JP3465248B2 - Antimicrobial agent - Google Patents

Description

Detailed Description of the Invention

[0001]

This invention relates to Zn and / or C
The present invention relates to a novel antimicrobial agent of an oxide solid solution and / or a hydrotalcite compound containing u as a main active ingredient, and an antimicrobial resin or rubber composition. More specifically, it is an antimicrobial agent which is nontoxic or extremely nontoxic in itself, has high heat resistance and weather resistance, and is excellent in dispersibility in resins, rubbers and paints, specifically, an antibacterial agent or The present invention relates to an antifungal agent and an antimicrobial resin or rubber composition containing the antimicrobial agent.

[0002]

2. Description of the Related Art Microorganisms easily grow in warm and humid places. For this reason, fungi and mold are likely to occur in many places. For example, there are cases where microorganisms are generated in drinking water, food, etc., and have a great influence on human life. Also food, cosmetics,
Plastic products, wallpaper, interior and exterior products for automobiles, building materials,
Electric wire, cable, synthetic leather, sealant, rubber hose,
Microbes are generated in adhesives, roofing, flooring materials, wood, paints, etc., causing discoloration, bad odor, and strength change. For example, if it is an electric wire, it may lead to electric leakage, which may cause a fire, electric shock, or the like. In addition, damage to valuable cultural properties by microorganisms, cancer caused by mold on plastics, outbreak of allergic pneumonia, outbreak of a large number of mites that feed on the bacteria, athlete's foot caused by Trichophyton fungus, and onset of scabies. And bring about a disaster. In recent years, there has been an increasing demand for safe, clean and comfortable living environments that prevent the above-mentioned microbial disasters. To respond to this, various antimicrobial agents are commercially available. The classification of these antimicrobial agents is as follows. Halides containing chlorine, bromine, iodine, etc .: Copper arsenite, cuprous oxide, silver nitrate, silver, inorganic compounds such as glasses containing copper, etc .: Nitrogen compounds such as amines, triazines: arsenic, copper, mercury , Organometallic compounds containing metals such as tin and zinc: isothiazolone, pyrithione,
Organic sulfur compounds such as thiocyanates: phenol compounds such as chlorinated phenol, bisphenol and o-phenylphenol.

[0003]

The growing consumer interest in safety is no exception in the field of antimicrobial agents. For this reason, the use of silver-supporting inorganic antimicrobial agents, which are relatively safe, is rapidly spreading. These are materials in which silver is supported on zeolite, apatite, silica, zirconium phosphate or the like. However, although these silver-based inorganic antimicrobial agents are less toxic than organic antimicrobial agents, they are still toxic. In addition, there are various problems that silver reacts with oxygen to be colored, foams when kneaded with a resin, and is expensive because expensive silver is used. The present invention provides an antimicrobial agent which is non-toxic or extremely less toxic in itself, has excellent heat resistance and weather resistance, is inexpensive, and has excellent dispersibility in resins, rubbers, paints, and the like, and the antimicrobial agent. It is an object to provide an antimicrobial resin or rubber composition containing the composition.

[0004]

The present invention provides a compound represented by the formula (1) [(M ₁ ²⁺ ) _y (M ₂ ²⁺ ) _1-y ] _1-x M ³⁺ _x-a O (1) ₁ ²⁺ is Zn ²⁺ and / or Cu
²⁺ , M ₂ ²⁺ is Mg ²⁺ and / or Ca
²⁺ , M ³⁺ is Al ³⁺ , Fe ³⁺ , Co ³⁺ , Cr
^{3+, In 3+, Bi 3 +} pressurized et selected showed at least one trivalent metal, x and y, 0.01 ≦ x <0.
5, preferably 0.1 ≦ x ≦ 0.4, 0 <y ≦ 1, preferably 0.01 ≦ y <0.5, x-a
Indicates that the number of M ³⁺ is reduced by a due to lattice defects], and the solid solution which is an oxide represented by
Is the formula (2) [(M ₁ ²⁺ ) _y (M ₂ ²⁺ ) _1-y ] _1-x M ³⁺ _x (O
^{_{H) 2 A n- y / n}} · mH 2 O (2) [ _wherein, ^M 1 _2+, ^{M 2 2+} and ^{M 3+} are as defined in the formula ^(1), the ^{A n-} is an n-valent anion Shows, x
Is 0.01 ≦ x <0.5, preferably 0.1 ≦ x ≦
0.4, y is 0 <y <0.5, preferably 0.01 ≦ y
A number of ≦ 0.3, m is a number of 0 ≦ m ≦ 2] is provided as an active ingredient. To do. Furthermore, in the present invention, 100 parts by weight of the resin or rubber is 0.001 to 50 parts by weight, preferably 0.001 to 50 parts by weight.
There is provided an antimicrobial resin, rubber or fiber composition comprising 15 parts by weight, more preferably 0.01 to 5 parts by weight of the above antimicrobial agent.

