JPH06135807A - Polymeric material - Google Patents

Abstract

PURPOSE:To obtain a polymeric material excellent in antimicrobial and antifungal properties and persistence thereof. CONSTITUTION:This polymeric material comprises a silver-coordinated compound of 2-(4-thiazolyl)benzimidazole (TBZ). The silver-coordinated compound of the TBZ can be obtained by, e.g. reacting the TBZ with silver as follows: That is, a silver salt soluble in water, e.g. silver nitrate, silver lactate or silver perchlorate is initially used as a silver source. The silver is preferably made to react with the TBZ at a reactional ratio of the silver to TBZ of 1-2mol TBZ to 1mol silver. The silver-coordinated compound of the TBZ is preferably blended in an amount of 0.01-10wt.%, especially 0.1-2wt.% based on the polymeric material. A method for adding and mixing the silver-coordinated compound with the polymeric material just before the molding is preferred; however, a method for adding and mixing the silver-coordinated compound with a monomer for good dispersion of particles is preferred in some cases.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polymer having excellent antibacterial and antifungal properties.

[0002]

2. Description of the Related Art Organic polymers are widely used as products from solids to highly viscous liquids. Water, nutrients, etc. are deposited on the network structure and foam of these polymers, and they are easily attacked by microorganisms. Therefore, efforts are being made to impart various antibacterial properties. These can be broadly classified into two types: an elution type, such as diphenyl ether, which elutes from the polymer to act on water, and a non-elution type, such as an organic silicon ammonium salt, which does not elute from the polymer. Of these, the elution type has a problem in safety for the human body because the antibacterial agent itself elutes. Further, since the antibacterial agent is eluted and the content in the polymer is reduced, the antibacterial activity is also inferior in sustainability.

The non-eluting type does not have these drawbacks, and it can be expected that, for example, conventionally known metal ions such as silver ions, copper ions and zinc ions are retained in a polymer to be used. However, this method has a drawback that the metal and the polymer are not well compatible with each other. Further, when silver is used, there is a problem that silver undergoes a chemical change and becomes black.

On the other hand, 2- (4-thiazolyl) benzimidazole (hereinafter abbreviated as TBZ) is known to have an antifungal action, and it has been made to retain it in a polymer. , TBZ alone has a narrow antibacterial spectrum, and therefore, a sufficient antibacterial effect cannot be obtained.

Therefore, a polymer having excellent antibacterial and antifungal properties has been desired.

[0006]

Under the circumstances, as a result of intensive studies by the present inventors, it was found that a polymer having excellent antibacterial and antifungal properties can be obtained by using a silver coordination compound of TBZ. Heading, completed the present invention.

That is, the present invention provides a polymer containing a silver coordination compound of TBZ.

The silver coordination compound of TBZ used in the present invention can be obtained, for example, by reacting TBZ with silver as follows. That is, first of all, as a silver source,
A silver salt soluble in water, for example, silver nitrate, silver lactate, silver perchlorate or the like is used. Regarding the reaction ratio of silver and TBZ, it is preferable to react 1 to 2 mol of TBZ with 1 mol of silver.

Examples of the solvent for reacting silver with TBZ include organic solvents and acid solutions. Examples of the organic solvent include dimethyl sulfoxide, dimethyl acetamide,
Examples thereof include dimethylformamide, methyl ethyl ketone, methanol, ethylene glycol and the like. Further, the acid solution must be one that does not react with silver to form a water-insoluble salt, and examples thereof include nitric acid, perchloric acid, borofluoric acid, hydrosilicofluoric acid, sulfuric acid, and malon. An aqueous solution of an acid such as an acid, maleic acid or sulphonic acid may be used. The acid concentration of these is preferably 0.1 to 1 mol / l.

When an organic solvent is used as the solvent, TBZ is dissolved in the organic solvent, and an aqueous solution of the above silver salt or an organic solvent solution is added thereto, and the mixture is heated at room temperature or in a water bath for several minutes to 30 minutes. It is performed with agitation. After completion of the reaction, the reaction product can be obtained by distilling off the organic solvent. When an acid solvent is used as the solvent, the reaction is
It is carried out by dissolving BZ in an acid solution, adding the aqueous solution of the silver salt to the solution, and stirring at a temperature of about 100 ° C. for several minutes. At this time, the reaction product of TBZ and silver precipitates and can be isolated by filtration or the like. The use of an acid solution as the solvent is particularly preferable because the desired reaction product can be obtained in a high yield by a simple operation and a high-purity product is easily obtained.

