JP3117383B2 - Bactericidal and antifungal composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fungicidal and fungicidal composition, and more particularly, to a fungicidal and fungicidal composition having a broad antibacterial spectrum and excellent in dispersion stability and storage stability. It is.

[0002]

2. Description of the Related Art Organic agents which have been used as antibacterial and fungicide agents include benzimidazoles, nitriles, isothiazolines, haloallylsulfones, iodopropargyls, benzothiazoles, phenols, and the like.
Examples thereof include organotin-based, pyridine-based, diphenylether-based, and chlorhexidine-based agents. Antibacterial properties have been imparted by adding these antibacterial and fungicides to paints, inks, and the like. On the other hand, heavy metals such as gold, silver, copper, and zinc and their metal compounds are extremely resistant to a wide variety of microorganisms such as various bacteria and fungi at extremely small concentrations in the state of metal ions. It is well known that it has a bactericidal effect.

Utilizing such an effect, a composition such as a paint, an ink, and a varnish is imparted with antibacterial properties by carrying antibacterial metal ions such as silver ions and zinc ions on the surface of ceramic fine particles such as zeolite. This has been done by adding a fungicide and fungicide. The antibacterial and antifungal composition has a broad antibacterial spectrum, reduces skin irritation, mucous membrane irritation, etc., has good dispersibility of the antibacterial and antifungal agent, and is economical due to a simple manufacturing process. Required. It can be said that these required characteristics largely depend on various characteristics of the antifungal agent contained in the antifungal composition.

A fungicidal / fungicidal composition to which the fungicidal / fungicidal agent is added does not sufficiently satisfy these required properties.

[0005]

When the above-mentioned organic fungicides and fungicides are added, many of them exhibit skin irritation, mucous membrane irritation and the like due to the safety of the medicine itself. Because of the appearance, there is a problem in applying these fungicides and fungicides to living environments. Further, antibacterial agents typified by supporting silver ions or the like on ceramics such as zeolite are not easily added to paints, inks, varnishes, etc. because of their insolubility in water. That is, the dispersion step and the addition of a dispersion aid are indispensable. Water-soluble antibacterial agents are also known, but when added to a non-aqueous resin solution, they lack dispersibility and storage stability, reduce the surface smoothness of the coating film, and furthermore, the antibacterial performance of the antibacterial agent Is also not satisfactory.

Accordingly, an object of the present invention is to provide a fungicidal and fungicidal composition having a broad antibacterial spectrum, easy dispersing of the fungicide and fungicide, excellent storage stability, and which does not deteriorate the physical properties of the coating film. It is to provide things.

[0007]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that the above-mentioned objects can be solved by the following means, and have completed the present invention. That is, the present invention comprises a water-soluble compound (A), a water-soluble resin (B) and a water-dispersible resin (C) containing a metal element having a fungicidal and fungicidal property. It relates to a moldy composition. Furthermore, the present invention relates to the above-mentioned antibacterial and fungicidal composition, wherein the water-soluble compound (A) containing a metal element having antibacterial and antifungal properties is a complex formed by coordinating silver ions.

Further, the present invention provides the above-mentioned antibacterial and fungicidal composition, wherein the water-soluble compound (A) containing a metal element having antibacterial and antifungal properties is a complex obtained by coordinating a thiol group-containing compound with silver ions. Composition. Further, the present invention relates to the above fungicidal and fungicidal composition, wherein the counter cation of the complex is selected from K +, Na +, Ca ++ and Ba ++. The water-soluble compound (A) containing a metal element having antibacterial and antifungal properties in the present invention is itself water-soluble, and therefore does not need to be supported on solid particles such as zeolite, and is used in paints, inks, varnishes, and the like. It can be easily added, and this antibacterial and antifungal composition has excellent dispersibility and storage stability.
The metal element (A) contains at least one selected from silver, copper, zinc and the like. This compound includes, for example, silver nitrate, silver fluoride, silver chlorate, silver perchlorate, a silver complex such as a silver ammine complex, a complex of a thiol group-containing compound and silver ion, copper acetate, copper gluconate, and sodium copper chlorophyllin. , Zinc acetate, zinc gluconate, zinc nitrate, zinc thiocyanate and the like. These may be used alone or as a mixture of two or more.

