide a production process for antifungal powder which is resistant to discoloration by light (ultraviolet light) and has excellent antifungal activity with high safety. CONSTITUTION:A silver nitrate solution and a disodium hydrogen phosphate solution are allowed to react with each other as a nitrogen gas is passed through the mixture. The precipitate formed is filtered, washed, dried and crushed into powder. The powder is heat-treated at 500 to 840 deg.C for 1 to 48 hours to give the objective antifungal crystals of Ag3PO4. The crystalline Ag3PO4 has a broad spectrum of antifungal and antibacterial activities, and shows very high stability to oxygen in the air and light and causes no deterioration and discoloration with the passage of time. Further, since it is hardly soluble in water, it is very stable in the solution as Ag3O4. Therefore, the crystalline powder of Ag3PO4 are effective as an antifungal powder and admixed to resins, coatings, papers and fibers to give them antimicrobial activities.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel antibacterial powder having an antibacterial effect against various bacteria and fungi and a method for producing the same, and further has an antibacterial coating, an antibacterial fiber and an antibacterial property. Paper, antibacterial resin, antibacterial film,
The present invention relates to antibacterial tile joints, antibacterial glass and cosmetics.

[0002]

2. Description of the Related Art It has long been known that silver, copper, zinc and lead have a bactericidal action. Therefore, the above metal compounds such as silver are adsorbed on activated carbon, alumina and silica gel zeolite and used for the purpose of sterilization, as disclosed in JP-A-62-241939 and 62-62.
Japanese Patent No. 238900 describes a polyolefin resin molded body containing zeolite that holds a metal having a bactericidal action in an ionic state, and paper. JP-A-3-181403, JP-A-3-20609
The publication discloses an antibacterial agent which is produced by reacting an N-long chain acylamino acid salt with a metal ion having an antibacterial activity.

Further, as an inorganic antibacterial agent, an antibacterial agent of an aluminosilicate compound represented by zeolite A has attracted attention and is disclosed in JP-A-60-181002 and JP-A-6-186002.
2-70220, JP-A-62-70221, JP-A-63-265809, and the like. These are Na ^{+ in} sodium aluminosilicate
Is substituted with metal ions having a bactericidal action, such as Ag ⁺ , Cu ²⁺ , Zn ^2+, etc. In addition, JP-A-3
No. 271209 discloses an antibacterial apatite in which antibacterial metal ions such as silver and zinc or copper are supported on apatite.

[0004]

Although the above-mentioned ones are relatively effective as an antibacterial action and a bactericidal action,
When using silver or a mixed substance of silver and other metal ions, silver easily oxidizes in the air, or light rays (ultraviolet rays)
The initial white substance discolors from blue gray to brown to black, and the entire substance discolors strongly, and not only the antibacterial activity and bactericidal action decrease over time, but also the product value itself significantly decreases due to the discoloration. It is what makes me. Further, the metal ion having an antibacterial action used is easily ionized, and when it is used as a liquid substance, it is likely to be eluted (flowed out), so that there is a problem in safety.

Therefore, the present invention solves the above-mentioned problems of the prior art, has a high antibacterial property and its durability, and is light (UV).
It is an object of the present invention to provide an antibacterial powder which prevents discoloration due to the above and is highly safe, and a method for producing the same. Further, an object is to provide an antibacterial coating material containing the antibacterial powder, an antibacterial fiber, an antibacterial paper, an antibacterial film, a joint for antibacterial tile, an antibacterial glass and a cosmetic. .

[0006]

[Means for Solving the Problems] As a result of intensive studies conducted by the present inventors in accordance with the above object, crystallized Ag ₃ PO _{4 was obtained.}
In addition to having a high antibacterial activity, it was stable to light or oxygen and did not cause discoloration, and completed the present invention. That is, the present invention is achieved by the following items.

An antibacterial powder composed of crystalline Ag ₃ PO ₄ . And an antibacterial powder obtained by coating crystalline Ag ₃ PO ₄ on an inorganic powder.

