JPH10130105A - Antibacterial and fungicidal composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an antibacterial and fungicidal composition which is excellent in resistance to water, chemicals and heat, persistency of its fungi- controlling effect and in antibacterial properties by using a fungi-controlling organic compound-supporting silicate salt and an inorganic antibacterial agent in combination. SOLUTION: This composition contains a mildew or fungi-controlling organic compound supported on a laminar silicate salt and an inorganic antibacterial agent. As the fungi-controlling organic compound, 2,3,5,6- tetrachloro-4-(methylsulfonyl)pyridine, N-(fluorodichloromethylthio)phthalimide and the like are cited. The laminar silicate salt is, for example, montimorillonite, mica or the like. The inorganic antibacterial agent is, for example, a compound of the formula [M<1> is a metal ion of, for example, silver, copper, zinc and the like; A is an alkali metal ion; M<2> is a tetravalent metal; (n) is 0<=n<=6, 1a+mb=1 ((1) is the valence of M<1> ; (m) is the valence of A). In this composition, the combination of the inorganic antibacterial agent with a compound selected from zinc oxide or titanium dioxide affords more increased antibacterial effect.

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 composition containing a fungicidal layered silicate and an inorganic antibacterial agent, and has a water resistance, chemical resistance, heat resistance and sustained antifungal effect. The present invention relates to an antibacterial and antifungal composition excellent in antibacterial properties and antibacterial properties, and particularly excellent in antifungal performance for inhibiting germination of spores. The composition of the present invention can be added to a material such as rubber or plastic, molded, or coated on the surface of a molded article, thereby imparting antibacterial and antifungal properties to the material or the molded article. Useful as an agent.

[0002]

2. Description of the Related Art Various antibacterial and fungicides have been developed for imparting antibacterial and fungicidal properties to desired materials. Organic and inorganic antibacterial and fungicides are known. As organic antibacterial fungicides, quaternary ammonium salt compounds such as benzalkonium chloride, sulfur-containing benzimidazole compounds such as 2,4-thiazolylbenzimidazole, bisthiocyanate compounds such as methylenebisthiocyanate,
Fungicides such as quinolinol compounds such as 8-quinolinol, alcohol compounds such as ethanol, aldehyde compounds such as formalin, phenol compounds such as cresol, and carboxylic acid compounds such as sorbic acid are known. On the other hand, as an antibacterial and antifungal agent of an inorganic type, one in which a metal ion having antibacterial properties such as silver, copper, and zinc is carried on activated carbon, apatite, zeolite, tetravalent metal phosphate and the like is known.

[0003] However, conventional antibacterial and fungicides have advantages and disadvantages in both organic and inorganic systems, and have a problem to be improved. That is, since an organic antibacterial and fungicide generally has poor heat resistance, when used in kneading into plastics or fibers, it causes problems such as discoloration and foaming, and volatilization and decomposition during processing, resulting in sufficient protection. The mold effect could not be exhibited. Furthermore, organic ones are also poor in chemical resistance,
Since it has a relatively high solubility in various solvents, it is eluted during use, and the fungicidal effect is reduced, and there is a concern that it may adversely affect the human body.
Further, although the inorganic antibacterial and fungicide are excellent in heat resistance and chemical resistance, there is a problem that the antifungal effect on fungi is inferior to the antibacterial effect on bacteria. As a technique for solving the above-mentioned problem, an antibacterial antifungal silicate obtained by replacing at least a part of the ion-exchangeable metal ion of a layered silicate with an antibacterial antifungal organic coordination compound is known (Japanese Patent Application Laid-Open (JP-A) No) 4-2
92410).

[0004]

However, organic antibacterial and antifungal agents tend to be inferior to inorganic ones in antibacterial effect on bacteria compared to fungi. Furthermore, in order to enhance the antibacterial effect against bacteria, there is known an antibacterial and fungicidal intercalation compound obtained by introducing a transition metal such as silver and an organic substance as a complex salt between layers of the layered compound (Japanese Patent Laid-Open No. 1-221304). ), The fungicide effect against fungi is not sufficient, and depending on the combination of the transition metal and the organic substance, the complex salt is often colored, which limits the application. The present invention has excellent antibacterial and antifungal properties,
In particular, it is an object of the present invention to provide an antibacterial and antifungal composition having excellent antifungal performance against fungi.