Among them, a silver compound is preferable, which has a particularly broad antibacterial spectrum, has little effect on other components used, and has a silver ion coordinated to a thiol group-containing compound from the viewpoint of safety. Are more preferred. Here, the thiol group-containing compound may have, for example, a carboxyl group, a hydroxyl group, or an amino group in the compound, and may contain thiosalicylic acid and a salt thereof,
Toluene thiol, 2-naphthalene thiol, thiomalic acid, thioglycolic acid and salts thereof, α-thiolactic acid, β
-Thiolactic acid, cysteine, thioglycerol, 5-mercapto- (1H) tetrazolylacetic acid sodium salt, 2-
Mercaptoethanol, mercaptosuccinic acid and its salts, 2,3-dimethylcaptosuccinic acid, 2-mercaptopropionic acid, mercaptoacetic acid, thiophenol, 2-
Examples include mercaptobenzimidazole, 2-mercaptobenzothiazole, thiouric acid, mercaptonicotinic acid, 2-thiouracil, and 2-mercaptohypoxanthine. Among them, thiosalicylic acid and salts thereof are preferred from the viewpoints of fungicidal and fungicidal activity and the stability of the compound. Also,
As a source of silver ions, a water-soluble silver salt is preferable from the viewpoint of simplicity in production of the complex and subsequent use.

The complex can be produced, for example, by reacting a thiol group-containing compound with silver ions in an aqueous solution, and adding an alcohol or the like to precipitate the complex. The above-mentioned complex is obtained by reacting 0.1 to 4 mol, preferably 0.5 to 2 mol of a ligand with respect to 1 mol of silver, and out of this range, durability such as weather resistance is poor. . Further, if the amount is less than 0.1 mol, the antibacterial and fungicidal activity is not sufficient, while if it exceeds 4 mol, an expensive silver compound is used in a large amount, which is not preferable. Note that the counter cation added to the above complex is K ⁺ , Na ⁺ , Ca ⁺⁺ and Ba from the viewpoint of the solubility and durability of the obtained complex.
^{++ and the} like are preferable.

Here, the term "antibacterial and antifungal performance" means bacteriostatic ability to inhibit the growth of fungi containing viruses, bacteria and fungi including molds and yeasts and / or bactericidal ability to kill the fungi. . Water-soluble resin (B) in the present invention
Not only water-soluble resins but also alkali-soluble resins. As (B), for example, polyvinyl alcohol, polyvinyl isobutyl ether, polyester,
Acrylic resin, styrene-maleic anhydride resin, styrene-maleic acid resin, styrene-acrylic acid copolymer,
Styrene-methacrylic acid copolymer, styrene-α-methylstyrene-acrylic acid copolymer, maleic acid resin and the like are included.

[0012] The water-dispersible resin (C) in the present invention can be used for the durability, water resistance, adhesive strength to a substrate, heat resistance, and the like of a coating film.
This (C) is a resin that can be emulsified and dispersed in water, is used as a so-called O / W emulsion, and is used for improving blocking resistance and flexibility. It can be roughly divided into resinous polymers,
Examples of the rubbery polymer include natural rubber, ethylene-propylene-diene rubber (EPDM), styrene-butadiene rubber (SBR), chloroprene rubber (CR), and acrylonitrile-butadiene rubber (NBR). Natural resins such as rosin, polyethylene, styrene-butadiene resin, vinyl resin (for example, polyvinyl acetate, ethylene-vinyl acetate copolymer, polyvinyl chloride), polyvinyl butyral, polystyrene,
Styrene-butadiene-based resin, urethane-based resin, silicon-based resin, acrylic resin and the like can be listed.

In the present invention, an emulsifier can be used if necessary in order to facilitate the production of (C) and increase its stability. In addition, an organic solvent such as ammonia or an amine, a crosslinking agent, a plasticizer, or an alcohol can be added to the antibacterial and fungicidal composition of the present invention, if necessary.
The solid weight ratio of (A) / (B) of the antibacterial and antifungal composition of the present invention is 0.05 / 100 to 10/100, preferably 0.1 / 100 to 5/100. (B)
/ (C) solid content weight ratio is 10 / 90-75 / 25,
Preferably it is 20 / 80-60 / 40. (A) /
In (B) / (C), 0.05 / 10/90 to 10/7
5/25, preferably 0.1 / 20/80 to 5/60 /
40.

The antibacterial and fungicidal composition of the present invention is used for various purposes, and is suitably used for surface treatment of paper, nonwoven fabric treatment, OP varnish and the like. The composition of the present invention can be applied or impregnated by a roll coating method, a dipping method, a printing method, or a spray coating method.

