JP2009096754A - Industrial antifungal composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To prevent the deterioration and putrefaction of various industrial raw materials and products comprising plastics such as polyvinyl chloride and ethylene-vinyl acetate copolymer, emulsion paint, oily paint, adhesive, sealing agent, ink, wood, leather, fiber, etc., by microorganisms such as bacteria, yeasts, fungi and algae. <P>SOLUTION: A new industrial antifungal composition is provided which includes (A) 1-[[2-(2,4-dichlorophenyl)-4-n-propyl-1,3-dioxolan-2-yl]methyl]-1H-1,2,4-triazole, (B) 2-n-octyl-4-isothiazolin-3-one and (C) 2-methoxycarbonylaminobenzimidazole or 2-(4-thiazolyl)benzimidazole as active components. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

The present invention relates to various industrial raw materials and products such as plastics such as polyvinyl chloride and ethylene vinyl acetate copolymer, emulsion paint, oil paint, adhesive, sealant, ink, wood, leather, fiber, etc. The present invention relates to a novel industrial antifungal composition for preventing deterioration and spoilage by microorganisms such as yeast, filamentous fungi and algae.

Up to now, various industrial antibacterial agents have been developed and used. Examples include 5-chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, 1,2-benzisothiazolin-3-one, Nn-butyl-1 , 2-benzisothiazolin-3-one, 2-n-octyl-4-isothiazolin-3-one, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, 2-methyl-4, Isothiazoline compounds such as 5-trimethylene-4-isothiazolin-3-one, 2-bromo-2-nitropropane-1,3-diol, 2,2-dibromo-2-nitroethanol, 2,2-dibromo-3 -Organic bromine compounds such as nitrilopropionamide, 1,2-dibromo-2,4-dicyanobutane, hexabromodimethylsulfone, formaldehyde, Aldehyde compounds such as aldehyde, o-phthalaldehyde, 3-methyl-4-isopropylphenol, 2-isopropyl-5-methylphenol, o-phenylphenol, 4-chloro-3,5-dimethylphenol, 2,4 , 4｀-trichloro-2｀-hydroxydiphenyl ether, phenolic compounds such as 4,4｀-dichloro-2｀-hydroxydiphenyl ether, orthophenylphenol, parachlorometaxylenol, 8-oxyquinoline, 2,3,5 Pyridine compounds such as 1,6-tetrachloro-4- (methylsulfonyl) pyridine, bis (2-pyridylthio-1-oxide) zinc, (2-pyridylthio-1-oxide) sodium, N, N ｀, N ｀ ｀ -Trishydroxyethylhexahydro-S-triazi , N, N ｀, N ト リ -trisethylhexahydro-S-triazine, 3,4,4｀-trichlorocarbanilide, 3-trifluoromethyl-4,4｀-dichlorocarbani Anilide compounds such as Lido, thiazole compounds such as 2- (thiocyanomethylthio) benzthiazole, imidazole compounds such as 2- (4｀-thiazolyl) benzimidazole, methyl 2-benzimidazole carbamate, 2, 4, Nitrile compounds such as 5,6-tetrachloroisophthalonitrile and 5-chloro-2,4,6-trifluoroisophthalonitrile, 4,5-dichloro-1,2-dithiolane-3-one, 3,3 , 4,4-tetrachlorotetrahydrothiophene-1,1-dioxide and other organic chlorine compounds, 3-iodo-2 Organic iodo compounds such as propynylbutyl carbamate, diiodomethyl-p-tolylsulfone, 2,3,3-triiodoallyl alcohol, p-chlorophenyl-3-iodopropargyl formal, N- (fluorodichloromethylthio) -phthalimide Phthalimide compounds and the like are known, and these antibacterial agents are also used in combination.

As an example in which a plurality of antifungal agents are used in combination, for example, a mixture of 2-n-octyl-4-isothiazolin-3-one and 2- (4-thiazolyl) -benzimidazole is described in (Patent Document 1). A mixture of 2-benzimidazolecarbamic acid lower alkyl ester containing methyl 2-benzimidazolecarbamate and 2-n-octyl-4-isothiazolin-3-one is disclosed in (Patent Document 2) and 2-pyridinethiol-1-oxide Alternatively, a mixture of the metal salt and 2- (4-thiazolyl) benzimidazole is 2 (Patent Document 3), and 2-pyridinethiol-1-oxide zinc salt and 2-n-octyl-4-isothiazolin-3-one Although the mixture is shown in (Patent Document 4), the antibacterial effect may not be sufficient, or it is highly toxic to human livestock. Or the amount is limited, or there is poor in residual effect over an extended period of time. Therefore, there has been a demand for an industrial antifungal composition with a smaller amount of use and a higher antifungal effect.

