JP2003095828A - Industrial antibacterial composition and antibacterial method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an industrial antibacterial composition having a potent antibacterial activity which is insufficient with conventional single compounds, for controlling microorganisms, and an antibacterial method. SOLUTION: This industrial antibacterial composition contains as a first component, at least one kind of compound selected from triazole-based compounds of propiconazole, tebuconazole, ciproconazole, hexaconazole, epoxiconazole, ipconazole, metconazole or prochloraz, and as a second component, at least one kind of compound selected from thiazoline-based compounds of 2-methyl-4-isothiazolin-3-one, 2-n-octylisothiazolin-3-one, 4,5-dichloro-2-n-octyl-4- isothiazolin-3-one or n-butyl-1,2-benzisothiazolin-3-one, and the antibacterial method by using these active ingredients is also provided.

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-butyl-1,2-benzisothiazolin-3-one, zinc salt of 2-pyridinethiol-1-oxide, Sodium salts, copper salts, pyridine compounds such as 2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine, diiodomethyl-p-tolylsulfone, 3-iodopropynylbutylcarbamate, triiodoallyl alcohol, etc. And iodo-based compounds or azole-based compounds such as cyproconazole, 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 present inventors 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, propiconazole, tebuconazole, cyproco Nazole, hexaconazole, epoxyconazole, ipconazole,
Metconazole or at least one compound selected from prochlorazo triazole compounds, and 2-methyl-4-isothiazolin-3-one as a second component, 2
-N-octylisothiazolin-3-one, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one
On, or by containing at least one compound selected from thiazoline compounds of n-butyl-1,2-benzisothizolin-3-one, it has an excellent antibacterial effect against a wide range of microorganisms at a low concentration. I found that.
That is, the present invention, propiconazole as the first component,
At least one compound selected from tebuconazole, cyproconazole, hexaconazole, epoxyconazole, ipconazole, metconazole or prochlorazo triazole compounds, and as the second component 2-
Methyl-4-isothiazolin-3-one, 2-n-octylisothiazolin-3-one, 4,5-dichloro-2
-N-octyl-4-isothiazolin-3-one or at least one compound selected from thiazoline compounds of n-butyl-1,2-benzisothizolin-3-one. The industrial antibacterial composition is a very excellent antibacterial composition having a good antibacterial activity even at a low concentration, and these active ingredients are used for various coatings,
The present invention relates to an excellent antibacterial method in which various resin products such as vinyl chloride and plastics, kneading into industrial products such as fibers and wood, and surface treatment or pressure treatment are used.

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 sulfonate, polyoxyethylene alkyl ether sulfate, polyoxyethylene alkylphenyl ether sulfate, dialkyl sulfosuccinate and the like can be mentioned. As the cationic surfactant, aliphatic amine salt and its quaternary ammonium salt can be used. Examples of amphoteric surfactants include, but are not limited to, betaine-type surfactants and aminocarboxylic acid salts. Further, these nonionic surfactants, anionic surfactants, cationic surfactants and amphoteric surfactants 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 6 The antibacterial compositions shown in Table 1 were prepared, and the performance was examined by test examples. The active ingredients in the table are indicated by the following abbreviations. In Examples 1, 2, 3, 4, 5, and 6, the composition shown in Table 1 was used to obtain an antibacterial composition by ordinary stirring at room temperature.

Cyproconazole: CAZ Hexaconazole: HAZ 2-n-octylisothiazolin-3-one: OI
T 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one: DCOIT

[0014]

[Table 1] Table 1 Examples

Comparative Examples 1 to 4 The antibacterial compositions shown in Table 2 were prepared, and the performance was examined by the test examples. In Comparative Examples 1, 2, 3, and 4, the composition shown in Table 2 was used to obtain an antibacterial agent composition by ordinary stirring at room temperature.

[0016]

[Table 2] Table 2 Comparative Example

Test Example: Antifungal test of paint "Preparation of test sample" Aqueous emulsion paint for exterior with no preservative, antifungal agent, or antialgal agent added. 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 and 4, 20% of water was added.
Added. Cut the prepared paint to a diameter of 3 cm N
o. 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 soaking for 2 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" The prepared sample is JIS Z 2911: 20.
00 8. A mildew proof test was conducted according to the paint test. That is, put the prepared sample on the following agar medium,
1 ml of a mixed spore suspension of the following test bacteria was sprinkled, and the mixture was cultured at a temperature of 28 ° C. and 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 pulluans "Test results" The test results were shown in Table 3 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 / 4. “Test results” The results are shown in Table 3 according to the judgment results of the test examples. “Discussion” As shown in Table 3, Comparative Examples 1, 2, 3, and 4
The results of the evaluation on the 7th day of the pharmaceutical products containing various active ingredients were + to +.
++++, while Example 1, 2, 3, 4, 5, 6
The evaluation results of the pharmaceutical products containing the two active ingredients are:
Then, it was confirmed that the coating material to which the formulation containing two active ingredients was added exhibited a remarkable antibacterial effect, as compared with the formulation containing each active ingredient alone.

[0018]

[Table 3] Table 3 Antifungal evaluation of paints

[0019]

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.

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Claims (2)

[Claims] 1. At least one selected from propiconazole, tebuconazole, cyproconazole, hexaconazole, epoxyconazole, ipconazole, metconazole, or prochlorazo triazole compounds.
Compounds and 2-methyl-4-isothiazolin-3-one, 2-n-octylisothiazolin-3-one, 4,
5-dichloro-2-n-octyl-4-isothiazolin-3-one or at least one compound selected from n-butyl-1,2-benzisothizolin-3-one thiazoline compounds Industrial antibacterial composition characterized by 2. The industrial antibacterial composition according to claim 1 is applied to an industrial product such as a paint, a resin product, a fiber or wood by kneading, surface treatment or pressure treatment. Antibacterial method to do.