[0015]

[Example 2]

Aqueous ammonia and ion-exchanged water were added so that the solid content of methyl vinyl ether-maleic anhydride copolymer GANTREZAN-149 manufactured by Gokyo Sangyo was 20%, and the mixture was stirred with a mixer until completely dissolved. Acrylic water-dispersed resin) was added to a solid content of 20%, and the mixture was stirred. Then, silver nitrate, a silver ammine complex, or a thiosalicylic acid / silver ion complex (1/1) was added.
1) is added to high quality paper, paperboard or non-woven fabric with a roll coater, and 0.1% of each is added at 110 ° C.
Dry for 0 minutes. [Example 3] (Preparation of acrylic resin) Styrene-maleic anhydride resin G manufactured by Gifu Shellac Works
Ammonia water and ion-exchanged water were added to a four-necked flask so that SM1002 had a solid content of 20%, and completely dissolved at 80 ° C. Then, styrene / methyl methacrylate / ethyl acrylate monomer was added at 80 ° C at 35% each.
% / 18% / 47% and a mixture of 0.5% of azobisisobutyronitrile were added dropwise over 2 hours. After completion of the dropping, the temperature was kept at 80 ° C. for 2 hours to obtain an acrylic resin. (Addition of antibacterial agent) A material obtained by adding 0.1% of silver nitrate, silver ammine complex, or thiosalicylic acid / silver ion complex (1/1) to the acrylic resin is applied to high quality paper, paperboard or nonwoven fabric, 1
Dry at 10 ° C. for 5 minutes. [Evaluation of antibacterial property] Escherichia coli (E. coli) as a coating product of the above antibacterial and fungicidal composition
And Bacillus subtilis (B. subtilis).

Each coating was cut into a circle of about 2 cm and placed in a well. The bacterium is 5m in soybin casein digest (SCD) liquid medium, one loop from the slant.
1 and inoculated at 35 ° C. for 24 hours with shaking. afterwards,
The resulting culture was diluted 100-fold for the E. coli-containing culture and 10-fold for the Bacillus subtilis-containing culture. Sample sheet (coated with antibacterial and antifungal composition; 3 samples, coated with no antimicrobial agent added (only component (A) is removed from the composition of Example); 3 samples, only sheet; One sample) and two wells for a total of 7 samples each containing only wells, and thus 14 wells were prepared for one strain. 0.1 ml of the diluted bacterial solution was inoculated into each well and stored at 35 ° C. for 24 hours.

Thereafter, each well and sheet were washed with sterile physiological saline to collect the bacteria. This was serially diluted 10-fold with sterile physiological saline, and 0.1 ml of each diluted solution was spread on two SCD agar media. After culturing at 35 ° C. for 24 hours, the number of colonies was counted. The results are shown in Table 1. [Dispersion Stability / Storage Stability] The antibacterial and fungicidal compositions of Examples 1 to 3 were stable even when left at room temperature for 6 months. Comparative Example In the compositions of Examples 1 to 3, instead of the water-soluble component (A), an antibacterial agent having silver ions and the like supported on zeolite was used and dispersed by a mixer.

However, sedimentation of the antibacterial agent was observed within a few hours,
I can no longer apply.

──────────────────────────────────────────────────続 き Continued on the front page (72) Munehiro Oda, Inventor 540, Narita, Odawara-shi, Kanagawa Prefecture Meiji Dairy Co., Ltd. Examiner Kenji Hara (56) References JP-A-1-125311 (JP, A) JP-A-7-48744 (JP, A) JP-A-6-227924 (JP, A) JP-A-7-316433 ( JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) A01N 59/16 A01N 25/10

Claims (4)

(57) [Claims] 1. A water-soluble compound (A) , a water-soluble resin (B), and a water dispersion containing a metal element having antibacterial and fungicidal properties.
A fungicidal and fungicidal composition comprising a conductive resin (C) . 2. A composition containing a metal element having antibacterial and antifungal properties.
That the water-soluble compound (A), Antibacterial and Antifungal composition according to claim 1, wherein a complex formed by coordination of silver ions. 3. It contains a metal element having an antibacterial and antifungal property.
The antibacterial and antifungal composition according to claim 2, wherein the water-soluble compound (A) is a complex obtained by coordinating a thiol group-containing compound with silver ions. Counter cation wherein the complex member is K +, Na +, Ca
++ and claim 2, characterized in that it is selected from Ba ++
Or the antibacterial and antifungal composition according to 3 .