JP 56-113706 A Japanese Patent Publication No. 61-31081 JP-A 63-196502 Japanese Patent Laid-Open No. 2000-191212

  As a result of intensive studies to solve such problems, the present inventors have found that (A) 1-[[2- (2,4-dichlorophenyl) -4-n-propyl-1,3-dioxolan-2-yl] Methyl] -1H-1,2,4-triazole, (B) 2-n-octyl-4-isothiazolin-3-one, (C) 2-methoxycarbonylaminobenzimidazole, or 2- (4-thiazolyl) ) By adding an industrial anti-fungal composition characterized by containing benzimidazole as an active ingredient, it is possible to prevent the growth of various microorganisms that degrade industrial raw materials and products over a long period of time with the use of a small dose. As a result, the present invention has been found. In particular, it exhibits excellent performance when mixed with polyvinyl chloride.

According to the present invention, (A) 1-[[2- (2,4-dichlorophenyl) -4-n-propyl-1,3-dioxolan-2-yl] methyl] -1H-1,2,4- Containing triazole, (B) 2-n-octyl-4-isothiazolin-3-one, and (C) 2-methoxycarbonylaminobenzimidazole or 2- (4-thiazolyl) benzimidazole as active ingredients. A featured industrial antifungal composition is provided.

(A) 1-[[2- (2,4-dichlorophenyl) -4-n-propyl-1,3-dioxolan-2-yl] methyl] -1H-1,2,4-triazole; (B) The mixing ratio of 2-n-octyl-4-isothiazolin-3-one is 10: 1 to 1:10 (A) 1-[[2- (2,4-dichlorophenyl) -4-n-propyl- by mass ratio. 1,3-dioxolan-2-yl] methyl] -1H-1,2,4-triazole and (B) 2-n-octyl-4-isothiazolin-3-one, (C) 2 The compounding ratio of -methoxycarbonylaminobenzimidazole or 2- (4-thiazolyl) benzimidazole is preferably 10: 1 to 1:10 by mass ratio.

(A) 1-[[2- (2,4-dichlorophenyl) -4-n-propyl-1,3-dioxolan-2-yl] methyl] -1H-1,2, which is an antifungal composition of the present invention , 4-triazole, (B) 2-n-octyl-4-isothiazolin-3-one, and (C) 2-methoxycarbonylaminobenzimidazole or 2- (4-thiazolyl) benzimidazole as active ingredients The dosage form of the industrial antifungal composition is not particularly limited, and may be either powder or liquid. In addition to containing these compounds, the present composition may contain a solvent, a dispersant, a bulking agent, a thickener, and the like as necessary.

Examples of the solvent include alcohol solvents such as methanol, ethanol and isopropanol, glycol solvents such as ethylene glycol, diethylene glycol, polyethylene glycol and propylene glycol, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether and propylene glycol monomethyl. Glycol ether solvents such as ether, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, isophorone, ether solvents such as dioxane, tetrahydrofuran, dimethyl ether, ethyl acetate, methyl benzoate, dimethyl phthalate, diethyl adipate, etc. Ester solvents, toluene, xylene, methylnaphthalene, etc. Aromatic solvents, aliphatic or cycloaliphatic hydrocarbon solvents such as n-hexane and cyclohexane, petroleum fraction solvents such as paraffins, kerosene and light oil, halogenated hydrocarbon solvents such as chloroform and methylene chloride, Examples thereof include polar solvents such as dimethylformamide and dimethyl sulfoxide, and water. These solvents may be used alone or in combination of two or more.

Dispersants include polyoxyethylene alkyl ether, polyoxyethylene sorbitan alkyl ester, sorbitan alkyl ester, polyoxyethylene styryl phenyl ether, polyoxyethylene polyoxypropylene copolymer and other nonionic types, polyoxyethylene alkyl sulfate, alkylbenzene Examples of the surfactant include anionic types such as sulfonate and alkylsulfosuccinate, cationic types such as alkyldimethylammonium chloride and alkyldimethylbenzylammonium chloride, and amphoteric types such as lauryldimethylaminoacetic acid betaine. Of course, it is not limited to these, It may be used independently and may use 2 or more types together.

Examples of the extender include inorganic minerals such as calcium carbonate, aluminum hydroxide, clay, kaolin, and talc. This extender is not limited to these examples, and may be used alone or in combination of two or more.

