JPH0987116A - Antibacterial and antifungal composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an antibacterial and antifungal composition improved in storage stability and dispersion stability and having a wide antimicrobial spectrum by remarkably lowering the particle diameter of a slightly water-soluble compound comprising a complex containing a coordinated silver ion with a specific compound. SOLUTION: This antibacterial and antifungal composition contains both (A) a slightly water-soluble compound comprising a complex containing a coordinated silver ion and (B) a water-soluble amine. (C) A water-dispersible resin may be added to the system. The compound (A) is preferably a complex formed by coordinating a silver ion in a thiol group-containing compound. The thiol group-containing compound is e.g. thiosalicylic acid, and a source for supplying the silver ion is preferably a water-soluble silver salt. The component (B) includes triethanolamine and dimethylaminoethanol. The component (C) includes natural rubber, ethylene-propylene-diene rubber, polyethylene and urethane resins. The component (A), the component (B) and purified water are used in a ratio of 1/0.01/98 to 20/10/70. The component (A) and the component (B) are used in a solid content weight ratio of 0.01/100 to 10/100.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an antibacterial and antifungal composition, and more particularly to an antibacterial and antifungal composition having a broad antibacterial spectrum and excellent dispersion stability and storage stability. .

[0002]

2. Description of the Related Art Organic agents used so far as antibacterial and antifungal agents (antibacterial and antifungal agents) include benzimidazole, nitrile, isothiazoline, haloallylsulfone, iodopropargyl, benzo. Thiazole,
Phenol-based, organotin-based, pyridine-based, diphenyl ether-based, chlorhexidine-based, and the like are listed, and antibacterial properties have been imparted by adding these antibacterial and antifungal agents to paints, inks, and the like. On the other hand,
Heavy metals such as gold, silver, copper and zinc, and these metal compounds have strong bactericidal effects against a wide range of microorganisms such as various bacteria and fungi at extremely low concentrations in the state of metal ions. Is well known.

Utilizing such an effect, it is possible to impart antibacterial properties to compositions such as paints, inks and varnishes by loading 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 antibacterial and antifungal agents. The antibacterial and antifungal composition has a broad antibacterial spectrum, reduced skin irritation, mucous membrane irritation, etc., good dispersibility of the antibacterial and antifungal agent, and economical efficiency due to a simple manufacturing process. It

It can be said that these required properties are highly dependent on various properties of the antibacterial and antifungal agent contained in the antibacterial and antifungal composition. The antibacterial and antifungal composition to which the above antibacterial and antifungal agent is added does not sufficiently satisfy these required characteristics.

[0005]

When the above-mentioned organic antibacterial and antifungal agents are added, many of them show skin irritation, mucous membrane irritation, etc. due to the safety of the drug itself, and the emergence of resistant bacteria. Therefore, there is a problem in applying these antibacterial and antifungal agents to the living environment. Further, an antibacterial agent represented by a ceramic such as zeolite carrying silver ions or the like has a large particle size, so that it is not easy to add it to paints, inks, varnishes and the like.

Water-soluble antibacterial agents are also known, but when added to a water-dispersed resin solution, the dispersibility and storage stability may be poor, and the antibacterial properties of coated products are I'm not satisfied. Therefore, an object of the present invention is to provide an antibacterial and antifungal composition which has a broad antibacterial spectrum, is easy to disperse the antibacterial and antifungal agent, has excellent storage stability, and does not deteriorate the physical properties of the coating film. Is.

[0007]

As a result of earnest studies, the present inventors have found that the above-mentioned problems can be solved by the following means, and have completed the present invention. That is, the poorly water-soluble compound (A), which is a complex formed by coordinating silver ions, generally has a coarse particle size and is difficult to disperse in water as it is, but as a result of various studies by the present inventors, It has been found that the combined use with the water-soluble amine (B) can improve storage stability and dispersion stability, and can be easily added to paints, inks, varnishes and the like. Although the reason why such an effect is obtained by using (B) is not always clear, it is likely that the particle size of (A) is significantly reduced.
It is considered that storage stability and dispersion stability are improved.

