JP2003073213A - Industrial antibacterial composition and antibacterial method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an industrial antibacterial composition having such strong antibacterial activity for controlling bacteria that any conventional antibacterial agent never gives when it is solely used, and to provide an antibacterial method. SOLUTION: This industrial antibacterial composition contains a first component and a second component, wherein the first component comprises 2-(4- thiocyanomethylthio)benzothiazole and the second component comprises a pyridine-based antibacterial compound comprising, preferably, at least one kind of compound selected from sodium salt of 2-pyridinethiol-1-oxide, zinc salt thereof, copper salt thereof, and 2,3,5,6-tetrachloro-4-(methylsulfonyl)pyridine. The antibacterial method comprises utilizing the components as active ingredients.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an industrial antibacterial composition and an antibacterial method for controlling microbial contamination of industrial products and the like.

[0002]

BACKGROUND ART Paints, resin products such as PVC and plastics,
Industrial products such as fiber and wood are contaminated with fungi (molds, mushrooms, yeasts, etc.), bacteria, or microorganisms such as algae, causing physical property deterioration and aesthetic defects. When it is used indoors, it may cause allergies. In the case of paints, when they are used for building exteriors, algae and mold grow on the outer walls, which causes aesthetic problems and deterioration of physical properties of surface coating films. Bacteria grow, which not only causes aesthetic problems but also causes allergies. When used as an interior material such as flooring and wallpaper, PVC has been a problem in terms of aesthetics and allergies due to the growth of mold and bacteria as in the case of paint. In addition, when used as a flooring material, the wood of the base may be damaged by mushrooms and decay. For various plastic products, triangular corners used in kitchens and bath tubs used in bathrooms cause slime due to bacteria, mold and yeast growing, which causes aesthetic and hygiene problems. There is. In the case of textile products, mold grows on the fiber surface during storage in the warehouse, causing an aesthetic problem and reducing the commercial value. In addition, when used as clothes, bacteria propagate due to nutrients such as sweat, which causes odors and poses a sanitary problem. With regard to wood, the growth of mold causes an aesthetic problem, which lowers its commercial value, and the growth of mushrooms after use as a building material causes decay and deterioration of strength.

In industrial products such as paints, resin products such as vinyl chloride and plastics, fibers, woods and the like, various chemicals have been used to prevent contamination by fungi (molds, mushrooms, yeasts, etc.) and microorganisms such as bacteria and algae. It was For example, 2- (4-
Thiazolyl) benzimidazole, 2-methoxycarbonylaminobenzimidazole and other imidazole compounds, 2-n-octylisothiazolin-3-one, 4,
Thiazoline compounds such as 5-dichloro-2-n-octyl-4-isothiazolin-3-one and n-butylbenzisothiazolin-3-one, 2-pyridinethiol-
Zinc salt, sodium salt, copper salt of 1-oxide, or
Pyridine compounds such as 2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine, iodo compounds such as diiodomethyl-p-tolylsulfone, 3-iodopropynylbutylcarbamate and triiodoallyl alcohol, or Azole compounds such as proconazole, tebuconazole, propiconazole, and hexaconazole have been used.

However, since continuous use of a single drug over a long period of time tends to cause the appearance of resistant bacteria, various antibacterial agents composed of two or three components have been used in the past. For example, for a combination of two components,
25-644 in combination with 2-methoxycarbonylaminobenzimidazole and 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, 2-pyridinethiol-in the registered patent 2999875.
A large number of combinations of 1-oxide and 3-iodopropynylbutylcarbamate are disclosed. In some cases, a combination of three components is also disclosed. These combinations have good antibacterial efficacy against industrial products where a single drug has been used for a long time, but 2
Since a drug composed of a combination of three components has become common as a means for controlling microorganisms, and resistant bacteria have emerged due to long-term use even in combination and combination, a drug having further effects has been desired. In addition, a single drug tended to increase the amount added to various industrial products due to its lack of efficacy, but by using a drug of a combination of two components and three components, the synergistic effect is increased, so that it is absolutely The amount added could be reduced and the load on the environment tended to be reduced.
However, it was expected that the amount added would be reduced by further effective combination.

[0005]

In order to meet the above-mentioned demands, the present invention provides a drug effective against a wide range of microorganisms, which has a strong antibacterial activity which was insufficient in the conventional combination. It is in.