Examples of the thickener include organic polymers such as xanthan gum, gum arabic, carboxymethyl cellulose, hydroxypropyl cellulose, and polyvinyl alcohol, and inorganic compounds such as silica. This thickener is also not limited to these examples, and may be used alone or in combination of two or more.

The present invention will be described in detail with reference to examples and test examples, but the present invention is not limited thereto. The blending ratios shown below are all parts by mass.

The antifungal compositions of Examples 1 to 4 and Comparative Examples 1 to 10 are shown in Table 1. In the table, OIT is 2-n-octyl-4-isothiazolin-3-one, BCM is an abbreviation for 2-methoxycarbonylaminobenzimidazole, TBZ is an abbreviation for 2- (4｀-thiazolyl) benzimidazole, and propiconazole Is an abbreviation for 1-[[2- (2,4-dichlorophenyl) -4-n-propyl-1,3-dioxolan-2-yl] methyl] -1H-1,2,4-triazole.

*
1) Carplex XR (Precipitated silica, manufactured by Shionogi & Co., Ltd.)
*
2) Super SS (light calcium carbonate, manufactured by Shiroishi Kogyo Co., Ltd.)
*
3) ZEST-PQLT (polyvinyl chloride, manufactured by Shin Daiichi PVC Co., Ltd.)
*
4) DINP (Diisononyl phthalate)

<Example 1>
(A) 1-[[2- (2,4-Dichlorophenyl) -4-n-propyl-1,3-dioxolan-2-yl] methyl] -1H-1,2,4-triazole (hereinafter propiconazole) 7.5 parts, (B) 10 parts of 2-n-octyl-4-isothiazolin-3-one (hereinafter abbreviated as OIT), and (C) 2-methoxycarbonylaminobenzimidazole (hereinafter abbreviated as OIT) , BCM) 25 parts, Super SS (light calcium carbonate, manufactured by Shiraishi Kogyo Co., Ltd.) 6 parts, ZEST-PQLT (polyvinyl chloride, manufactured by Shin-Daiichi PVC Co., Ltd.) 7 parts, and DINP (phthalate) Example 1 was obtained by mixing 44.5 parts of diisononyl acid).

<Example 2>
Example 2 was prepared by blending 25 parts of 2- (4-thiazolyl) -benzimidazole (hereinafter abbreviated as TBZ) in place of BCM.

<Example 3>
Example 3 was prepared by blending 10 parts of propiconazole, 7.5 parts of OIT, 25 parts of BCM, 6 parts of Super SS, 7 parts of ZEST-PQLT, and 44.5 parts of DINP.

<Example 4>
In Example 3, instead of BCM, 25 parts of TBZ was added as Example 4.

<Comparative Example 1>
Comparative Example 1 was prepared by mixing 7.5 parts of propiconazole, 10 parts of OIT, and 82.5 parts of DINP.

<Comparative example 2>
Comparative Example 2 was a mixture of 7.5 parts of propiconazole, 25 parts of BCM, 6 parts of Super SS, 7 parts of ZEST-PQLT, and 54.5 parts of DINP.

<Comparative Example 3>
In Comparative Example 2, Comparative Example 3 was prepared by blending 25 parts of TBZ instead of BCM.

<Comparative example 4>
A mixture of 10 parts of OIT, 25 parts of BCM, 6 parts of Super SS, 7 parts of ZEST-PQLT, and 52 parts of DINP was used as Comparative Example 4.

<Comparative Example 5>
In Comparative Example 4, Comparative Example 5 was prepared by blending 25 parts of TBZ instead of BCM.

<Comparative Example 6>
A mixture of 25 parts of BCM, 25 parts of TBZ and 50 parts of Carplex XR was used as Comparative Example 6.

<Comparative Example 7>
A mixture of 30 parts of propiconazole and 70 parts of DINP was used as Comparative Example 7.

<Comparative Example 8>
A mixture of 30 parts of OIT and 70 parts of DINP was used as Comparative Example 8.

<Comparative Example 9>
A mixture of 30 parts BCM, 6 parts Super SS, 7 parts ZEST-PQLT, and 57 parts DINP was used as Comparative Example 9.

<Comparative Example 10>
In Comparative Example 9, Comparative Example 10 was prepared by blending 25 parts of TBZ instead of BCM.