The above-mentioned antibacterial powder is reacted by mixing silver nitrate and dinatrihydrogen hydrogenphosphate in an aqueous system while bubbling an inert gas, collecting the formed precipitate, drying and
A heat treatment is performed at 00 to 840 ° C. for 1 to 48 hours to produce an antibacterial crystalline Ag ₃ PO ₄ powder, and the inorganic powder is previously dispersed in a reaction water system, and Ag _{3 is} deposited on the surface of the inorganic powder. PO ₄
Of the antibacterial crystalline Ag ₃ P after heat treatment at 500 to 840 ° C. for 1 to 48 hours.
An O ₄ coated inorganic powder is produced.

By incorporating the above-mentioned antibacterial crystalline Ag ₃ PO ₄ powder or antibacterial crystalline Ag ₃ PO ₄ coated inorganic powder, antibacterial paint, antibacterial fiber, antibacterial paper, antibacterial resin It is possible to provide an antibacterial film, a joint for antibacterial tile, an antibacterial glass and a cosmetic.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The crystalline Ag ₃ PO _{4 according} to the present invention is one in which the presence of an amorphous substance is hardly recognized,
It is distinguished from Ag ₃ PO ₄ which is conventionally known and which is composed of an amorphous material or has a low composition ratio of a crystalline material.

In more detail, Ag ₃ PO ₄ produces a yellow precipitate when silver nitrate and disodium hydrogen phosphate are mixed in an aqueous system. This yellow precipitate, Ag ₃ PO ₄ , whose crystal system is equiaxed cubic,
The crystallinity is very low, and most of them are composed of amorphous. This low crystalline Ag ₃ PO ₄ gradually turns black (changes to silver oxide) when exposed to light (especially ultraviolet rays), which not only lowers the antibacterial property but also lowers the quality value.

The crystalline Ag ₃ PO _{4 according} to the present invention is subjected to a bubbling process using an inert gas such as N ₂ gas, He gas, Ar gas and Xe gas during the reaction and a heat treatment process for the formed precipitate in the above method. It is manufactured by adding. That is, bubbling with an inert gas is introduced during the reaction step of silver nitrate and disodium hydrogenphosphate to produce (low crystalline) Ag ₃ PO ₄ . The precipitate is separated and preferably washed with water repeatedly until Ag ⁺ does not remain in the washing solution, dried, and optionally pulverized. When the powdered material is heat-treated, crystallization is promoted and crystalline Ag ₃ PO ₄ is produced.

The crystalline Ag ₃ PO ₄ thus obtained
Is extremely stable against ultraviolet rays and oxygen in the air,
It is an excellent antibacterial powder that has a broad antibacterial action against mold and bacteria.

A powder obtained by coating the above-mentioned crystalline Ag ₃ PO ₄ with an inorganic powder is also an excellent antibacterial powder. In a water system in which the inorganic powder is dispersed, while bubbling with an inert gas, silver nitrate is reacted with disodium hydrogen phosphate to deposit (low crystalline) Ag ₃ PO ₄ on the surface, which is preferable. Is a crystalline Ag ₃ having a crystal structure stabilized by washing with water, drying and then heat treatment in the range of 500 to 840 ° C.
A PO ₄ coated inorganic powder is produced. Examples of the inorganic powder used here include talc, kaolin, and sericite.

The coverage of the crystalline Ag ₃ PO ₄ is preferably such that the entire surface of the inorganic powder is coated, usually 2 to 25% by weight based on the total weight of the inorganic powder. In particular, 2 to 5% by weight for powder of normal size (diameter unit), 20 to 2 for fine particle powder (diameter unit).
It is preferably coated at a rate of 5% by weight. If the coverage of the crystalline Ag ₃ PO ₄ with respect to the inorganic powder is less than 2% by weight, the antibacterial action is not sufficiently exhibited. In addition, since the crystalline Ag ₃ PO _{4 on the} surface of the outermost layer of the powder exhibits an antibacterial action, even if it is coated thicker than necessary, no difference in effect is exhibited, which is not preferable in terms of production efficiency, and 25% by weight is the upper limit. Is considered to be.

Here, points to be noted in the method for producing the crystalline Ag ₃ PO ₄ powder or the crystalline Ag ₃ PO ₄ coated inorganic powder according to the present invention will be shown below.