[0006]

Means for Solving the Problems The inventors of the present invention have confirmed the effects of the combination of various components in order to solve the problems, and as a result of intensive studies, as a result, as the first component, 2-
It has been found that by containing (4-thiocyanomethylthio) benzothiazole and a pyridine antibacterial compound as the second component, it has an excellent antibacterial effect against a wide range of microorganisms at a low concentration. As the pyridine antibacterial compound, 2-
It is preferable to contain at least one selected from sodium salt of pyridinethiol-1-oxide, zinc salt, copper salt, or 2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine. . That is, in the present invention, 2- (4-thiocyanomethylthio) benzothiazole is used as the first component, and a pyridine-based antibacterial compound is used as the second component, preferably 2-pyridinethiol-
1-oxide sodium salt, zinc salt, copper salt or 2,3,5,6-tetrachloro-4-
An industrial antibacterial composition containing at least one pyridine compound selected from (methylsulfonyl) pyridine is a very excellent antibacterial composition having good antibacterial activity even at a low concentration. , And these active ingredients, various paints, various resin products such as PVC and plastics,
The fact that kneading or surface-treating an industrial product such as fiber or wood is an excellent antibacterial method.

As the antibacterial method of the present invention, an antibacterial composition containing two or more kinds of the above active ingredients may be added, or the above active ingredients may be added separately. Other antimicrobial agents can be added to further broaden the antimicrobial spectrum. In addition, when insect damage such as wood is also observed, it is preferable to use an insecticide as a mixture or add it separately.

The active ingredient of the present invention may be added to various paints, various resin products such as vinyl chloride and plastics, and industrial products such as fibers and woods either individually or as a mixture prepared at the time of production of each industrial product. There is no particular limitation on the solvent, surfactant, etc. used in the conversion. However, the solvent and surfactant used for formulation are limited to some extent by the object to which antibacterial properties are to be imparted. For example, the solvents used for antibacterial agents for PVC, which are widely used as wallpaper and floor materials, are often non-polar solvents, because the raw materials used for PVC wallpaper and floor materials are often oil-based. The antibacterial agent used for is diluted with water and subjected to immersion treatment, so that a polar solvent is desirable. Further, the dosage form of the preparation is not particularly limited, and may be a solid preparation or a liquid preparation. In the case of a liquid agent, it may be a water-soluble liquid agent, an oil-soluble liquid agent, or a (water-based or oil-based) flowable agent. Further, in the case of a solid formulation, it can be formulated into an appropriate dosage form such as powder and wettable powder, and can be appropriately selected depending on the object to which antibacterial properties are to be imparted.

As the polar solvent, ethylene glycol,
Glycol-based solvents such as propylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, hexylene glycol, polyethylene glycol, diethylene glycol monomethyl ether,
A glycol ether solvent such as diethylene glycol monoethyl ether or diethylene glycol monobutyl ether, an alcohol solvent such as isopropyl alcohol or ethanol, a solvent such as dimethylacetamide, dimethyl sulfoxide, γ-butyrolactone, methyl ethyl ketone, or water can be used. These may be used alone or in combination of two or more. As the non-polar solvent, dioctyl phthalate, plasticizer such as diisononyl phthalate, xylol, toluene, isophorone, phenylxylylethane, diethylene glycol monobutyl ether acetate, propylene carbonate, liquid paraffin, kerosene, coconut oil, rapeseed oil, cottonseed oil,
A solvent such as castor oil or soybean oil can be used. These may be used alone or in combination of two or more. Further, two or more kinds of polar solvent and non-polar solvent may be combined.

The surfactant may or may not be used. When it is used, any of a nonionic surfactant, an anionic surfactant, a cationic surfactant and a zwitterionic surfactant is used. It doesn't matter. Examples of the nonionic surfactant include polyoxyethylene alkylphenyl ether, polyoxyethylene styryl phenyl ether, polyoxyethylene alkyl ether, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, and the like, and as the anionic surfactant, Alkylbenzene sulfate, polyoxyethylene alkyl ether sulfate, polyoxyethylene alkylphenyl ether sulfate, dialkyl sulfosuccinate, etc., and cationic surfactants include aliphatic amine salts and their quaternary ammonium salts. Examples of amphoteric surfactants include, but are not limited to, betaine-type surfactants and aminocarboxylic acid salts. In addition, these nonionic surfactants, anionic surfactants,
The cationic surfactant and the amphoteric surfactant may be used alone or in combination of two or more.