The polymer used in the present invention is not particularly limited as long as it is a synthetic or semi-synthetic organic polymer, and examples thereof include polyethylene, polypropylene, polystyrene, polyvinyl chloride and polyvinylidene chloride. , Polyamide, polyester, polyvinyl alcohol, polycarbonate, polyacetal, ABS resin,
Thermoplastic synthetic polymer such as acrylic resin, fluororesin, polyurethane elastomer, polyester elastomer, thermosetting synthetic polymer such as phenol resin, urea resin, melamine resin, unsaturated polyester resin, epoxy resin, urethane resin, rayon, cupra , Regenerated or semi-synthetic polymers such as acetate and triacetate.

The polymer of the present invention can be produced by adding a silver coordination compound of TBZ to an organic polymer. Here, the silver coordination compound of TBZ is 0.01 to 10% by weight, particularly 0.1 to 2% by weight, based on the polymer.
It is preferable to mix them. The timing and method of addition and mixing are not particularly limited, and an optimum method may be used depending on the properties of the organic polymer used, the characteristics in the process, and the like. Usually, the method of adding and mixing immediately before molding is suitable, but in some cases, it is preferable to add and mix with the monomer for good dispersion of particles.

The polymer of the present invention can be produced by a conventional method except that a silver coordination compound of TBZ is added, and in addition to the above components, an organic solvent, a polymerization catalyst, a stabilizer and a matting agent. , Whitening agents, organic or inorganic pigments, inorganic fillers, vulcanizing agents, vulcanization accelerators, foaming agents, bubble stabilizers, antioxidants, various plasticizers and the like within the range that does not impair the effects of the present invention. can do.

The polymer of the present invention can be molded into various shapes and sizes, and the shape and size are not particularly limited, and examples thereof include granules, films, fibers, various containers, pipes and the like. It can be an arbitrary molded body.

The polymer of the present invention can be used in an extremely wide range of applications requiring sterilizing power. Although its use is not particularly limited, for example, daily necessities such as bath and kitchen sponges and cosmetic mats; medical devices such as catheters; building materials such as wallpaper, heat insulating materials and soundproofing materials; toys such as sports balls and play equipment; mattresses , Bedding such as cushions;
In addition, it can be applied to fibers, films, cushioning materials for transportation, packaging materials and the like.

[0016]

The polymer of the present invention has excellent antibacterial and antifungal properties and its durability.

[0017]

EXAMPLES Next, the present invention will be further described with reference to examples, but the present invention is not limited to these examples.

Reference Example Preparation of TBZ Silver Coordination Compound: Commercial Grade Methanol 1
2.0 g of TBZ was added to 00 ml and heated on a water bath for T
BZ was dissolved to prepare a solution of TBZ. To this solution, a 0.05 mol / l silver methanol solution 20 derived from special grade silver nitrate
0 ml was added and stirred for 30 minutes. Then, the solvent was evaporated on a water bath, washed with water, and dried to obtain 1.8 g of a TBZ silver coordination compound.

Example 1 A NBR foam was produced by the following method, and its antibacterial activity and mold resistance were evaluated. The results are shown in Table 2. (Manufacturing method) 100 parts by weight of NBR latex, 4 parts by weight of colloidal sulfur as a vulcanizing agent and zinc white as a vulcanization accelerator, 1 part by weight of foaming agent potassium oleate, 2 parts by weight of a foam stabilizer trimene base aqueous solution, Antiaging Agent Nocrac # 20
0.1 parts by weight and the silver coordination compound of TBZ (produced in Reference Example) in an amount shown in Table 2 were mixed and mechanically foamed, and then 2 parts by weight of sodium silicofluoride was added as a gelling agent to form a gel. And vulcanize at 100 to 120 ° C. for about 40 minutes, then wash with water and dry. The foam obtained is machined into the desired shape.

(Evaluation method) (1) Antibacterial activity A molded polymer body as a sample was shredded to give 1 × 1 test bacteria.
1.5 ± 0.1 g is added to 70 ml of phosphate buffer solution (pH 7.2) inoculated so as to be 0 ^{4 to} 2 × 10 ⁴ (CFU / ml). Shaking was performed at 25 ± 2 ° C., and the viable cell count after 6 hours was measured to determine the reduction rate of viable cell count.