When silver nitrate and disodium hydrogen phosphate are mixed and reacted in an aqueous system, bubbling of an inert gas expels excess oxygen in the mixed solution by stirring, and Ag ⁺ is gradually oxidized by the oxygen. To prevent discoloration. The bubbling step is preferably performed immediately after the silver nitrate is dissolved until the reaction with disodium hydrogen phosphate is completely completed.

This step of bubbling an inert gas is very effective, and the powder remains yellow to yellowish green even when the reaction is completed and aged. If this bubbling is removed, the powder will change from green to brown. In addition, the bubbling treatment of Ag ₃ PO ₄ does not change much even if it is washed with water after fractionation and is yellowish green, while it changes from brown to blackish brown if the bubbling treatment is not carried out.

After the completion of drying, the temperature is 1-48 at 500-840 ° C.
When heat treatment is carried out for a time, preferably 600 to 750 ° C. for 2 to 10 hours, crystallization of Ag ₃ PO ₄ occurs and becomes stable, and deterioration due to light (especially ultraviolet light) does not occur. After the heat treatment, the color of the powder is restored to the yellow color at the beginning of the reaction, and even if the powder is left in the atmosphere or forcibly irradiated with UV for 30 hours, no discoloration is observed. In the case where this heat treatment is not performed, the surface layer of Ag ₃ PO ₄ changes from brown to blackish brown when left in the air for a long time. If this heat treatment step is performed at a temperature lower than 500 ° C., crystallization of Ag ₃ PO ₄ does not proceed sufficiently. On the other hand, since Ag ₃ PO ₄ has a melting point of 849 ° C., it is melted at a temperature higher than that, so that it is preferably performed at 840 ° C. or lower.

Further, in the reaction for producing silver phosphate between silver nitrate and disodium hydrogen phosphate, it is preferable to react in the presence of an excessive amount of disodium hydrogen phosphate. If a large amount of silver nitrate is present, A that remains unreacted after fractionation
Since g ⁺ produces Ag ₂ O by heat treatment and the powder is colored blackish, it should be avoided. On the other hand, when the disodium hydrogen phosphate is present in excess, it is easily removed by washing with water. Alternatively, washing, those Ag ₃ PO ₄ becomes undergo some oxidation Ag ₂ O in the subsequent drying step or the like, in subsequent heat treatment process, the Ag ₂ O
Reacts with the remaining disodium hydrogen phosphate,
Again it can be Ag ₃ PO ₄ . That is, the disodium hydrogen phosphate is preferably at least twice the reaction amount (2 mol or more relative to 3 mol of silver nitrate), and the weight ratio of silver nitrate: disodium hydrogen phosphate is 1: 0.5 to 1: 3.
Is preferred. The disodium hydrogen phosphate of 3 times or more is wasted, which is not preferable in terms of production efficiency.

Next, crystalline Ag ₃ PO ₄ powder and crystalline A
A general method for producing g ₃ PO ₄ -coated inorganic powder will be described.

[0022]

[Manufacturing Method 1] Crystalline Ag ₃ PO ₄ powder 3.5 to 5.0 parts of A in 400 ml to 2,000 ml of purified water
Dissolve gNO ₃ . The solution is reacted at 5 to 60 ° C. while blowing an inert gas. Bubbling continues until the reaction process is complete. A solution prepared by dissolving 0.5 to 15 parts of disodium hydrogen phosphate in 50 ml to 1000 ml is gradually added to the bubbling solution while stirring. After completion of the addition, stirring is continued for 1 to 6 hours to complete the reaction and ripen. After that, after washing with water and filtering,
Repeated washing with ethanol and acetone at 40-60 ° C for 1-
Dry for 24 hours and grind. The crushed Ag ₃ PO ₄ is heat-treated at 500 to 840 ° C. for 1 to 48 hours in an electric furnace and taken out.