[0005]

The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems. As a result, the present inventors have found that a fungicidal layered silicate in which a fungicidal organic compound is supported on a layered silicate is used. The present inventors have found that the above problem can be solved by coexisting with an antibacterial agent, and have completed the present invention. That is, the present invention is an antibacterial and antifungal composition comprising an antifungal layered silicate obtained by supporting an antifungal organic compound between layers of a layered silicate and an inorganic antibacterial agent.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. ○ Antifungal organic compound The antifungal organic compound in the present invention is not particularly limited,
Those which are soluble in a polar organic solvent or those which are soluble in an acid or alkali are preferred. As preferred fungicidal organic compounds, (a) a compound having a heterocyclic six-membered ring structure in the molecule and containing one or more nitrogen atoms in the ring, (b) a haloalkylthio compound or (c) an azole derivative compound; There are quaternary ammonium compounds such as benzalkonium chloride and the like,
The compounds (a), (b) and (c) are particularly preferred.

Preferred examples of the above (a) include the following compounds. That is, 2,3,5,6-tetrachloro-4
Pyridine compounds such as-(methylsulfonyl) pyridine and 2-pyridinethiol-1-oxide zinc, pyridazine compounds, pyrimidine compounds, triazine compounds, pyrazine compounds, quinoline compounds, quinazoline compounds, phenanthrozine compounds Compounds, phenanthroline compounds, phenazine compounds and the like.

The preferred compound (b) is a compound represented by the following general formula [2].

[0009]

Embedded image

(In the above formula, X, Y, and Z are halogens, which may be the same or different, and R is an organic group.)

X, Y and Z in the above equation are F, Cl and Br
Or I, and preferred R is an organic group having an imide group in the structure. Preferred specific examples of the above (b) include the following compounds. That is, N- (fluorodichloromethylthio) phthalimide, N, N-dimethyl-N '-(dichlorofluoromethylthio) -N'-phenylsulfamide, N, N-dimethyl-N'-(dichlorofluoromethylthio) -N '-Trisulfamide, N- (trichloromethylthio) phthalimide, tetrachloroethylthiotetrahydrophthalimide, N-trichloromethylthio-
4-cyclohexene-1,2-dicarboximide and the like.

Preferred specific examples of the above (c) include the following compounds (note that the names in parentheses are common names). That is,
α- [2- (4-chlorophenyl) ethyl] -α-
(1,1-dimethylethyl) -1H-1,2,4-triazol-1-yl-ethanol << debuconazole >>,
1- (4-chlorophenoxy) 3,3-dimethyl-1-
(1H-1,2,4-triazo-1-yl-2-butanone << triadimefone >>, β- (4-chlorophenoxy) -α- (1,1-dimethyl-ethyl) -1H-1,
2,4-triazole-1-ethanol Triazole-based compounds such as << triadimenol >>, << hexaconazole >>, methyl 2-benzimidazolecarbamate, methylbenzimidazolylcarbamate (BCM), methyl 1- (butylcarbamoyl)- 2-benzimidazole carbamate (benomyl), 2- (2'-freel)-
Benzimidazole compounds such as 1H-benzimidazole and 2- (4′-thiazolyl) benzimidazole (TBZ), 1- [ortho-chloro-β-[(para-
Imidazole compounds such as chlorobenzyl) oxy] phenethyl] -imidazole mononitrate; thiazole compounds such as 1,2-benzisothiazolin-3-one and 2- (4-thiocyanomethylthio) benzthiazole; indazole compounds; pyrazole Compounds, isothiazole compounds and the like.

The antifungal organic compound according to the present invention comprises
It may have antibacterial properties in addition to antifungal properties, may be one kind, or may use two or more kinds in combination.

Layered silicate The layered silicate can be used without any particular limitation as long as the crystal layer units are stacked on each other to form a layered structure, and may be either a natural product or a synthetic product. Preferred layered silicates include clay minerals, and specific examples thereof include the following. That is, smectites such as montmorillonite, beidellite, hectorite, saponite, balmcurite, illite, muscovite, phlogopite,
Mica such as biotite, brittle mica such as margarite and clintite, chlorite such as sudoite, kaolinite,
Kaolins such as halloysite; serpentine family such as antigorite; Other preferred layered silicates include: That is, Magadiite, Kenyaite,
Examples include layered sodium silicates such as kanemite, macatite and Ilarite, layered calcium silicates such as tobermorite, and synthetic mica in which anions such as hydroxyl ions are substituted with fluorine ions.

