JP3164494B2 - Antibacterial 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 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 which have been used as antibacterial and antifungal agents (antibacterial and antifungal agents) include benzimidazoles, nitriles, isothiazolines, haloallylsulfones, iodopropargyls, benzoides and the like. Thiazole,
Examples thereof include phenol-based, organotin-based, pyridine-based, diphenyl ether-based, and chlorhexidine-based agents, 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 their metal compounds have a strong bactericidal effect against a wide range of microorganisms such as various bacteria and fungi at extremely small concentrations in the form of metal ions. Is well known.

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 antibacterial and antifungal agents. The antibacterial and antifungal composition is required to have a broad antibacterial spectrum, reduce skin irritation, mucous membrane irritation, etc., have good dispersibility of the antibacterial antifungal agent, and be economical due to a simple manufacturing process. You.

It can be said that these required characteristics largely depend on various characteristics 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 properties.

[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 furthermore, emergence of resistant bacteria. Therefore, there is a problem in applying these antibacterial and antifungal agents to a living environment. Further, antibacterial agents typified by supporting silver ions and the like on ceramics such as zeolite have a large particle size, so that it is not easy to add them to paints, inks, varnishes and the like.

[0006] Water-soluble antibacterial agents are also known, but when added to a water-dispersed resin solution, dispersibility and storage stability may be lacking. Not satisfactory. Accordingly, an object of the present invention is to provide an antibacterial and antifungal composition having a broad antibacterial spectrum, easily dispersing an antibacterial and antifungal agent, having excellent storage stability, and not deteriorating the physical properties of a coating film. It is.

[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 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 storage stability and dispersion stability can be improved by the combined use with the water-soluble amine (B), and it can be easily added to paints, inks, varnishes and the like. Although the reason why such an effect can be obtained by using (B) is not necessarily 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 poorly water-soluble compound (A), which is a complex coordinated with silver ions, and a water-soluble amine (B). The antibacterial and antifungal composition of the present invention has excellent storage stability and dispersion stability. The antibacterial and antifungal composition according to claim 2 further comprises a water-dispersible resin (C). The antibacterial and antifungal composition according to claim 3 is characterized in that the poorly water-soluble compound (A), which is a complex formed by coordinating silver ions according to claims 1 and 2, comprises:
It is a complex obtained by coordinating a thiol group-containing compound with a silver ion.

The poorly water-soluble compound (A) according to the present invention is a complex formed by coordinating silver ions, such as a complex formed by coordinating silver ions with a thiol group-containing compound. 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 include thiosalicylic acid, p-toluenethiol, 2-naphthalentol, 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 include mercaptopropionic acid, mercaptoacetic acid, thiophenol, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, thiouric acid, mercaptonicotinic acid, 2-thiouracil, and 2-mercaptohypoxanthine. Among them, thiosalicylic acid is preferred from the viewpoints of antibacterial and antifungal activity and the stability of the compound. Further, as a supply 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 ethanol to precipitate the complex. The complex is used in an amount of from 0.1 to 4 mol, preferably from 0.5 to 1 mol, per mol of silver.
It is obtained by reacting 2 moles of the ligand. Outside this range, durability such as weather resistance is poor. Further, if it is less than 0.1 mol, the antibacterial and antifungal activity 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 ability means a bacteriostatic ability to inhibit the growth of fungi containing viruses, bacteria, and fungi including molds and yeasts and / or kill them.

The (B) of the present invention includes triethanolamine, dimethylaminoethanol, ethylamine, diethylamine, diisopropylamine, 2-aminoethanol, diethanolamine, 2-dimethylaminoethanol, isoamylamine, N-methylethanolamine and the like. No. The water-soluble amine is preferably a tertiary amine. To add to the resin solution, (A), (B) and purified water are added in a weight ratio of 1 / 0.01 / 9
8.99-20 / 10/70, preferably 5 / 0.5 /
94.5 to 10/4/86, and titania beads,
Add zirconia beads or zircon beads and shake for 1 hour or more with a paint conditioner.

[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 rubber-like polymer include natural rubber, ethylene-propylene-diene rubber (EPDM), styrene-butadiene rubber (SBR), chloroprene rubber (CR), acrylonitrile-butadiene rubber (NBR), and the like. 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 resin, urethane resin Resins, silicon-based 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. In addition, an organic solvent such as a crosslinking agent, a plasticizer, an antifoaming agent, or an alcohol can be added to the germicidal and fungicidal composition of the present invention, if necessary. The solid weight ratio of (A) / (C) of the antibacterial and antifungal composition of the present invention is as follows:
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 suitably used for surface treatment of paper, nonwoven 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 addition, the part in an example shows a weight part, and% shows weight%, respectively. 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-methylolacrylamide /
26 parts / 52 parts / 17 parts / 3 of each monomer of acrylic acid
Parts / parts, and a 40% solids acrylic emulsion solution 10 emulsion-polymerized by adding a nonionic surfactant.
No. 0, 1.6 parts of the antibacterial agent dispersion was added, and the mixture was stirred and mixed. 6. Coat the non-woven fabric with a bar coater
Dry at 20 ° C. for 10 minutes.

Example 2 Polysol EVA AD-6910 manufactured by Showa Kogaku KK
No. 0, 2.1 parts of the antibacterial agent dispersion described in Example 1 was added, and the mixture was stirred and mixed. 9 was applied to a vinyl chloride sheet with a bar coater 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%
To 100 parts of butadiene-based latex, 2 parts of the antibacterial agent dispersion described in Example 1 was added and mixed by stirring. The coated paper was coated on a high-quality paper with a bar coater of No. 6 and dried at 120 ° C. for 10 minutes.

[Evaluation of antibacterial property] The antibacterial property of Escherichia coli (E. coli) of the coated product of the above antibacterial and antifungal composition was evaluated. Each coating was cut into a circle of about 2 cm and placed in the well. The bacteria were inoculated into 5 ml of a soybin casein digest (SCD) liquid medium from the slant in loops and cultured with shaking at 35 ° C. for 24 hours. Then, the obtained culture solution was diluted 100-fold. Each well was inoculated with 0.1 ml of the diluted bacterial solution described above and stored at 35 ° C. for 18 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 three SCD agar media. After culturing at 35 ° C. for 24 hours, the number of colonies was measured. The results are shown in Table 1.

[0019]

[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 The compositions of Examples 1 to 3 were added without addition of triethanolamine to the thiosalicylic acid / silver ion complex and then dispersed by a mixer. However, 1
The antimicrobial agent settled out on the day, making it impossible to apply.

Continuation of the front page (51) Int.Cl. ⁷ Identification symbol FI A01N 33:04) (A01N 55/02 33:08) (72) Inventor Hiroyuki Ito 540 Narita, Odawara-shi, Kanagawa Meiji Health Science Co., Ltd. In the laboratory (72) Inventor Sadatoshi Sakuma 540 Narita, Odawara-shi, Kanagawa Prefecture Meiji Dairy Products Co., Ltd.Cell Engineering Center Examiner Shoei Hoshino (56) References JP-A-8-245325 (JP, A) 7-316433 (JP, A) JP-A-6-306082 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) A01N 55/02 A01N 25/10 A01N 25/22 A01N 59 / 16

Claims (3)

(57) [Claims] An antibacterial and antifungal composition comprising a poorly 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, further comprising a water-dispersible resin (C). 3. The antibacterial and antifungal composition according to claim 1, wherein (A) is a complex comprising a thiol group-containing compound coordinated with silver ions.