[0011]

EXAMPLES Examples and comparative examples of the present invention will be described below, but the present invention is not limited thereto.
All the compounding ratios shown in the table below are weight%.

Examples 1 to 7 The antibacterial compositions shown in Table 1 were prepared, and the performance was examined by Test Example 1 and Test Example 2. The active ingredients in the table are indicated by the following abbreviations. In Example 1, the composition shown in Table 1 was used to obtain an antibacterial composition by ordinary stirring at room temperature. In addition, in Examples 2, 3, 4, 5, 6, 7, 8, and 9, the compounds shown in Table 1 were mixed, glass beads having a diameter of 1 mm were mixed, and the mixture was pulverized for about 15 minutes using a pearl mill and filtered with a wire net. By doing so, an antibacterial agent dispersion composition was obtained.

[0013] 2- (4-thiocyanomethylthio) benzothiazole: TCM TB 2-Pyridinethiol-1-oxide sodium salt: Na PT Zinc salt of 2-pyridinethiol-1-oxide: ZP T Copper salt of 2-pyridinethiol-1-oxide: Cu PT 2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine: TC MSP

[0014]

[Table 1] Table 1 Examples

Comparative Examples 1 to 9 The antibacterial compositions shown in Table 2 were prepared and tested in Test Example 1, Test Example 2,
To investigate its performance. In Comparative Examples 1, 2, and 6, the antibacterial agent compositions having the formulations shown in Table 2 were obtained by ordinary stirring at room temperature. Further, Comparative Examples 3, 4, 5, 7, 8, and 9 were mixed by the composition shown in Table 2, mixed with glass beads having a diameter of 1 mm, pulverized with a pearl mill for about 15 minutes, and filtered with a wire net to obtain antibacterial properties. An agent dispersion composition was obtained.

[0016]

[Table 2] Table 2 Comparative Example

Test Example 1 PVC antifungal test "Preparation of test sample" A predetermined amount of the antibacterial agents of Examples 7, 8, 9 and Comparative Examples 6, 7, 8, 9 was added to the following vinyl chloride formulation, and the mixture was heated to 150 ° C.
Knead for a few minutes with the two-roll machine set to. The kneaded sample is pressed by a press machine set at 180 ° C for several minutes to be molded, and then cooled by the press machine to obtain 5 cm x 5 cm.
The sample cut into pieces was used as a test sample for antifungal test. PVC-blended PVC resin 100.0 parts Diisononyl phthalate 50.0 parts Epoxidized soybean oil 3.0 parts Phosphite stabilizer 3.0 parts Ba / Zn stabilizer 0.5 parts "Test method" Prepared PVC sample Was subjected to a mold prevention test according to ASTM G21. That is, the prepared vinyl chloride sample was placed on the following inorganic salt agar medium, and 1 ml of a mixed spore suspension of the following test bacteria was sprinkled on the medium at a temperature of 28 ° C. and a humidity of 95.
% And cultivated for 28 days. Inorganic salt Agar medium Potassium dihydrogen phosphate 0.7 g Magnesium nitrate 0.7 g Ammonium nitrate 1.0 g Sodium chloride 0.005 g Ferrous sulfate 0.002 g Zinc sulfate 0.002 g Manganese sulfate 0.001 g Agar 15.0 g Distilled water 1000 ml Test bacterium Aspergillus niger Penicillium funiculosum Chaeatomium globosum Gliocladium virens Aureobasidium pullulans "Test results" The test results were shown in Table 3 below. -: No mold growth was observed on the test piece. +: The area of the mold growing portion on the test piece does not exceed 1/4 of the total area. ++: The area of mold growth on the test piece is 1 of the total area
Do not exceed / 2. +++: The area of mold growth on the test piece is 3 of the total area.
Do not exceed / 4. ++++: The area of mold growth on the test piece is 3 of the total area.
More than / 4. [Discussion] As shown in Table 3, the evaluation results on the 28th day of the preparations of Comparative Examples 6, 7, 8 and 9 containing the single active ingredient were ++
~ ++++, whereas the evaluation results of the preparations of the two active ingredient combinations of Examples 7, 8 and 9 are-~ ++, in comparison with the preparations of the respective active ingredients alone. It was confirmed that the vinyl chloride to which the pharmaceutical product containing the mixture of two active ingredients was added exhibited a remarkable antibacterial effect.