The particle size, water content, cation exchange capacity, color and the like of the layered silicate in the present invention are not particularly limited, but when used for kneading into plastics, rubber or fibers, the average particle size is 10 μm or less. Is more preferable, and more preferably a powder having an average particle size of 0.1 to 7 μm, and more preferably a narrow particle size distribution and a uniform particle size. In order to exhibit a sufficient antifungal effect when the antifungal layered silicate is used, the cation exchange capacity is 0.1 me.
It is preferably at least q / g. One of these layered silicates may be used alone, but two or more of them may be used in combination for controlling the sustained release.

The above-mentioned layered silicate may be used by replacing some or all of the ion-exchangeable metal ions contained therein with other metal ions. The metal ion to be exchanged is not particularly limited as long as it is an ion-exchangeable metal ion, but lithium, calcium, sodium and the like are preferable.

The lower limit of the preferable amount of the fungicidal organic compound supported between the layers of the fungicidal layered silicate in the present invention is 100 parts by weight (hereinafter simply abbreviated to "part"). ), More preferably 1 part, particularly preferably 5 parts. If the amount is too small, the antifungal effect is reduced. The upper limit of the supported amount is naturally determined depending on the types of the layered silicate and the fungicidal organic compound, and the antifungal layered silicate unnecessarily supported in a large amount is discolored when kneaded into a plastic or the like. Therefore, it is preferable to set a suitable upper limit of the amount of the carrier by a preliminary test.

The method of supporting the fungicidal organic compound on the layered silicate is not particularly limited. Basically, the fungicidal organic compound and the layered silicate may be brought into contact with each other. Can be introduced in any state of solid phase, liquid phase and gas phase. For example, in the case where the antifungal organic compound is in the liquid phase, the antifungal organic compound is mixed and stirred with the layered silicate,
Thereafter, drying and pulverization are performed, or a solution in which a fungicidal organic compound is dissolved in a highly soluble solvent is mixed and stirred with a layered silicate, followed by filtration and washing, followed by further drying and pulverization, whereby the fungicide is prevented. A fungicidal layered silicate in which a hydrophilic organic compound is supported on the layered silicate can be obtained. In addition, you may dry and grind as it is without washing.

The conditions for preparing the above-mentioned antifungal composition are not particularly limited, and can be suitably changed depending on the kind of the antifungal organic compound and the layered silicate to be used and the amount of the antifungal organic compound to be carried. Specifically, for example, the pH of the solvent is 0.1
-13, the stirring time is 0.5-72 hours, the stirring temperature is from room temperature to, for example, about 40 ° C to 60 ° C, and the number of stirring is
It may be 0 times / minute.

Inorganic antibacterial agent In the present invention, the inorganic antibacterial agent is not particularly limited as long as it is an inorganic compound carrying antibacterial metal ions known as antibacterial metal ions such as silver and copper. Examples of the inorganic compound for supporting an antibacterial metal ion include the following. That is, inorganic adsorbents such as activated carbon, activated alumina and silica gel, inorganic ion exchange such as zeolite, hydroxyapatite, zirconium phosphate, titanium phosphate, potassium titanate, hydrated bismuth, hydrated zirconium, and hydrotalcite compounds. There is a body. The method of supporting the antibacterial metal ion on these inorganic compounds is not particularly limited, and any of the supporting methods known so far can be adopted, for example, a method of supporting by physical adsorption or chemical adsorption, by an ion exchange reaction, A method of supporting, a method of supporting with a binder, a method of supporting an antibacterial metal compound by driving it into an inorganic compound, a method of forming a thin film of an antibacterial metal compound on the surface of the inorganic compound by a thin film forming method such as vapor deposition, dissolution deposition reaction, and sputtering. There is a method of supporting by forming a layer.

Among the above inorganic compounds, an inorganic ion exchanger is preferred because it can firmly carry antibacterial metal ions, and a tetravalent metal phosphate ion exchanger represented by the following general formula [3] is particularly preferred. a compound, particularly preferred antimicrobial agent is represented by the following general formula a _b M ²² is a compound represented by _{[4] (PO 4) 3} · nH 2 0 [3] (a is an alkali metal ion, alkaline earth metal ions,
M ² is a tetravalent metal, n is a number satisfying 0 ≦ n ≦ 6, and b is a positive number satisfying mb = 1. Here, m is the valence of A. ) M ¹ _{a Ab} M ²² (PO ₄ ) ₃ .nH ₂ 0 [4] (M ¹ is silver, copper, zinc, tin, mercury, lead, iron, cobalt,
At least one metal ion selected from nickel, manganese, arsenic, antimony, bismuth, barium, cadmium or chromium, and A is at least one metal ion selected from alkali metal ions, alkaline earth metal ions, ammonium ions or hydrogen ions And M ²
Is a tetravalent metal, n is a number satisfying 0 ≦ n ≦ 6,
a and b are positive numbers satisfying la + mb = 1. However,
l is the valence of M ¹ and m is the valence of A. )