The present inventors have made extensive efforts to develop an antimicrobial agent having characteristics such as low toxicity, low cost, and excellent heat resistance. As a result, a compound in which ZnO and / or CuO is solid-dissolved in MgO and / or CaO, and further a trivalent metal ion such as Al ³⁺ is solid-dissolved is
It was found that the antimicrobial activity is remarkably improved as compared with ZnO and CuO. It has been conventionally known that Zn ions and Cu ions released from ZnO and CuO exhibit antimicrobial activity similarly to Ag ions. However, the activity of Zn ions and Cu ions is weaker than that of Ag ions. Accordingly, MgO and / or CaO is solid-soluted with ZnO and / or CuO, and a solid solution of an oxide of these divalent metals is solid-dissolved with a trivalent metal ion such as Al ³⁺ , and Mg (OH ) ₂ and / or Ca (OH) ₂ with Zn (OH) ₂ and / or Cu (OH) ₂ in solid solution and trivalent metal ions such as Al ³⁺ in solid solution It has been found that the antimicrobial activity is improved.

Since the antimicrobial agent of the present invention uses inexpensive raw materials, it is less expensive than existing antimicrobial agents such as silver-supporting inorganic antimicrobial agents. Since the heat resistance is also extremely excellent, the problem of foaming at the processing temperature of resin or rubber does not occur.
Furthermore, the ZnO-based and Zn (OH) ₂ -based solid solution antimicrobial agents of the present invention are far less toxic than silver-supported inorganic antimicrobial agents, as well as organic antimicrobial agents, and are less toxic to a few humans. It is one of the safest compounds. Zn and Cu oxides and hydroxides act as decomposing agents when blended with polyvinyl chloride. On the other hand, the antimicrobial agent of the present invention is MgO and / or CaO, or Mg (OH)
₂ and / or Ca (OH) ₂ , which act as stabilizers for polyvinyl chloride,
It has the advantage of masking the action of the oxides and hydroxides as a decomposer. ZnO and Zn (O
The H) ₂ -containing solid solution system is white and does not have the problem of discoloring like silver.

The compounds represented by the formulas (1) and (2) of the present invention are divalent metal oxides or hydroxides (M ₁ ²⁺ , M ₂ ²⁺ ) and trivalent metal oxides. Alternatively, it is a solid solution with a hydroxide, and the main component is an oxide or hydroxide of a divalent metal. Therefore, the diffraction pattern by powder X-ray diffraction has the following features. The compounds of the invention show a divalent metal oxide or hydroxide diffraction pattern, but not a trivalent metal oxide or hydroxide diffraction pattern. This is because the trivalent metal oxide or hydroxide is in solid solution with the divalent metal oxide. However, since spinel is by-produced during high temperature firing at about 900 ° C. or higher, a weak diffraction pattern of spinel type (M ₁ ²⁺ or M ₂ ²⁺ ) M ³⁺ ₂ O ₄ appears. The compound of formula (1) shows that M ₁ increases as x increases.
²⁺ O becomes fine crystals and the antimicrobial activity is improved. However, when it is 0.5 or more, a large amount of spinel type compounds are produced as a by-product, and the antimicrobial activity tends to decrease. M
₂ ²⁺ forms a solid solution with M ₁ ²⁺ O, or M ₁ ²⁺ forms a solid solution with M ₂ ²⁺ O,
It is presumed that mutual inhibition of crystal growth leads to microcrystals, resulting in enhanced antimicrobial activity. Further, by forming a solid solution containing a trivalent metal ion such as Al ³⁺ , a fine oxide is formed, the specific surface area is increased, and the release and elution of Zn ²⁺ and / or Cu ²⁺ with respect to water is enhanced. . In the compound of the formula (2), when x exceeds 0.4, M ³⁺ exceeds the solid solubility limit and M ³⁺ hydroxide and the like are by-produced, and as a result, the antimicrobial effect also decreases. Tend to come. The tendency is remarkable when x is 0.5 or more. When x is 0.4 or less, fine crystals are obtained, and the microbial effect is enhanced.
Mg (OH) ₂ and / or Ca (OH) ₂ are essential components for exhibiting antibacterial activity and improving heat resistance.
When y is 0.5 or more, dehydration decomposition occurs from about 150 ° C.