Test Example 1 (Anti-mold test of polyvinyl chloride sheet)
100 parts of ZEST-1000S (polyvinyl chloride, manufactured by Shin-Daiichi PVC Co., Ltd.), 50 parts of diisononyl phthalate, 3 parts of CK-39 (epoxidized soybean oil, manufactured by Kyodo Yakuhin Co., Ltd.), KH-650W (phosphite series) 3 parts of stabilizer, manufactured by Kyodo Yakuhin Co., Ltd., kneaded vinyl chloride sol prepared by thoroughly mixing 0.5 part of barium / zinc stabilizer (150 parts) at 150 degrees using a roll molding machine, A polyvinyl chloride sheet was prepared by heating at 180 degrees for 2 minutes 30 seconds using a press molding machine.
A polyvinyl chloride sheet to which Examples 1 to 4 and Comparative Examples 1 to 10 were added at the concentrations shown in Table 2 during kneading by a roll forming machine was cut into a size of 35 mm × 35 mm, and an inorganic salt agar medium (composition: phosphorus Potassium dihydrogen phosphate 0.7 g, dipotassium hydrogen phosphate 0.7 g, ammonium nitrate 1 g, magnesium sulfate heptahydrate 0.7 g, sodium chloride 0.005 g, ferrous sulfate heptahydrate 0.002 g, Zinc sulfate heptahydrate 0.002 g, manganese sulfate heptahydrate 0.001 g, agar 15 g, ion-exchanged water 1000 ml) 5 types of mixed spore suspension (Aspergillus niger IFO 6341, Penicillium) funiculosum IAM 7013, Paecilomyces variotiii IAM 5001, Gl ocladium virens IFO 6355, were cultured in Chaetomium globosum IFO 6347) a sprinkling 26 degrees was observed the growth conditions of mold piece over time test.

The results are shown in Table 2. Judgment criteria are as follows. As can be seen from the results, (A) 1-[[2- (2,4-dichlorophenyl) -4-n-propyl-1,3-dioxolan-2-yl] methyl] -1H of Examples 1 to 4 -1,2,4-triazole, (B) 2-n-octyl-4-isothiazolin-3-one, (C) 2-methoxycarbonylaminobenzimidazole, or 2- (4-thiazolyl) benzimidazole. The industrial antibacterial antifungal composition characterized by containing as an active ingredient showed good antifungal activity at a lower concentration relative to polyvinyl chloride.
0: growth of mold was not observed with the naked eye and under a microscope 1: growth of mold was not observed with the naked eye, but could be confirmed under a microscope 2: growth of mycelia was observed with the naked eye, and the area of the growth part was the total area of the sample 3: Less than 25% of mycelia: growth of mycelium is observed with the naked eye, and the area of the growing part is 25% or more of the total area

As described above, (A) 1-[[2- (2,4-dichlorophenyl) -4-n-propyl-1,3-dioxolan-2-yl] methyl] -1H-1,2, It contains 4-triazole, (B) 2-n-octyl-4-isothiazolin-3-one, and (C) 2-methoxycarbonylaminobenzimidazole or 2- (4-thiazolyl) benzimidazole as active ingredients. The industrial antifungal composition characterized by this can impart excellent antifungal properties to various industrial materials and products including polyvinyl chloride with a smaller dosage.

Claims (3)

(A) 1-[[2- (2,4-dichlorophenyl) -4-n-propyl-1,3-dioxolan-2-yl] methyl] -1H-1,2,4-triazole; (B) Industrial defense comprising 2-n-octyl-4-isothiazolin-3-one and (C) 2-methoxycarbonylaminobenzimidazole or 2- (4-thiazolyl) benzimidazole as active ingredients Mold composition. (A) 1-[[2- (2,4-dichlorophenyl) -4-n-propyl-1,3-dioxolan-2-yl] methyl] -1H-1,2,4-triazole; (B) The mixing ratio of 2-n-octyl-4-isothiazolin-3-one is 10: 1 to 1:10 by mass ratio, (A) 1-[[2- (2,4-dichlorophenyl) -4-n-propyl -1,3-dioxolan-2-yl] methyl] -1H-1,2,4-triazole and (B) 2-n-octyl-4-isothiazolin-3-one, (C) The industrial antifungal composition according to claim 1, wherein the mixing ratio of 2-methoxycarbonylaminobenzimidazole or 2- (4-thiazolyl) benzimidazole is 10: 1 to 1:10 by mass ratio. object. The object is a variety of industrial raw materials and products such as plastics such as polyvinyl chloride and ethylene vinyl acetate copolymer, emulsion paint, oil paint, adhesive, sealant, ink, wood, leather, fiber, etc. The industrial antifungal composition according to claim 1 or 2.