The compound represented by the general formula [4] is an amorphous or crystalline compound belonging to the space group R3c, and represents a compound in which each constituent ion forms a three-dimensional network structure. As the phosphate antibacterial agent, a crystalline compound having a three-dimensional network structure is preferable because discoloration upon exposure to sunlight is small. M ¹ in the general formula [4] is:
All are known as antibacterial metals,
Among them, silver is particularly effective as a metal capable of enhancing fungicidal, antibacterial, and algicidal properties in addition to safety.

A in the general formula [4] is at least one ion selected from the group consisting of an alkali metal ion, an alkaline earth metal ion, an ammonium ion and a hydrogen ion. Preferred examples thereof include lithium, sodium and potassium. There are alkali metal ions such as, alkaline earth metal ions such as magnesium or calcium, or hydrogen ions. Among these, potassium, lithium, sodium,
Ammonium ions and hydrogen ions are the preferred ions.

In the general formula [4], M ² is a tetravalent metal, and preferable specific examples include zirconium, titanium and tin. In view of the safety of the compound, zirconium and titanium are particularly preferable. It is a valent metal.

The following are specific examples of the phosphate antibacterial agent represented by the general formula [4]. Ag _0.005 Li _0.995 Zr ₂ (PO ₄ ) ₃ Ag _0.01 (NH ₄ ) _0.99 Zr ₂ (PO ₄ ) ₃ Ag _0.05 Na _0.95 Zr ₂ (PO ₄ ) ₃ Ag _0.2 K _0.8 Ti ₂ (PO ₄ ) ₃ Ag _0.1 H _0.9 Zr ₂ (PO ₄ ) ₃ Ag _0.5 Na _0.25 H _0.25 Zr ₂ (PO ₄ ) ₃ Ag _0.9 Na _0.1 Zr ₂ (PO ₄ ) ₃ and the same charge amount as silver ions per mole of the above compound While there is a compound in which Ag in each of the above formulas is replaced with Zn, Mn, Ni, Pb, Hg, Sn or Cu.

The method for synthesizing the phosphate antibacterial agent includes a baking method, a wet method and a hydrothermal method, all of which are known methods.

In the composition of the present invention, in order to exhibit antibacterial properties, it is better that the value of a in the general formula [4] is large, but if the value of a is 0.001 or more, the antibacterial properties are sufficiently high. Can be demonstrated. However, the value of a is 0.00
If it is less than 1, it may be difficult to exhibit antibacterial properties for a long time, so it is preferable to set the value of a to a value of 0.01 or more. Furthermore, in order to maintain the moldability and product strength of the resin and to exert sufficient antibacterial properties for a long time, a
Is preferably 0.03 or more, and the addition amount of the compound represented by the general formula [4] to the resin is preferably reduced.
Also, in consideration of economy, it is appropriate that the value of a is 0.7 or less.

The phosphate antibacterial agent is stable to exposure to heat and light, and is 500 ° C., and sometimes 800 ° C.
Even after heating at １1100 ° C., the structure and composition do not change at all, and no discoloration occurs even when irradiated with ultraviolet rays. In addition, the phosphate antibacterial agent does not come into contact with water in a liquid state or change in skeletal structure even in an acidic solution. Therefore, processing and storage when obtaining various molded products,
Furthermore, unlike the conventional antibacterial agents, there is no restriction on the heating temperature or the light-shielding conditions during use.

The antibacterial effect of the present invention can be further enhanced by using the inorganic antibacterial agent of the present invention in combination with the following specific metal oxides.

Metal oxide The metal oxide is at least one compound selected from zinc oxide and titanium dioxide.

The zinc oxide may be either a natural product or a synthetic product, and is not particularly limited in properties and production method. In addition to zinc oxide, which is commonly used as a pigment as zinc white, inks, fillers, ultraviolet absorbers, ceramic raw materials, cosmetics, dental raw materials, solvent dispersants, photoconductors, pharmaceuticals, catalysts, electronic materials, phosphors, batteries And the like used as the above can be used.