[0018]

[Table 3] Table 3 Anti-mold evaluation of PVC

Test Example 2 Antifungal Test of Paint "Preparation of Specimen Sample" Exterior water-based emulsion paint containing no preservative, antifungal agent, or antialgal agent Page # 70 (solid content: about 50)
%, Manufactured by Shinto Paint Co., Ltd.) in Examples 1, 2, 3, 4, 5, 6,
After adding a predetermined amount of Comparative Examples 1, 2, 3, 4, and 5, water was added to 2
Added 0%. The prepared paint was cut into a piece having a diameter of 3 cm. The No. 2 filter paper was dipped and dried at room temperature for 2 days.
Prepare the prepared sample in 200 ml of water for each test piece.
After being soaked for 8 hours, the sample was dried at room temperature for 2 hours and then dried at 80 to 85 ° C. for 2 hours as a test sample. "Test method" Prepared sample is JIS Z 2911: 2000
8. A mildew proof test was conducted according to the paint test. That is, the prepared sample was placed on the following agar medium, sprinkled with 1 ml of a mixed spore suspension of the following test bacteria, and the temperature was 28 ° C.
The culture was performed at a humidity of 95% or more for 7 days. Agar medium Glucose 40 g Peptone 10 g Agar 25 g Purified water 1000 ml Test bacterium Aspergillus niger Penicillium funiculosum Cladosporium cladosporioides Gliocladium virens Aureobasidium pullulans “Test results” The test results were shown in Table 4 below. -: No mold growth is observed on the test piece. +: The area of mold growth on the test piece is 1 of the total area
Do not exceed / 4. ++: The area of mold growth on the test piece is 1 of the total area
Do not exceed / 2. +++: The area of mold growth on the test piece is 3 of the total area.
Do not exceed / 4. ++++: The area of mold growth on the test piece is 3 / of the total area
More than four. “Test Results” The results are shown in Table 4 in accordance with the judgment results of Test Example 1. "Discussion" As shown in Table 4, Comparative Examples 1, 2, 3, 4, 5
The results of the evaluation on the 7th day of the pharmaceutical product containing one active ingredient of
+ To +++, while Examples 1, 2, 3, 4,
The evaluation results of the pharmaceutical products containing the two active ingredients of 5 and 6 are-
It was confirmed that, in the range from + to +, the paint to which the formulation containing two active ingredients was added exhibited a remarkable antibacterial effect, as compared to the formulation containing each active ingredient alone.

[0020]

[Table 4] Table 4 Antifungal evaluation of paint

[0021]

Industrial Applicability When the present invention is applied, it is possible to provide an industrial antibacterial composition having a strong antibacterial activity or an antibacterial method.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08K 5/3432 C08K 5/3432 C08L 101/00 C08L 101/00 C09D 5/14 C09D 5/14 7/12 7/12 201/00 201/00 F-term (reference) 4F006 AA17 AB65 AB66 BA17 CA00 DA04 4H011 AA02 AA03 BA01 BA06 BB09 BB10 BC01 BC06 BC18 BC19 BC22 DA01 DA14 DD07 DH02 DH03 4J002 BD031 EU046 EV327 FD186 FD187 GL01 4J0101 KA06 KA08 NA01 NA27 PB05

Claims (3)

[Claims] 1. An industrial antibacterial composition comprising 2- (4-thiocyanomethylthio) benzothiazole and a pyridine antibacterial compound. 2. The pyridine antibacterial compound is sodium salt, zinc salt or copper salt of 2-pyridinethiol-1-oxide or 2,3,5,6-tetrachloro-4-.
The industrial antibacterial composition according to claim 1, which is at least one compound selected from (methylsulfonyl) pyridine. 3. An antibacterial method comprising using the industrial antibacterial composition according to claim 1 in an industrial product such as paint, resin product, fiber or wood by kneading or surface treatment.