The compound of the formula (1) has the formula (2): [(M ₁ ²⁺ ) _y (M ₂ ²⁺ ) _1-y ] _1-x M ³⁺ _x (OH) ₂ A ^n- _{y / n} MH ₂ O (2) [wherein, M ₁ ²⁺ , M ₂ ²⁺ and M ³⁺ have the same meanings as in formula (1), A ⁿ⁻ represents an n-valent anion, and x represents a formula (1). 1) shows a number in the same range as above, where y represents a number in the range of 0 <y ≦ 1, m represents a number in the range of 0 ≦ m ≦ 2], 2000 ° C. or lower, preferably 1500 ° C. or lower, more preferably about 300 to 1
It is produced by baking at 300 ° C., particularly preferably at about 400 to 1000 ° C. for about 0.1 to 10 hours. The baked product can be used as it is. In addition, when blended with a resin or rubber, in order to improve the dispersibility, the surface may be treated with a conventional surface treatment agent as exemplified below. Higher fatty acids, alkali metal salts or alkaline earth metal salts of higher fatty acids, phosphoric acid esters, silane-based, titanate-based or aluminum-based coupling agents, esters of polyhydric alcohols and higher fatty acids, and the like.

The following is a more specific example of what is preferably used as the surface treatment agent. Higher fatty acids having 10 or more carbon atoms such as stearic acid, erucic acid, palmitic acid, lauric acid and behenic acid; alkali metal salts of the higher fatty acids; sulfuric acid ester salts of higher alcohols such as stearyl alcohol and oleyl call; polyethylene glycol ether Sulfate ester salt, amide bond sulfate ester salt, ester bond sulfate ester salt, ester bond sulfonate, amide bond sulfonate, ether bond sulfonate, ether bond alkyl allyl sulfonate, ester bond alkyl allyl sulfonate, amide Anionic surfactants such as bound alkylallyl sulfonates; mono- or diesters of orthophosphoric acid and oleyl alcohol, stearyl alcohol, etc., or a mixture of both, in their acid form or alkali metal salt or acid Phosphoric acid esters such as vinyl salts; vinylethoxysilane, vinyl-tris (2-methoxy-ethoxy) silane, gamma-methacryloxypropyltrimethoxysilane, gamma-aminopropyltrimethoxysilane, beta- (3,4-epoxycyclohexyl) ) Silane coupling agents such as ethyltrimethoxysilane, gamma-glycidoxypropyltrimethoxysilane, and gamma-mercaptopropyltrimethoxysilane; isopropyltriisostearoyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, isopropyl tri ( Titanate coupling agents such as N-aminoethyl-aminoethyl) titanate and isopropyltridecylbenzenesulfonyl titanate; acetoalkoxy aluminum diiso Aluminum coupling agents such as Ropireto; glycerol monostearate, esters of polyhydric alcohols and fatty acids such as glycerol monooleate.

The surface coating treatment of the compound of formula (1) with the surface treating agent can be carried out by a dry method or a wet method known per se. As a dry method, the powder of the compound of the formula (1) is added in a liquid, emulsion or solid state to the surface treatment agent with a mixer such as a Henschel mixer under sufficient stirring, and the mixture is sufficiently mixed with or without heating. Good. As the wet method, the surface treatment agent dissolved in water may be added to the slurry of the compound of formula (2) with stirring. The addition amount of the surface treatment agent can be appropriately selected, but the formula (1) and the formula (2)
It is preferably about 0.1 to about 10% by weight, based on the weight of the compound. After the surface treatment of the compounds of the formulas (1) and (2), if necessary, for example, granulation, drying, pulverization, classification, etc. may be appropriately selected and carried out to obtain a final product form. .