Titanium dioxide may be either a natural product or a synthetic product, may be amorphous or crystalline, and is not particularly limited in properties and production method. Titanium dioxide is classified into anatase, rutile, and brookite according to the crystal structure, and any crystal structure may be used in the present invention. Because it is easily available industrially,
Anatase and rutile are preferred. In addition to titanium dioxide which is generally used as a pigment, inks, cosmetics, pharmaceuticals, glazes, dental materials, organic titanium raw materials, ceramic raw materials, abrasives, reinforcing agents, catalysts, and those used as electronic materials can be used. .

There is no particular limitation on the particle size and shape of the metal oxide. Taking into account the dispersibility in the resin, the preferred average particle size is 10 μm or less, and the preferred particle shape is cubic, rectangular, spherical, or acicular. Further, the metal oxide may be subjected to a surface treatment for improving dispersibility and reducing surface activity. The surface treatment method may be either a wet method or a dry method. There is no limitation on the surface treatment agent, commonly used aluminum,
Soluble salts such as zinc and silica can be used.

When the inorganic antibacterial agent and the above-mentioned metal oxide are used in combination in the present invention, the preferable mixing ratio of the metal oxide is 5 parts based on the total of 100 parts of the inorganic antibacterial agent and the metal oxide. ~ 90 parts. When the compounding ratio of the metal oxide is less than 5 parts, it may be difficult to improve the antibacterial effect by the combined use of the metal oxide and the inorganic antibacterial agent,
If the amount of the metal oxide is more than 90 parts, it may be difficult to exert the antibacterial effect of the inorganic antibacterial agent. In order to exhibit a sufficient antibacterial effect, the content of the antibacterial metal ion in the mixture of the inorganic antibacterial agent and the metal oxide is preferably 0.5% by weight or more,
More preferably, it is 1% by weight or more.

The preferred compounding ratio of the fungicidal layered silicate and the inorganic antibacterial agent in the composition of the present invention is as follows:
The amount of the inorganic antibacterial agent is 1 to 90 parts, more preferably 10 parts.
To 80 parts, particularly preferably 30 to 70 parts.
If the ratio of the inorganic antibacterial agent is less than 1 part, a sufficient antibacterial effect cannot be obtained, and if it exceeds 90 parts, a sufficient antifungal effect may not be obtained. When an inorganic antibacterial agent and a metal oxide are used in combination, the total amount of both is defined as the weight of the inorganic antibacterial agent. The method of blending the antifungal layered silicate and the inorganic antibacterial agent is not particularly limited as long as both can be uniformly mixed.

Use The antibacterial and fungicidal composition of the present invention is useful as an antibacterial and fungicidal agent which imparts an excellent antibacterial and fungicidal effect when blended with various materials. Materials that can be compounded include, for example, rubbers such as silicone and acrylic; vinyl chloride, polyolefin,
There are plastics such as polyurethane, ABS, polystyrene, vinyl acetate, and polycarbonate. The composition of the present invention can be imparted with antibacterial and fungicidal properties to a molded article by blending with a material and molding or coating the surface of the molded article. Various shapes such as fibers, films, sheets, plates, blocks, etc. can be obtained according to the method.

Further, the antibacterial and antifungal composition of the present invention is prepared by suspending a composition in a liquid medium such as water or an organic solvent, by spray coating, coater coating, dipping, or the like.
It can also be applied to the surface of various metals, plastics, ceramics, etc. to form a film by ordinary application means such as brush coating, roll coating, etc., and thus the growth of bacteria and fungi on articles of various materials Can be prevented. The preferable ratio of blending the composition of the present invention with various materials is as follows.
The amount is 0.1 to 30 parts, more preferably 0.5 to 10 parts, per 00 parts.

Specific uses of the material or molded article containing the composition of the present invention include textile products such as towels, carpets, curtains, and clothing; leather; refrigerators, washing machines, dish dryers, vacuum cleaners, and air conditioners. , Televisions, telephones, and other electrical appliances; wallpaper, tiles, bricks, concrete, screws, joints, and other building materials; washbasins, toothbrushes, brooms, hoses, slippers,
Sunday miscellaneous goods such as trash boxes and scrubbers; kitchenware such as cutting boards, triangular corners, kitchen knives; toiletry supplies; various coating materials, paints and adhesives. Hereinafter, the present invention will be described in more detail with reference to Examples.

