JPH07126432A - Antimicrobial and antifungal resin composition and masterbatch - Google Patents

Abstract

PURPOSE:To obtain an antimicrobial and antifungal resin composition, having low toxicity, reduced in skin and mucosal irritancies, excellent in persistence of activities and safety and useful as fiber, films, etc., by dispersing a complex in which a thiol group-containing compound is coordinated with silver ions in a resin. CONSTITUTION:This antimicrobial and antifungal resin composition is obtained by dispersing a complex in which a thiol group-containing compound such as thiosalicylic acid is coordinated with silver ions in a resin such as PE. Furthermore, this masterbatch is prepared by dispersing preferably 10-80wt.% complex in the resin.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a resin composition having antibacterial and antifungal properties. More specifically, it relates to a resin composition in which a complex in which a thiol group-containing compound having antibacterial and antifungal properties is coordinated with silver ions is dispersed.

[0002]

2. Description of the Related Art In recent years, with the increasing hygiene of consumers, antibacterial and antifungal agents are added to various resins to impart antibacterial and antifungal properties, and the obtained resins are antibacterial and antifungal fibers, films and containers. Attempts have been made to apply it to various products used in the living environment. Conventionally, as antibacterial and antifungal agents added to these resins, benzimidazole-based,
Many compounds such as thiabendazole-based, thiazoline-based, triazine-based, phenol ether-based, alkylamine-based, and organic tin-based compounds have been used.

However, the above-mentioned antibacterial and antifungal agents do not show an antibacterial effect depending on the type of bacteria, and many cannot obtain a sufficient effect. Also, the long-lasting antibacterial and antifungal action,
There were many problems in terms of safety such as acute oral toxicity, skin irritation and mucous membrane irritation. Therefore, many problems similar to the above were found in the resins to which these antibacterial and antifungal agents were added to impart the antibacterial and antifungal effect.

[0004]

DISCLOSURE OF THE INVENTION The inventors of the present invention have conducted extensive studies to solve the above-mentioned problems, and as a result, a complex in which a thiol group-containing compound is coordinated with silver ions is dispersed in a resin. The resin composition exhibits a wide range of antibacterial and antifungal properties, has a long-lasting effect of these, and is further highly safe with toxicity, skin irritation, and mucous membrane irritation being significantly reduced, leading to the present invention. It was

[0005]

The present invention provides an antibacterial and antifungal resin composition in which a complex in which a thiol group-containing compound is coordinated with silver ions is dispersed in a resin.

The thiol group-containing compound serving as the ligand of the complex dispersed in the resin may be any compound containing a thiol group, such as carboxyl group, hydroxyl group,
There is no problem even if it has a functional group such as an amino group. For example, thiosalicylic acid and salts thereof, p-toluenethiol, 2-naphthalenethiol, thiomalic acid, thioglycolic acid, α-thiolactic acid, β-thiolactic acid, cysteine,
Thioglycerol, 5-mercapto- (1H) tetrazolyl acetic acid sodium salt, 2-mercaptoethanol,
2,3-dimercaptosuccinic acid, thiophenol, 2-
Examples thereof include mercaptobenzimidazole, 2-mercaptobenzothiazole, thiourea, mercaptonicotinic acid, 2-thiouracil and 2-mercaptohypoxanthine.

As a source of silver ions, water-soluble silver salts such as silver nitrate are preferable.

The complex formed from these exemplified compounds is preferably silver / ligand = 1 mol / 0.5 to 2 mol.

The resin includes a natural resin, a semi-synthetic resin, and a synthetic resin, and may be thermoplastic or curable. As the thermoplastic resin, polyethylene, polypropylene, vinyl chloride, acrylonitrile-butadiene-styrene copolymer resin, ethylene-vinyl acetate copolymer resin, nylon, polyester, polyvinylidene chloride,
Polyamide resin, polystyrene, polyacetal, polyvinyl alcohol, polycarbonate, acrylic resin,
Fluorine resin, polyurethane resin, rayon, cupra and the like can be mentioned.

Examples of the curable resin include phenol resin, urea resin, melamine resin, unsaturated polyester resin, epoxy resin, polyvinyl alcohol, acrylic polyol, polyisocyanate and functional group-containing polyester. The curing mechanism of the curable resin may be heat or energy rays.

As a method for preparing the antibacterial and antifungal resin composition in which the thiol group-containing compound-silver ion complex is dispersed in the above resin, a method of directly dispersing a predetermined amount of the complex in the resin may be used. It is preferable to use the masterbatch method in order to further increase the temperature. That is, if necessary, the complex is previously dispersed in a high concentration with a dispersant that is usually used for a resin (master batch), and the master batch is made of the same resin or a resin having high compatibility with the resin. Adjust to the specified concentration by diluting. The content of the complex in the masterbatch is preferably 5% by weight or more, more preferably 10 to 80% by weight.

Further, even when the resin is in a liquid state or in a liquid state, it is preferable to use a method according to the masterbatch system (in this case, the complex high-concentration paste). In the antibacterial and antifungal resin composition of the present invention, there is no particular limitation on the addition amount of the thiol group-containing compound-silver ion complex dispersed in the resin, and it can be arbitrarily selected according to the intended use.