[0023]

[Production Method 2] Crystalline Ag ₃ PO ₄ coated inorganic powder: 3.5 to 5.0 parts of A in 400 ml to 2,000 ml of purified water.
50 to 200 inorganic powder in a solution in which gNO ₃ is dissolved
Disperse the parts. Blow an inert gas into this solution 5
Bubble at a temperature of 60 ° C. until the reaction process is complete. A solution in which 1.5 to 15 parts of disodium hydrogen phosphate is dissolved is gradually added to this bubbling solution while stirring. After completion of the addition, stirring is continued for 1 to 6 hours to complete the reaction and ripen. Then, after washing with water and filtration, washing with ethanol and washing with acetone were repeated,
Dry at 60 ° C. for 1 to 24 hours and grind. The crushed A
g ₃ PO ₄ coated inorganic powder at 500 ~ 840 ℃ in an electric furnace 1
Heat-treat for ~ 48 hours and remove.

The above-mentioned crystalline Ag ₃ PO ₄ powder or crystalline Ag ₃ PO ₄ coated inorganic powder according to the present invention is contained in various substances such as paint, fiber, paper, resin, glass, cosmetics and the like. Antibacterial properties can be imparted to these substances by allowing them to adhere to the surface. Further, in the antibacterial resin, an antibacterial film is produced by selecting a resin that can be film-formed by spreading such as a polyolefin resin, and if an adhesive resin such as a vinyl acetate resin is selected,
An antibacterial tile jointing agent is manufactured.

The above-mentioned antibacterial substance is replaced with known antibacterial substances of these antibacterial substances, and crystalline Ag ₃ PO ₄ powder and crystalline Ag ₃ PO ₄ coated inorganic powder according to the present invention are added to the above substances. It is manufactured by containing or adhering. For example, a paper having antibacterial properties is produced by using the crystalline Ag ₃ PO ₄ powder of the present invention in place of the zeolite holding a metal having a bactericidal action described in JP-A-62-238900. In addition, 2 described in JP-A-3-20609
Crystalline Ag ₃ PO ₄ powder or crystalline A of the present invention in place of the N-long chain acylamino acid salt to which one or more antibacterial metals are bound
Antibacterial resin, antibacterial film, joints for antibacterial tile, antibacterial fiber, antibacterial paper, antibacterial paint, antibacterial glass, antibacterial cosmetics, etc. are manufactured using g ₃ PO ₄ coated inorganic powder. To be done.

The content of the antibacterial powder according to the present invention in the antibacterial substance is preferably 0.001 to 10% by weight, more preferably 0.01 to 3% by weight, in the antibacterial resin, based on the total weight. , 0.01 to 10% by weight for antibacterial paints, 0.05 to 3% by weight for antibacterial papers, more preferably 0.1 to 1% by weight, 0.01 to 10% by weight for antibacterial cosmetics, more preferably 0.01% by weight. -3% by weight, antibacterial glass is about 10-30% by weight, particularly preferably about 20% by weight.

In any case, if the amount of the antibacterial powder according to the present invention is less than the lower limit value, the antibacterial effect is not sufficiently exhibited. On the other hand, the antibacterial effect is saturated at a predetermined amount or more, and there is no difference in the antibacterial effect. Therefore, it is economically not preferable to blend the antibacterial powder in excess of the upper limit.

[0028]

The crystalline Ag ₃ PO _{4 according} to the present invention has remarkably improved photostability against light, especially against ultraviolet rays, and does not discolor even when exposed to sunlight or artificial light.
It maintains stability for a long period of time and has a continuous antibacterial action.

That is, the crystalline Ag ₃ PO ₄ powder and the crystalline Ag ₃ PO ₄ coated inorganic powder according to the present invention are stable against ultraviolet rays and oxygen in the air, and further against bacteria and mold. Has a broad antibacterial spectrum and excellent antibacterial activity. It has almost no solubility in water (0.63 mg / 100 ml or less), and the mechanism of antibacterial action is unknown, but since Ag in crystalline Ag ₃ PO ₄ exists as an active phosphate, it does not affect microorganisms. It is presumed that it has a bactericidal action.

Therefore, cosmetics, paints, fibers, papers, resins,
The crystalline Ag ₃ PO ₄ powder or crystalline Ag according to the present invention can be applied to a target substance such as a film, a joint for tiles, and glass.
_By incorporating ₃ PO ₄ -coated inorganic powder inside or adhering it to the surface, antibacterial properties can be imparted to these substances.