[0039]

【Example】

(Reference Example 1) [Preparation of Ca-type layered silicate] 0.1 mol / l CaCl ₂
To 1.0 liter of the aqueous solution, 100.0 g of Na-type fluorine-substituted synthetic moth, which is a layered silicate, was added, followed by stirring at 300C for 4 hours (300 rpm). The obtained suspension was washed with ion-exchanged water until the conductivity of the filtrate became 100 μS / cm or less, then dried and ground at 100 ° C. to obtain a Ca-type layered silicate.

(Reference Example 2) [Preparation of fungicidal layered silicate A] α- [2- (4-chlorophenyl) ethyl] -α- (1,1-) which is an azole derivative compound as a fungicidal organic compound Dimethyl-1H-
1,2,4-triazol-1-yl-ethanol7.
5 g and 42.5 g of the Ca-type layered silicate obtained in Reference Example 1
In addition, after sufficiently stirring in a mortar, the mixture was directly heated at 120 ° C. The obtained composite precursor was washed with pure water, dried in vacuum at 100 ° C., and aged. After drying, pulverization was performed to obtain a white mold-resistant layered silicate A.

(Reference Example 3) [Preparation of fungicidal layered silicate B] A complex 6 in the molecule was prepared as an antifungal organic compound in 500 ml of 70% acetone / water solution.
5.0 g of 2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine, an organic compound having a membered ring structure and containing one or more nitrogen atoms in the ring, was added and completely dissolved. . The Ca-type layered silicate obtained in Reference Example 1 was
After adding 5.0 g and stirring at room temperature for 1 hour, the mixture was dried as it was in an electric furnace and pulverized to obtain a white mold-resistant layered silicate B.

(Reference Example 4) [Preparation of fungicidal layered silicate C] N- (fluorodichloromethylthio) phthalimide, which is a haloalkylthio-based organic compound, in 500 ml of a 70% acetone / water solution was used as a fungicidal organic compound. Was added and dissolved completely.
Thereto, 45.0 g of the Ca-type layered silicate obtained in Reference Example 1 was added, and the mixture was stirred at room temperature for 1 hour, dried in an electric furnace as it was, and pulverized to obtain a white mold-resistant layered silicate C.

(Example 1) [Preparation of antibacterial and antifungal composition A] The antifungal layered silicate A obtained in Reference Example 2 and an inorganic antibacterial agent X represented by the following formula [5] are equi-weighted. The mixture was mixed uniformly using a small Henschel mixer to obtain an antibacterial and antifungal composition A. Ag _0.53 Na _0.17 H _0.30 Zr ₂ (PO ₄ ) ₃ [5]

(Example 2) [Preparation of antibacterial and fungicidal composition B] The procedure of Example 1 was repeated except that the fungicidal layered silicate B obtained in Reference Example 3 was used in place of the fungicidal layered silicate A. Similarly, an antibacterial and antifungal composition B was obtained.

(Example 3) [Preparation of antibacterial and fungicidal composition C] The procedure of Example 1 was repeated except that the fungicidal layered silicate C obtained in Reference Example 4 was used in place of the fungicidal layered silicate A. Similarly, an antibacterial and antifungal composition C was obtained.

(Example 4) [Preparation of antibacterial and antifungal composition D] The inorganic antibacterial agent X represented by the above formula [5] and zinc oxide were used.
Are uniformly mixed at a ratio of 0.7 times the weight of the antifungal layered silicate A obtained in Reference Example 2 to obtain an antibacterial and antifungal composition D. Was.

(Comparative Example 1) The antifungal layered silicate A obtained in Reference Example 2 was replaced with the antifungal layered silicate A in Example 1.
The case of using only one is referred to as Comparative Example 1.

(Comparative Example 2) The antifungal layered silicate B obtained in Reference Example 3 was replaced with the antifungal layered silicate A in Example 1.
The case of using only one is referred to as Comparative Example 2.

(Comparative Example 3) The antifungal layered silicate C obtained in Reference Example 3 was replaced with the antifungal layered silicate A in Example 1.
The case of using only one is referred to as Comparative Example 3.