[0021]

[Equation 1]

A: Number of viable cells per 1 ml after shaking B: Number of viable cells per 1 ml before shaking In addition, both the measurement of the viable cells and the pre-culture, the medium was Nutrient
Agar (Difco) was used, and S was used as the test bacteria.
taphylococcus aureus, Pseu
Domonus aeruginosa was used.

(2) Mold resistance By the wet method of the mold resistance test method specified in JIS Z-2911-1976, a mold spore dispersion is sprayed onto a polymer molded body to be a sample, and the temperature is 28 ± 2 ° C. Humidity (RH) 95 ±
After culturing at 5% for 28 days, the sample was observed and evaluated according to the criteria shown in Table 1. In addition, as the test bacteria, Aspergi
llus niger, Penicillium fu
For the preculture, a potato dextrose agar medium (Eiken) was used.

[0024]

[Table 1]

[0025]

[Table 2]

Further, the above sample was subjected to JIS L-0217.
After washing in accordance with (105 method) and repeating 10 times, the antibacterial activity and mold resistance were evaluated in the same manner. The results are shown in Table 3.

[0027]

[Table 3]

As is clear from the results of Tables 2 and 3,
The polymer containing the silver coordination compound of TBZ of the present invention is
It was confirmed that it has strong antibacterial activity and mildew resistance, and is also excellent in its durability.

Example 2 Antibacterial and antifungal soft elastic polyurethane foam:

[Table 4]
(Parts by weight) (1) Polyether prepolymer (Pluronic L61: 66.7, Tetronic 701: 33.3, Tolylene diisocyanate: 33.8) 100.0 (2) Dimethyl silicone oil 0.4 (3) N-methylmorpholine 1.0 (4) Triethylamine 0.2 (5) Water 2.3 (6) TBZ silver coordination compound (reference example) 0.5

The components (1) to (6) are mixed with a high speed stirrer and foamed to obtain an antibacterial and antifungal soft elastic polyurethane foam.

Example 3 Antibacterial and antifungal flexible polyester foam:

[Table 5]
(Parts by weight) (1) Diethylene glycol / trimethylol propane polyester of adipic acid (molar ratio 16: 16: 1) 100.0 (2) Water 2.4 (3) Castor oil sodium sulfonate (50% aqueous solution) 4. 2 (4) ethoxylated benzylhydroxydiphenyl 1.5 (5) N-dimethylbenzylamine 1.4 (6) paraffin oil 0.1 (7) tolylene diisocyanate 55.0 (8) TBZ silver coordination compound ( Reference example) 1.0

The components (1) to (8) are mixed with a high speed stirrer and foamed to obtain an antibacterial and antifungal soft polyester foam.

Example 4 Antibacterial and antifungal polyester foam:

[Table 6]
(Parts by weight) (1) Diethylene glycol / trimethylol propane polyester of adipic acid (molar ratio 16: 16: 1) 100.0 (2) Tolylene diisocyanate 47.0 (3) N-diethylaminoethanol adipate 3.0 ( 4) Ammonium oleate 1.0 (5) Sulfonated castor oil 1.5 (6) Paraffin oil 0.5 (7) TBZ silver coordination compound (reference example) 1.0

The components (1) to (7) are mixed with a high speed stirrer and foamed to obtain an antibacterial and antifungal polyester foam.

Example 5 Antibacterial and antifungal leather-like sheet:

[Table 7]
(Parts by weight) (1) Butadiene / acrylonitrile / methacrylic acid copolymer (69 parts / 26.5 parts / 4.5 parts) 100.0 (2) Zinc oxide 5.0 (3) Sulfur 0.5 (4) Vulcanization accelerator 1.5 (5) Antioxidant 2.0 (6) Silver coordination compound of TBZ (reference example) 0.5 (7) 10% solution of polyvinyl chloride in dimethylformamide

A. Components (1) to (6) are mixed in a rubber mill to obtain a 25% dimethylamide solution of this mixture. B. A: (7) is mixed at a ratio of 65:35. C. A solution of 20% water and 80% dimethylamide was added to 10% of B.
The mixture is added to 0 part, mixed, defoamed, and coated on one side of the fiber fabric with a doctor knife to obtain an antibacterial and antifungal leather-like sheet.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Shigeyoshi Momose 48-18 Sakaemachi, Kita-ku, Tokyo Kose Research Institute Co., Ltd.

Claims (1)

[Claims] 1. A polymer containing a silver coordination compound of 2- (4-thiazolyl) benzimidazole.