Next, production examples of the crystalline Ag ₃ PO ₄ powder and the crystalline Ag ₃ PO ₄ coated inorganic powder according to the present invention will be described.

[0032]

[Production Example 1] 20.2 g of disodium hydrogen phosphate and purified water 2
Dissolve completely in 20 g. While blowing N ₂ gas into this uniform solution, 184 ml of 0.5 M silver nitrate aqueous solution was added, and the mixture was stirred at room temperature for 2 hours to form a beautiful yellow precipitate. After that, it is repeatedly washed with water and filtered, and washed with water until silver ions do not elute, and the color changes to yellow-green. At the end of washing with water, it was discolored to dark brown when dried for 48 hours with a warm air dryer at 45 ° C. 2 in an electric furnace in an oxidizing atmosphere
Heat treatment is performed at 750 ° C. for 0 hours. After cooling, it was taken out and pulverized to obtain a clean yellow powder.

[0033]

[Comparative Production Example 1] 20.2 g of disodium hydrogen phosphate was completely dissolved in 220 g of purified water. 0.5 in this homogeneous solution
When 184 ml of M silver nitrate aqueous solution is added and stirred at room temperature for 2 hours, a clear yellow precipitate is formed. After that, it is washed with water until silver ions do not elute, and after repeated filtration, it turns yellow green. After that, when it is dried with a warm air dryer at 45 ° C. for 48 hours, the color changes to brown. When this was ground, a light brown powder was obtained.

[0034]

[Production Example 2] 150 g of sericite is dispersed while stirring a solution in which 5.05 g of disodium hydrogen phosphate is dissolved in 2000 ml of purified water. While blowing N ₂ gas into this dispersion liquid, 46 ml of 0.5M silver nitrate aqueous solution was added to 8 ml.
When dropped at a dropping rate of / min, silver phosphate is deposited on the surface of sericite, and pale yellow sericite is produced. The pale yellow sericite is washed with water and repeatedly filtered until Ag ions are no longer eluted. Then, it was dried at 50 ° C. for 48 hours and heat-treated at 600 ° C. in an electric furnace in an oxidizing atmosphere for 10 hours to obtain pale yellow sericite.

[0035]

[Production Example 3] 100 g of sericite and 50 g of talc were stirred into a solution prepared by dissolving 10.1 g of disodium hydrogen phosphate and 10 g of a hydrophilic nonionic activator in 2000 ml of purified water.
Disperse g. While blowing N ₂ gas into this dispersion, 92 ml of 0.5 M AgNO ₃ was dropped at a dropping rate of 1.0 ml / min, and Ag ₃ P was formed on the surfaces of sericite and talc.
Washing with water is repeated until O ₄ is deposited and a yellow powder is obtained, and filtration is repeated until Ag ⁺ does not elute. Then 40
When dried at 72 ° C. for 72 hours and then heat-treated at 550 ° C. for 20 hours, a yellow mixed powder of sericite and talc is obtained.

The above crystalline Ag ₃ PO ₄ powder or crystalline Ag
An antibacterial cosmetic material and an antibacterial glass are shown below as examples of substances to which antibacterial properties are imparted by blending ₃ PO ₄ coated inorganic powder. Unless otherwise specified, the unit is% by weight.

[0037]

[Example 1] Water white

Manufacturing method A is put in a reincubator and B is added little by little and dispersed uniformly. C is added to the dispersed liquid, D is further added, and the product is filled in a container.

[0039]

[Example 2] Powder foundation

Manufacturing method A is mixed with a Henschel mixer and then ground with a grinder. After that, A is transferred to a Hensiel mixer and stirred.
After adding B to it and coating it, it is taken out, crushed by a crusher, and press-filled in an inner plate to obtain a product.

[0041]

[Example 3] Liquid foundation

Manufacturing Method A and B are separately dissolved and kept at 80 ° C., B is added little by little to A, and the mixture is sufficiently stirred to emulsify. When the emulsification is complete, add C, stir at 80 ° C for 30 minutes, cool with water and 40 ° C.
It is cooled down and filled in a take-out container to obtain a product.