The antibacterial and antifungal composition of the present invention is characterized by containing a sparingly water-soluble compound (A) which is a complex formed by coordinating silver ions and a water-soluble amine (B). The antibacterial and antifungal composition of the present invention is excellent in storage stability and dispersion stability. The antibacterial and antifungal composition according to claim 2 further comprises a water-dispersible resin (C). In the antibacterial and antifungal composition according to claim 3, the sparingly water-soluble compound (A), which is a complex formed by coordinating the silver ions according to claims 1 and 2,
It is characterized in that it is a complex in which silver ions are coordinated to a thiol group-containing compound.

The poorly water-soluble compound (A) according to the present invention is a complex in which silver ions are coordinated, and examples thereof include a complex in which silver ions are coordinated in a thiol group-containing compound. Here, the thiol group-containing compound, for example, may have a functional group of a carboxyl group, a hydroxyl group, an amino group in the compound, thiosalicylic acid, p-toluenethiol, 2-naphthalenethiol, thiomalic acid,
Thioglycolic acid, α-thiolactic acid, β-thiolactic acid, cysteine, thioglycerol, 5-mercapto- (1H)
Tetrazolylacetic acid, 2-mercaptoethanol, mercaptosuccinic acid, 2,3-dimethylcaptosuccinic acid, 2-
Examples thereof include mercaptopropionic acid, mercaptoacetic acid, thiophenol, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, thiouric acid, mercaptonicotinic acid, 2-thiouracil, and 2-mercaptohypoxanthine. Among them, thiosalicylic acid is preferable from the viewpoints of antibacterial and antifungal activity and compound stability. In addition, as a source of silver ions, a water-soluble silver salt is preferable from the viewpoint of ease of production of the complex and its subsequent use.

The complex can be produced, for example, by reacting a thiol group-containing compound with silver ion in ethanol to precipitate the complex. The amount of the complex is 0.1 to 4 mol, preferably 0.5 to 1 mol, based on 1 mol of silver.
It is obtained by reacting 2 mol of the ligand, and outside this range, the durability such as weather resistance is poor. Further, if it is less than 0.1 mol, the antibacterial and antifungal ability is not sufficient, while if it exceeds 4 mol, an expensive silver compound is used in a large amount, which is not preferable. Here, the antibacterial and antifungal performance means the bacteriostatic ability to suppress the growth and / or the bactericidal ability to kill the fungi containing viruses, bacteria and fungi including fungi including fungi and yeast.

The term (B) of the present invention means triethanolamine, dimethylaminoethanol, ethylamine, diethylamine, diisopropylamine, 2-aminoethanol, diethanolamine, 2-dimethylaminoethanol, isoamylamine, N-methylethanolamine and the like. Can be mentioned. The water-soluble amine is preferably a tertiary amine. Before adding to the resin solution, the weight ratio of (A) and (B) to purified water is 1 / 0.01 / 9.
8.99-20 / 10/70, preferably 5 / 0.5 /
94.5 to 10/4/86 mixed, titania beads,
Add zirconia beads or zircon beads and shake in paint conditioner for at least 1 hour.

The water-dispersible resin (C) according to the present invention has durability of coating film, water resistance, adhesive strength to a substrate, heat resistance,
This (C) is added in order to improve blocking resistance, flexibility and the like. This (C) is a resin that can be emulsified and dispersed in water and is used as a so-called O / W type emulsion. It can be roughly divided into resinous polymers,
Examples of the rubber-like polymer include natural rubber, ethylene-propylene-diene rubber (EPDM), styrene-butadiene rubber (SBR), chloroprene rubber (CR), and acrylonitrile-butadiene rubber (NBR). Examples of the resin-like polymer include Natural resin such as pine resin, polyethylene, styrene-butadiene resin, vinyl resin (for example, polyvinyl acetate, ethylene-vinyl acetate copolymer, polyvinyl chloride), polyvinyl butyral, polystyrene, styrene-butadiene resin, urethane resin Resins, silicone resins, acrylic resins 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. If necessary, a cross-linking agent, a plasticizer, an antifoaming agent, an organic solvent such as alcohol can be added to the antibacterial and antifungal composition of the present invention. The (A) / (C) solid content weight ratio of the antibacterial and antifungal composition of the present invention is
0.01 / 100 to 10/100, preferably 0.05
/ 100 to 5/100. The antibacterial and antifungal composition of the present invention is used for various purposes, and is preferably used for surface treatment of paper, non-woven fabric treatment, overprint (OP) varnish and the like.