The fields of application of the antimicrobial agent of the present invention are various fields which may be adversely affected by microorganisms. Next, those fields will be exemplified. Drinking water, food, resin, rubber, wallpaper, bathroom interior materials, cement, sanitary ware, writing instruments, underwear, electric wires, floor materials, shower curtains, urethane foam, buoy rope, vinyl sheets, agricultural films, synthetic leather, electrical products , Its parts, wax, cutting oil, tableware,
Bathtubs, adhesives, packaging materials, animal housing, sealants, building materials, furniture, textile products such as cloth, tents, socks, non-woven fabrics, antifouling agents (ship bottom paints), paints, adhesives, wood, bamboo materials, cosmetics,
Pool sterilizers, cooling towers, agricultural disinfectants, etc., which are typically used in the field of substituting copper agents such as lime bordeaux solution. When added to the resin, rubber or fiber, the amount of the antimicrobial agent of the present invention is usually 0.001 to 50 parts by weight, preferably 0.01 to 100 parts by weight of the resin, rubber or fiber.
The amount is from 10 to 10 parts by weight, more preferably from 0.1 to 5 parts by weight, but an appropriate amount is selected according to the application.

The antimicrobial agent of the present invention may be fine particles having an average secondary particle diameter of about 0.1 to 1 μm. Further, the hydroxide of the formula (2) is stable at a processing temperature of at least about 300 ° C. and the oxide of the formula (1) is at least about 1300 ° C., and is stable to ultraviolet rays and radiation. For example, it is also possible to melt-knead the antimicrobial agent of the present invention before spinning the fiber and then spin it. For this reason,
The drawbacks of conventional antimicrobial agents, which become less effective by washing, are solved. In the production of sanitary ware and tableware porcelain, the baking temperature after application of pongee in the final process is about 120.
It does not substantially lose its antimicrobial effect even if it is baked at a temperature of more than 0 ° C.
When compounded with resin, rubber or fibers, it does not cause troubles such as evaporation of water and the like at these processing temperatures to foam the molded article, and also has good dispersibility with respect to resin and rubber, and has good mechanical strength. The loss is small and the appearance of the molded product is excellent. It contributes to a resin such as polyvinyl chloride as a heat stabilizer, and solves the problem of decomposing polyvinyl chloride, which is a defect of oxides and hydroxides of Cu and Zn.

Examples of the resin, rubber or fiber used in the present invention are as follows, but the invention is not limited thereto. Polyethylene, copolymers of ethylene and other α-olefins, copolymers of ethylene and vinyl acetate, ethyl acrylate or methyl acrylate, polypropylene, copolymers of propylene and other α-olefins, polybutene- 1. Polystyrene, copolymer of styrene and acrylonitrile or butadiene, copolymer of ethylene and propylene diene rubber or butadiene,
Vinyl acetate, polyacrylate, polymethacrylate,
Thermoplastic resin such as polyurethane, polyester, polyether, polyamide, polyvinyl chloride, copolymer of vinyl chloride and vinyl acetate, polyvinylidene chloride, polyphenylene oxide, polycarbonate; phenol resin, melamine resin, epoxy resin, unsaturated polyester Thermosetting resin such as resin and alkyd resin; EPDM, SB
Rubbers such as R, NBR, butyl rubber, isoprene rubber, chlorosulfonated polyethylene; acrylic fiber, acetate fiber, nylon fiber, pulp, vinylidene fiber, vinylon fiber, non-woven fabric, polyacetal fiber, polyurethane fiber, polyester fiber, polyethylene fiber, polypropylene fiber .

The present invention will be described in more detail with reference to the following examples. In the following examples,% and parts mean% by weight and parts by weight, respectively, unless otherwise specified.