In the antibacterial and antifungal resin composition of the present invention, at least one kind of the above-mentioned thiol group-containing compound-silver ion complex and at least one kind of resin are used in a two-roll, three-roll, kneader, extruder or colloid. Mill, homomixer, using various machines capable of applying shearing force such as a ball mill, in the case of a thermoplastic resin, while appropriately heating considering the melting point or softening point of the resin, In the case of a heat or energy ray-curable resin, it can be obtained by applying only a shearing force and dispersing under the condition of not heating.

[0014]

The present invention will be described in more detail based on the following examples. In the examples, parts and% represent parts by weight and% by weight, respectively. [Examples 1 and 2 and Comparative Example 1] (Example of thermoplastic resin) Polyethylene wax ("Sun Wax 1" manufactured by Sanyo Kasei Co., Ltd.)
31-P ", softening point 108 ° C) 60 parts, 40 parts of the antibacterial / antifungal agent shown in Table 1 which has been preliminarily heated and dried is melt-dispersed on a three roll heated to 110 to 120 ° C to prepare a masterbatch. Created. Furthermore, 2.5 parts of the obtained masterbatch and low density polyethylene (“Suntech F-1920” manufactured by Asahi Kasei)
97.5 parts of the softening point of 220 ° C) were kneaded and diluted on a two-roll roll heated to 210 to 230 ° C. 0.5 at 210-230 ℃
The pressure was applied at 150 kg / m ² for 1 minute to prepare a test sample having a thickness of 1 mm.

[Examples 3 and 4 and Comparative Example 2] (Example of thermoplastic resin) Polypropylene ("J-109G" manufactured by Ube Industries, Ltd., softening point 260)
1 part of the antibacterial and antifungal agent shown in Table 1 which had been heated and dried in advance, was melt-dispersed in the pressure kneader at around 250 ° C. This was pressed at 260 to 280 ° C. for 0.5 minutes at 150 Kg / m ² to prepare a test sample having a thickness of 1 mm.

[Examples 5 and 6 and Comparative Example 3] (Example of thermosetting resin) Epoxy resin ("Araldite GY-2 manufactured by Ciba Geigy")
60 "), 50 parts of the antibacterial and antifungal agent shown in Table 1 which had been heated and dried in advance was kneaded and dispersed by a three-roll to prepare a paste containing a high concentration of the antibacterial and antifungal agent. Further, 2 parts of this high-concentration paste and 88.1 parts of the epoxy resin were kneaded and diluted with a three-roll mill, and 9.9 parts of a curing agent (“HY-951” manufactured by Ciba-Geigy) was mixed. This was poured into a mold and cured to prepare a test sample having a thickness of 1 mm.

Examples 7 and 8 and Comparative Example 4 (Example of Thermosetting Resin) Acrylic polyol (“Acridic A-850” manufactured by Dainippon Ink and Chemicals, Inc., solid content 70%) was added to 100 parts by weight. 1 part of the antibacterial and antifungal agent shown in Table 1 which had been heated and dried in advance was kneaded with a muller, and 40 parts of polyisocyanate (“Bernock DN-950” manufactured by Dainippon Ink and Chemicals, Inc., solid content 75%) was mixed. This was poured into a mold and cured to prepare a test sample having a thickness of 1 mm.

(Antibacterial Test) The surface of the test sample of 5 × 5 cm ² obtained in Examples 1 to 8 and Comparative Examples 1 to 4 was sprayed with the bacterial solution of the bacteria shown in Table 1 and cultured for 24 hours. After culturing, the antibacterial activity was evaluated by comparing the growth degree of the bacteria with a control test sample containing no antibacterial and antifungal agent. The antibacterial activity was defined as-when the growth of the bacteria was similar to the control growth level, + when up to about 50% of the control growth level, and ++ when the growth was almost completely suppressed. The results are shown in Table 1.

[0019]

[Table 1]

* 1 Thiabendazole manufactured by San-ai Oil Co., Ltd. * 2 manufactured by Daiwa Chemical Industry Co., Ltd.

[0021]

Industrial Applicability According to the present invention, an antibacterial and antifungal resin composition exhibiting a wide range of antibacterial and antifungal properties and having significantly reduced toxicity, skin irritation and mucous membrane irritation and having high safety can be obtained.

Continuation of front page (51) Int.Cl. ⁶ Identification number Internal reference number FI Technical display location C08L 101/00 (72) Inventor Yasunori Suzuki 540 Narita, Odawara-shi, Kanagawa Meiji Dairy Co., Ltd.

Claims (4)

[Claims] 1. An antibacterial and antifungal resin composition, characterized in that a complex in which a thiol group-containing compound is coordinated with silver ions is dispersed in a resin. 2. The antibacterial and antifungal resin composition according to claim 1, wherein the resin is a thermoplastic resin. 3. The antibacterial and antifungal resin composition according to claim 1, wherein the resin is a heat or energy ray curable resin. 4. A masterbatch obtained by dispersing the complex according to claim 1 in a resin at a high concentration.