The composition of the present invention can be applied and impregnated by a roll coating method, a dipping method, a printing method or a spray coating method.

[0015]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be specifically described below based on embodiments. In the examples, “part” means “part by weight” and “%” means “% by weight”. Example 1 (Dispersion of Antibacterial Agent) Thiosalicylic acid / silver ion complex / triethanolamine / purified water = 5 parts / 1 part / 94 parts were mixed, titania beads were added, and the mixture was shaken with a paint conditioner for 3 hours. (Addition of antibacterial agent) ethyl acrylate / butyl acrylate / acrylonitrile / n-methylol acrylamide /
26 parts / 52 parts / 17 parts / 3 of each monomer of acrylic acid
Parts / 2 parts, emulsion polymerization was carried out by adding a nonionic surfactant, and an acrylic emulsion solution having a solid content of 40% 10
No. 0 part was added with 1.6 parts of the antibacterial agent dispersion and mixed by stirring. Apply to a non-woven fabric with a 6 bar coater and 1
Dry at 20 ° C. for 10 minutes.

Example 2 Polysol EVA AD-6910 manufactured by Showa High Polymer Co., Ltd.
2.1 parts of the antibacterial agent dispersion described in Example 1 was added to 0 parts of the mixture, and the mixture was stirred and mixed. It was applied to a vinyl chloride sheet with a bar coater No. 9 and dried at 120 ° C. for 10 minutes.

Example 3 Styrene having a glass transition point (Tg) of 2 ° C. and a solid content of 49%
2 parts of the antibacterial agent dispersion described in Example 1 was added to 100 parts of the butadiene-based latex, and the mixture was stirred and mixed. The fine paper was coated with a bar coater No. 6 and dried at 120 ° C. for 10 minutes.

[Evaluation of Antibacterial Property] The antibacterial property of the coating of the antibacterial and antifungal composition against Escherichia coli (E. coli) was evaluated. Each coating was cut into a circle of about 2 cm and placed in the well. The fungus was inoculated in 1 ml each of platinum loops from a slant into 5 ml of a liquid medium of soybin-casein digest (SCD), and cultured by shaking at 35 ° C. for 24 hours. Then, the obtained culture solution was diluted 100 times. Each well was inoculated with 0.1 ml of the diluted bacterial solution and stored at 35 ° C. for 18 hours.
Then, each well and the sheet were washed with sterile physiological saline to collect the bacteria. This was serially diluted 10-fold with sterilized physiological saline, and 0.1 ml of each diluted solution was spread on 3 SCD agar media, cultured at 35 ° C. for 24 hours, and the number of colonies was measured. The results are shown in Table 1.

[0019]

[Table 1]

[Dispersion Stability / Storage Stability] The antibacterial and antifungal 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, triethanolamine was added to the thiosalicylic acid / silver ion complex without adding and dispersing it, and dispersed with a mixer. However, 1
The antibacterial agent settled out day by day, and it became impossible to coat.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Reference number within the agency FI Technical display location A01N 33:04) (A01N 55/02 33:08) (72) Inventor Munehiro Oda Odawara City, Kanagawa Prefecture Narita 540 Meiji Dairy Industry Co., Ltd. Cell Engineering Center (72) Inventor Hiroyuki Ito 540 Narita, Odawara City, Kanagawa Prefecture Meiji Dairy Co., Ltd. Health Science Research Institute (72) Inventor Sadato Sakuma Narita, Odawara City, Kanagawa Prefecture 540 Meiji Dairy Industry Cell Engineering Center Co., Ltd.

Claims (3)

[Claims] 1. An antibacterial and antifungal composition comprising a sparingly water-soluble compound (A) and a water-soluble amine (B) which are complexes formed by coordinating silver ions. 2. The antibacterial and antifungal composition according to claim 1, which contains a water-dispersible resin (C). 3. The antibacterial and antifungal composition according to claim 1 or 2, wherein (A) is a complex in which silver ions are coordinated to a thiol group-containing compound.