Example 1 A mixed aqueous solution of zinc nitrate and aluminum nitrate (Zn ²⁺ =
0.7 mol / liter, Al ³⁺ = 0.3 mol / liter) 2 liters of 2 mol / liter sodium hydroxide aqueous solution 2 liter and 0.6 mol / liter sodium carbonate aqueous solution 0.5 liter The whole amount was added to the mixed solution under stirring for about 2 minutes to cause reaction (reaction temperature about 30
C). The resulting reaction product slurry was filtered under reduced pressure, washed with water, and dried. The powder obtained by pulverizing the dried product was put into a silicon knit furnace and fired at 400 ° C. for 1 hour. The chemical composition of the calcined product was measured by the chelate titration method, the crystal structure was identified by the powder X-ray diffraction method, and the BET specific surface area was measured by the nitrogen adsorption method. The antibacterial test was performed by smearing the bacterial species solution on an agar plate medium and culturing, and then adding the antibacterial agent solution of the present invention adjusted to a predetermined concentration, and defining the minimum inhibitory concentration as the lowest concentration that inhibits the growth of bacteria. . The lower the concentration, the higher the antibacterial activity. The diffraction pattern of the fired product was slightly shifted to the higher angle side, but the diffraction pattern was only for ZnO. Therefore, Al _{2 is} added to ZnO.
It can be seen that O ₃ is in solid solution. Table 1 shows the evaluation results of the fired product. The chemical composition of the fired product is shown below. Zn _0.7 Al _0.3-a O

Example 2 A mixed aqueous solution of zinc chloride and magnesium chloride and aluminum chloride (Zn ²⁺ = 0.1 mol / liter, Mg ²⁺ =
0.6 mol / liter, Al ³⁺ = 0.3 mol / liter) 4 liters, and 2 mol / liter sodium hydroxide 4 liters were placed in a reaction tank with an overflow of 2 liters using a metering pump. While stirring, they were added at a rate of about 50 ml / min and about 35 ml / min, respectively. During this time, the pH is about 9.0 and the temperature is about 30.
Hold at ℃. After filtering the obtained reaction product slurry under reduced pressure,
It was washed with 5 liters of a 0.2 mol / liter sodium carbonate aqueous solution, further washed with water, dried and pulverized. The obtained powder was fired at 500 ° C. for 1 hour using a silicon knit furnace.
The X-ray diffraction pattern of this product was only MgO. Therefore, it is understood that both ZnO and Al ₂ O ₃ are solid-dissolved in MgO. Table 1 shows the evaluation results of the fired product. The chemical composition of the fired product is shown below. Zn _0.1 Mg _0.6 Al _0.3-a O

Example 3 A mixed aqueous solution of Cu nitrate and aluminum nitrate (Cu ²⁺ = 0.
8 mol / l, Al ³⁺ = 0.2 mol / l) 2
2 liters of mixed aqueous solution of zinc nitrate and aluminum nitrate
A powder of the fired product was obtained in the same manner as in Example 1 except that the powder was used instead of the liter. The X-ray diffraction pattern of this product is
Although slightly shifted to the high angle side, a diffraction pattern of only CuO was shown. Therefore, it is understood that Al ₂ O ₃ is solid-dissolved in CuO. Table 1 shows the evaluation results of the fired product. The chemical composition of the fired product is shown below. Cu _0.8 Al _0.2-a O

Example 4 A mixed aqueous solution of copper nitrate, magnesium nitrate and aluminum nitrate (Cu ²⁺ = 0.1 mol / liter, Mg ²⁺ = 0.
65 mol / liter, Al ³⁺ = 0.25 mol / liter) 2 liters were used in place of 2 liters of the mixed aqueous solution of zinc nitrate and aluminum nitrate of Example 1 in the same manner as in Example 1. A fired product powder was obtained. This thing X
The line diffraction pattern was MgO only. Therefore, C
It can be seen that uO and Al ₂ O ₃ form a solid solution with MgO.
Table 1 shows the evaluation results of the fired product. The chemical composition of the fired product is shown below. Cu _0.1 Mg _0.65 Al _0.25-a O