Evaluation of antifungal property 1 [Minimum inhibitory concentration (M
Measurement of IC)] The antibacterial and fungicidal compositions prepared in Examples 1 to 4 and Comparative Examples 1 to 3 were placed in 8 ml of potato dextrose medium for 500, 2
50, 125, and 67.5 ppm were added, and mold spores were applied thereon, and the state of mold growth one week later was judged. Molds include black koji mold (Aspergills niger) and black mold (Clad
osporium cladospolies). Table 1 shows the results of the MIC measurement using black mold, and Table 2 shows the MIC results of the use of black mold. Further, in each table, as reference data, the evaluation results in the case of using the inorganic antibacterial agent X instead of the antibacterial and antifungal composition are also shown. The meanings of the symbols in each table are as follows. ：: Mold growth was inhibited. ×: Mold growth is observed.

[0051]

[Table 1]

[0052]

[Table 2]

(Use Examples 1-4) 2.5 g of each of the antibacterial and antifungal compositions prepared in Examples 1 to 4 was added to 147.5 g of the composition shown in Table 3 below, and the mixture was heated at 150 ° C with a heating roll. After kneading for 5 minutes, press (170 ° C, 100Kg / c
m ² ), formed into a plate having a thickness of 2 mm, a length of 12 cm and a width of 10 cm, and cut out to a size of 3 cm square to prepare a test piece. The correspondence between the use example number and the type of the antibacterial and antifungal composition used in each use example is as follows.使用 Usage example No. Kinds of antibacterial and antifungal composition No. 1 Antibacterial and antifungal composition A 2 Antibacterial and antifungal composition B 3 Composition C 4 Antibacterial and antifungal composition D

[0054]

[Table 3]

* 1: TS1100 (manufactured by Toagosei Co., Ltd.) * 2: manufactured by Toho Rika Kogyo Co., Ltd. * 3: 300K (manufactured by Daicel Chemical Industries, Ltd.) * 4: ADK STAB 37 (trade name, manufactured by Asahi Denka Kogyo Co., Ltd.) * 5: ADK STAB 102 (trade name, manufactured by Asahi Denka Kogyo Co., Ltd.)

(Comparative Use Examples 1 to 3) Test pieces were prepared in the same manner as in Use Example 1 except that the antifungal layered silicate prepared in Comparative Examples 1 to 3 was used instead of the antibacterial and antifungal composition. Produced.
In addition, the correspondence between the comparative use example number and the kind of the mildew-resistant layered silicate used in each comparative use example is as follows.比較 Comparative usage example No. Kinds of antifungal layered silicate １ 1 Antifungal layered silicate A 2 Antifungal layered silicate B 3 Antifungal layered silicate C ─────────────────────────

(Comparative Use Examples 4 to 6) In place of the antibacterial and antifungal composition, 149.75 g of the following antifungal organic compound (a), (b) or (c) was used instead of the antifungal organic compound. 0.2 each
A test piece was prepared in the same manner as in Use Example 1 except that 5 g was added. (A) α- [2- (4-chlorophenyl) ethyl] -α
-(1,1-dimethyl-1H-1,2,4-triazol-1-yl-ethanol (b) 2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine (c) N- ( Fluorodichloromethylthio) phthalimide The correspondence between the comparative use example numbers and the types of the antifungal organic compound used in each comparative use example is as follows. ──────────── Comparative use example No. Kind of antifungal organic compound ───────────────────────── 4 (B) 5 (b) 6 (c) ─────────────────────────

(Comparative Use Example 7) A test piece was prepared in the same manner as in Use Example 1 except that the inorganic antibacterial agent X represented by the above formula [5] was used instead of the antibacterial and antifungal composition. .

Evaluation of antifungal property 2 [Measurement of number of spores by wrap method] Spore suspension containing malt extract (0.05%) on test pieces prepared in Use Examples 1-4 and Comparative Use Examples 1-7 (Spore count concentration: 4.5 × 10 ⁴ / ml) was dropped in 100 μl, adhered tightly with a 2.5 cm square wrap, and dried at 25 ° C. and 90% humidity at 48%.
After keeping for a time, the change in the number of spores before and after was measured. Black koji mold (Aspergills niger) was used as a mold for evaluation. The results of the antifungal test obtained as described above are shown in Table 4 below.

Evaluation of antifungal property 3 [Evaluation of antifungal property by halo method] Test pieces prepared in Use Examples 1 to 4 and Comparative Use Examples 1 to 7
It was allowed to stand in warm water at 0 ° C. for 7 days, and after 1 day and 7 days, the antifungal property was measured to evaluate the time-dependent change of the antifungal effect. As a method for evaluating the antifungal property, the test piece was placed on a potato dextrose agar medium, and the antifungal property was evaluated by measuring the width of the inhibition zone after 14 days of culture. In addition, black koji mold (Aspergills niger) was used as a mold for evaluation. The results of the antifungal test obtained as described above are shown in Table 4 below.