[0043]

Example 4 Antibacterial glass SiO ₂ 15 parts, PbO 68 parts, Ag ₃ PO ₄ 20 parts,
Place 0.2 parts of MgO in an alumina crucible and place in an inert atmosphere for 8
Melt at 20 ° C. The melt is stirred and homogenized, then poured into a preheated mold, molded and gradually cooled.

[0044]

[Evaluation test 1] Antibacterial spectrum test Fungi: Medium E. E. coli (concentration of bacterial solution 10 ⁸ cells / ml): Tween 80. Lecithin-free TSA S. aureus (10 ⁸ / ml): Tween 80. Lecithin-free TSA A. niger (10 ⁷ cells / ml): Tween 80. Lecithin-free SDA P. citricum (10 ⁷ / ml): Tween 80. Lecithin-free SDA

Method (cup method) 0.2 ml of each of the above-mentioned bacterial solutions is placed in a Petri dish. Further, about 20 ml of the above-mentioned medium suitable for each bacterial solution is poured, mixed well and solidified. A sterilized cup (diameter 8 mm) is placed in the center of the dish. Pour the sterilized sample dispersion shown in Table 1 into the cup (about 0.2 ml). Prepare each sample dispersion with distilled water to 1.0% and 0.5% respectively. Bacteria (E. coli, S. aureus)
Were cultured at 37 ° C. for 24 hours, and the fungus (A. niger,
P. Citrum) is incubated at 30 ° C. for 48 hours, and the size of the inhibition circle is measured. The results are shown in Table 1.

[0046]

[Table 1]

As shown in Table 1, the crystalline Ag according to the present invention
₃ PO ₄ showed broad antibacterial activity against molds (fungi) and bacteria. Further, the cosmetics containing the crystalline Ag ₃ PO ₄ coated inorganic powder according to the present invention also have a sufficient antibacterial effect.

[0048]

[Evaluation test 2] X-ray structure analysis measurement method The powder of Production Example 1 was lightly crushed again using an agate mortar and pestle to prepare a sample, which was packed in an aluminum standard sample frame and measured by the reflection method.

The measurement conditions are shown below. Wide-angle X-ray diffraction (diffractometer method) 1) X-ray generator RU-200R (rotating anticathode type) X-ray source manufactured by Rigaku Denki Co., Ltd .: CuKα ray, curved crystal monochromator output 50 kV 200 mA 2) Goniometer Rigaku Denki 2155D type Slit system: 1 ° -0.15mm-1 ° Detector Scintillation counter 3) Counting recorder RAD-B type manufactured by Rigaku Denki 4) Scan method 2θ / θ scan Continuous scan 5) Measuring range (2θ) 5 ~ 100 ° 6) Counting step (2θ) 0.02 ° 7) Scan speed 2 ° / min

Results The wide-angle X-ray diffraction pattern of the sample is shown in FIG. Wide angle X of sample
After performing data processing of smoothing and background removal on the line diffraction pattern, the diffraction data (surface spacing d corresponding to each diffraction peak, diffraction angle 2θ, measured intensity and relative intensity) shown in Table 2 and FIG. 2 were selected. The crystalline constituents of the sample were searched and identified from this diffraction data.

[0051]

[Table 2]

The search / identification was performed by selecting a substance having a corresponding interplanar spacing and relative intensity from the JCPDS ^* standard diffraction data.

As a result, the presence of the following substances was confirmed as a crystalline constituent substance. The standard diffraction data for this material are shown in Table 3 and a diagram comparing this standard diffraction data with the wide angle X-ray diffractogram is shown in FIG. The diffraction peaks of the sample are almost explained by the following substances, and the presence of crystalline constituent substances other than the following substances is not confirmed.

Ag ₃ PO ₄ JCPDS No. 6-505 * Joint Committiee on Powder Diffraction Standards.

[0055]

[Table 3]

In the diffraction pattern of the sample, a broad peak corresponding to the amorphous substance was not recognized, and it is considered that the amorphous constituent substance is hardly present.