Example 5 A mixed aqueous solution of copper nitrate, calcium nitrate and aluminum nitrate (Cu ²⁺ = 0.5 mol / liter, Ca ²⁺ = 0.1)
2 liters of 2 mol / liter, Al ³⁺ = 0.4 mol / liter) were added to 2 liters of a 2 mol / liter sodium hydroxide aqueous solution with stirring (reaction temperature 27
C). The resulting reaction product slurry was filtered, washed with water under reduced pressure, and then dried and pulverized. The obtained powder is 60 using a silicon knit furnace.
Baking at 0 ° C. for 1 hour. The X-ray diffraction pattern of this product is
The diffraction patterns of CuO and a trace amount of CuAl ₂ O ₄ are shown. The chemical composition of the fired product is shown below. Cu _0.5 Ca _0.1 Al _0.4-a O

Example 6 A mixed aqueous solution of copper sulfate, zinc sulfate, magnesium sulfate and aluminum sulfate (Cu ²⁺ = 0.2 mol / liter, Z
2 liters of n ²⁺ = 0.1 mol / liter, Mg ²⁺ = 0.4 mol / liter, Al ³⁺ = 0.3 mol / liter) in 2 liters of 2 mol / liter sodium hydroxide aqueous solution The reaction mixture was added to the bottom (reaction temperature 30 ° C.). The resulting reaction product slurry was filtered under reduced pressure, washed with 3 liters of a 0.2 mol / liter sodium carbonate aqueous solution, further washed with water, dried and pulverized. The obtained powder was fired at 500 ° C. for 1 hour using a silicon knit furnace. The X-ray diffraction pattern of this product was only the diffraction pattern of MgO. Therefore, it can be seen that CuO, ZnO and Al ₂ O ₃ form a solid solution with MgO. Table 1 shows the evaluation results of the fired product. The chemical composition of the fired product is shown below. Cu _0.2 Zn _0.1 Mg _0.4 Al _0.3-a O

Example 7 The X-ray diffraction pattern of the ground powder obtained in Example 2 before firing was found to be substantially the same as that of hydrotalcite. The BET specific surface area and antimicrobial effect of this powder were measured. The evaluation results are shown in Table 1. The chemical composition of this product is shown below. Zn _0.1 Mg _0.6 Al _0.3 (OH) ₂ (CO ₃ ) _0.15 · 0.
55H ₂ O

Example 8 As a result of examining the X-ray diffraction pattern of the ground powder obtained in Example 4 before firing, it was substantially the same as hydrotalcite. The BET specific surface area and antimicrobial effect of this powder were measured. The evaluation results are shown in Table 1. The chemical composition of this product is shown below. Cu _0.1 Mg _0.65 Al _0.25 (OH) ₂ (CO ₃ ) _0.125・
0.625H ₂ O

Example 9 The dry powder obtained in Example 2 before firing was stored at 1200 ° C. for 1 hour.
Burned for hours. The X-ray diffraction pattern of this product was MgO and a trace amount of (MgZn) Al ₂ O ₄ . The diffraction pattern of MgO is slightly shifted to the lower angle side than that of pure MgO, and it can be seen that ZnO is in solid solution. The evaluation results of this fired product are shown in Table 1. The chemical composition of the fired product is shown below. Zn _0.1 Mg _0.6 Al _0.3-a O

Comparative Examples 1 to 3 Table 1 shows the results of evaluation of antibacterial properties of the reagent grade cupric oxide, zinc oxide, and commercial copper-supported borosilicate glass antibacterial agents.

Table 1 BET specific surface area Antibacterial m ² / g E. coli Staphylococcus aureus Example 1 210 0.125 0.05 2 275 0.10 0.05 3 184 0.05 0.025 4 305 0.025 0.01 5 276 0.025 0.025 6 280 0.0125 0.0125 7 104 0.8 0.8 0.4 8 118 0.8 0.8 0.2 9 13 13 0.2 0.1 Comparative Example 1 6 1.0 Above 1.0 or above 2 7 1.0 or above 1.0 or above 3 − 1.0 0.5 Note: Comparative Example 1; CuO, Comparative Example 2; ZnO, Comparative Example 3; Copper-supported borosilicate glass