Antibacterial test The antibacterial activity of the test pieces prepared in Use Examples 1 to 4 and Comparative Use Examples 1 to 7 was evaluated by the following method. Escherichia coli was used as a test bacterium, and a diluent was prepared so that the number of bacteria was about 10 ⁵ . Next, 100 μl of the diluting solution was dropped onto a test piece (3 cm square), and the test piece (3 cm square) was adhered with a 1.5 cm square wrap.
Stored at ° C. 0 hours from the start of storage (initial bacterial count: 2.6 ×
10 ⁵ / ml) and stored for 6 hours, the surviving bacteria on the test piece were washed out with a medium for measuring the number of bacteria (SCDLP liquid medium), and this washing solution was used as a test solution. For this test solution, a pour plate culture method using a medium for measuring the number of bacteria (37 ° C. for 2 days)
The number of viable bacteria was measured by the above method and converted to the number of viable bacteria per ml. The number of target bacteria was 8.3 × 10 ⁴ / ml, and the number of blank bacteria was 4.1 × 10 ⁴ / ml. Table 4 below shows the results of the antibacterial raw test obtained as described above.

[0062]

[Table 4]

Note: The symbols in the table mean the following. [Column of spore count]-: Growth of hypha was observed at the time of washing out 48 hours later, and it was impossible to measure the number of spores. [Hello method column] A: Growth inhibition zone was formed. ×: No growth inhibition zone was formed. [Comprehensive Evaluation Column] A: Both antibacterial and antifungal properties are excellent. B: At least one of antibacterial and antifungal properties is slightly inferior. C: At least one of antibacterial and antifungal properties is inferior.

As can be seen from Table 4, the antifungal layered silicate of the present invention has both excellent antibacterial properties and antifungal properties, and can be washed for a longer time as compared with the case where an organic compound having an antifungal agent is directly blended. Does not lose the antifungal property, and is excellent in persistence of the antifungal effect. In addition, it is particularly excellent in fungicidal ability for inhibiting germination of spores belonging to fungi.

[0065]

Industrial Applicability The antibacterial and antifungal composition of the present invention is excellent in both antibacterial and antifungal properties, and especially in antifungal properties against fungi. Due to this property, the antibacterial and antifungal composition of the present invention can be made of various rubbers, plastics and other materials and films and sheets formed thereof, molded articles such as sheets, and various fibers,
It is useful as an antibacterial and antifungal agent applied to paper, leather, paints, adhesives, heat insulators, caulks and the like.

Continuation of the front page (51) Int.Cl. ⁶ Identification code FI A01N 61/00 A01N 61/00 (72) Inventor Hideki Kato 1-1, Funamicho, Minato-ku, Nagoya-shi, Aichi Nagoya Sogo Co., Ltd. Inside

Claims (4)

[Claims] An antibacterial and antifungal composition comprising an antifungal layered silicate having an antifungal organic compound carried between layers of the layered silicate and an inorganic antibacterial agent. 2. The antifungal organic compound is an organic compound having a heterocyclic six-membered ring structure in the molecule and containing one or more nitrogen atoms in the ring, a haloalkylthio organic compound or an azole derivative compound. The antibacterial and antifungal composition according to claim 1, characterized in that: 3. The method according to claim 1, wherein the inorganic antibacterial agent is a compound represented by the following general formula [1].
The antibacterial and antifungal composition according to the above. M ¹ _{a Ab} M ²² (PO ₄ ) ₃ .nH ₂ 0 [1] (M ¹ is silver, copper, zinc, tin, mercury, lead, iron, cobalt,
At least one metal ion selected from nickel, manganese, arsenic, antimony, bismuth, barium, cadmium or chromium, and A is at least one metal ion selected from alkali metal ions, alkaline earth metal ions, ammonium ions or hydrogen ions And M ²
Is a tetravalent metal, n is a number satisfying 0 ≦ n ≦ 6,
a and b are positive numbers satisfying la + mb = 1. However,
l is the valence of M ¹ and m is the valence of A. ) 4. The antibacterial and antifungal composition according to claim 1, further comprising at least one metal oxide selected from zinc oxide and titanium dioxide.