From the above, it is confirmed that the constituent substance of the sample is crystalline Ag ₃ PO ₄ .

[0058]

[Effect] The crystalline Ag ₃ PO ₄ of the present invention has a broad antibacterial action against fungi and bacteria, is extremely stable against oxygen and light in the atmosphere, and deteriorates and discolors over time. Absent. Further, since it has almost no solubility in water, it is stable as Ag ₃ PO ₄ in an aqueous solution and is safe without elution. Therefore, the crystalline Ag ₃ PO ₄ powder and the crystalline Ag ₃ PO ₄ -coated inorganic powder are excellent powders having a sufficiently long-term stable and antibacterial action. Further, these crystalline Ag ₃ PO ₄ powder and crystalline Ag ₃ PO ₄ coated inorganic powder are contained in cosmetics, paints, fibers, papers, resins, films, tile joints, glass, etc. or attached to the surface. As a result, the substance can be provided with antibacterial properties. In particular, cosmetics containing crystalline Ag ₃ PO ₄ -coated inorganic powder have excellent antibacterial properties and are safe against the skin, so that they can be used safely in a clean state for a long period of time.

[Brief description of drawings]

FIG. 1 shows a high-angle X-ray diffraction diagram of the crystalline Ag ₃ PO ₄ powder of the present invention in Production Example 1.

FIG. 2 shows diffraction data of Production Example 1 after the data processing is performed in FIG. 1 (see Table 2).

FIG. 3 JCPDS standard diffraction data (see Table 3) and FIG.
It is the figure which contrasted with the high angle X-ray diffraction pattern of FIG.

Claims (16)

[Claims] 1. An antibacterial powder comprising crystalline Ag ₃ PO ₄ . 2. An antibacterial powder obtained by coating an inorganic powder with crystalline Ag ₃ PO ₄ . 3. The antibacterial powder according to claim 2, wherein the inorganic powder is selected from talc, kaolin and sericite. 4. The antibacterial powder according to claim 2, wherein the coverage of the crystalline Ag ₃ PO ₄ is 2 to 25% by weight based on the inorganic powder. 5. Silver nitrate and disodium hydrogen phosphate are mixed by reacting in an aqueous system while bubbling an inert gas, the precipitate formed is separated, dried and heated at 500 to 840 ° C. for 1 to 48 hours. Antibacterial crystalline Ag ₃ obtained by applying
Method for producing PO ₄ powder. 6. The antibacterial crystalline Ag ₃ PO ₄ powder according to claim 5, wherein silver nitrate and disodium hydrogen phosphate are mixed in a weight ratio of 1: 0.5 to 1: 3. Manufacturing method. 7. In a water system in which an inorganic powder is dispersed, silver nitrate and disodium hydrogenphosphate are mixed while bubbling an inert gas, Ag ₃ PO ₄ is deposited on the surface of the inorganic powder, and fractionation is performed. Then, a method for producing an antibacterial crystalline Ag ₃ PO ₄ -coated inorganic powder, which is dried and then heat-treated at 500 to 840 ° C. for 1 to 48 hours. 8. The antibacterial crystalline Ag ₃ PO ₄ coated inorganic material according to claim 7, wherein silver nitrate and disodium hydrogen phosphate are mixed in a weight ratio of 1: 0.5 to 1: 3. Powder manufacturing method. 9. An antibacterial coating material containing the antibacterial powder according to any one of claims 1 to 4. 10. An antibacterial resin containing the antibacterial powder according to any one of claims 1 to 4. 11. An antibacterial film comprising the antibacterial resin according to claim 10. 12. A joint for antibacterial tile, which comprises the antibacterial resin according to claim 10 as a component. 13. An antibacterial fiber containing the antibacterial powder according to any one of claims 1 to 4. 14. An antibacterial glass containing the antibacterial powder according to any one of claims 1 to 4. 15. A paper having antibacterial properties, characterized in that it contains the antibacterial powder according to any one of claims 1 to 4 or adheres to the surface thereof. 16. A cosmetic comprising the antibacterial powder according to any one of claims 1 to 4.