Examples 10 and 11 Comparative Examples 4 and 5 Polyvinyl chloride (average degree of polymerization 1300) 100 parts Dioctyl phthalate 50 parts Ca / Zn-based composite stabilizer 2 parts Antimicrobial agent 2 parts After mixing, using a roll,
The mixture was melt-kneaded at 0 ° C. for 3 minutes. Then, using a press molding machine, a sheet having a thickness of about 1 mm was formed at 170 ° C. for 2 minutes under a pressure of 200 kg / cm ² . Blue mold was sprinkled on this sheet, and the state of subsequent mold growth was observed. As the antimicrobial agent, Example 10 compares the antimicrobial agent obtained in Example 1, Example 11 compares the antimicrobial agent obtained in Example 5, and Comparative Example 4 compares CuO of Comparative Example 1. In Example 5, ZnO of Comparative Example 2 was used.

Table 2 Antimicrobial Evaluation Results (Days of Culture) 7 14 21 28 (days) Example 10 0 0 0 1 11 11 0 0 0 0 Comparative Example 4 2 3 3 4 5 3 4 4 4 4 Note: Evaluation method 0 Mold growth is not recognized 1; mold growth is slightly recognized 2; mold growth is slightly recognized 3; mold growth is moderate 4; mold growth is severely recognized

[0028]

INDUSTRIAL APPLICABILITY According to the present invention, there is provided a novel antimicrobial agent containing, as an active ingredient, an oxide solid solution containing copper and / or zinc as a main active ingredient. The antimicrobial agent of the present invention is fine particles that are non-toxic or almost non-toxic and have high heat resistance and weather resistance. Further, the antimicrobial agent of the present invention has the advantages that it has high dispersibility in resins, rubbers, fibers, paints, does not impair the strength of the resin itself, and does not impair the appearance of molded articles. .

Continuation of front page (58) Fields surveyed (Int.Cl. ⁷ , DB name) A01N 59 / 16,59 / 20,25 / 10 CA (STN) REGISTRY (STN)

Claims (4)

(57) [Claims] 1. Formula (1) [(M ₁ ²⁺ ) _y (M ₂ ²⁺ ) _1-y ] _1-x M ³⁺ _x-a O (1) [wherein, M ₁ ²⁺ is Zn ²⁺ and / or Cu
²⁺ , M ₂ ²⁺ is Mg ²⁺ and / or Ca
²⁺ , M ³⁺ is Al ³⁺ , Fe ³⁺ , Co ³⁺ , Cr
^{3+, In 3+, Bi 3 +} pressurized et selected showed at least one trivalent metal, x and y, 0.01 ≦ x <0.
5, 0 <y ≦ 1 and x−a indicates that the number of M ³⁺ is reduced by a due to lattice defects], and the solid solution and / or the formula (2) [(M ₁ ²⁺ ) _y (M ₂ ²⁺ ) _1-y ] _1-x M ³⁺ _x (O
^{_{H) 2 A n- y / n}} · mH 2 O (2) [ _wherein, ^M 1 _2+, ^{M 2 2+} and ^{M 3+} are as defined in the formula ^(1), the ^{A n-} is an n-valent anion , X and y represent numbers in the range of 0.01 ≦ x <0.5 and 0 <y <0.5, and m represents a number in the range of 0 ≦ m ≦ 2]. An antimicrobial agent comprising a talcite compound as an active ingredient. 2. An antimicrobial resin, rubber or fiber composition, characterized in that 100 parts by weight of the resin, rubber or fiber contains 0.001 to 50 parts by weight of the antimicrobial agent according to claim 1. . 3. A hydrotalcite compound of a solid solution of the formula according to claim 1, wherein (1) _(2), ^{M 1 2+} is ^{Zn 2+} and / or ^Cu _2+, ^{M 2 2+} is ^{Mg 2+}
And / or Ca ²⁺ , and M ₃ ³⁺ is Al ³⁺ . 4. The compound of formula (1) and / or formula (2) is a higher fatty acid, an alkali metal salt of a higher fatty acid, a phosphoric acid ester, a silane coupling agent, a titanate coupling agent, an aluminum cup. An antimicrobial agent, which is surface-treated with a ring agent and at least one surface treatment agent selected from esters of polyhydric alcohols and fatty acids.