JP2003277208A - Industrial antifungal and antiseptic composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To solve the problem that there is a demand for a further effective antifungal and antiseptic agent because fungi outside the conventional antifungal spectra emerge in spite of attempts to combine various antifungal agents or to stabilize antifungal spectra, the enhancement of effectiveness, etc. <P>SOLUTION: It has been found out that when combining the three compounds of 3-iodo-2-prpopynylbutyl carbamate, methylenebisthiocyanate and methyl 2- benzimidazolecarbamate as the active ingredient, the compounds exhibit improved antifungal and antiseptic effectiveness as compared with the case in which they are used singly or in the form of a two-component mix. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to wood, pulp,
The present invention relates to an antifungal preservative composition for industrial raw materials and products such as paper, fibers, adhesives, paints, resin products such as vinyl chloride and plastics.

[0002]

2. Description of the Related Art Conventionally, halogenated phenol compounds and organotin compounds have been widely used as industrial fungicides. However, since these compounds have strong acute and chronic toxicity and are relatively difficult to decompose, there is a concern of secondary pollution due to accumulation, and they have become unsuitable for use as industrial fungicides and preservatives. Therefore, development of safer industrial antifungal preservatives has been actively conducted, and compounds such as 3-iodo-2-propynylbutylcarbamate (hereinafter abbreviated as IPBC) have been provided, wood,
In many industrial fields such as pulp, paper, fibers, adhesives, and paints, it is often added to prevent the generation of mold and decay. However, the use of a single component of IPBC alone does not provide sufficient efficacy due to the limited species of microorganisms having efficacy, and often the amount of the drug used increases and the cost often increases. Methylenebisthiocyanate (hereinafter abbreviated as MBTC) is also known as an industrial antifungal preservative, but when applied alone, it often causes microbial resistance and its application concentration must be considerably high. If you do not get enough effect. Also MB
TC was not sufficient in terms of stability and markedly lacked suitability as an antifungal preservative.

[0003]

For this reason, attempts have been made to combine various antifungal preservatives to stabilize the antifungal antiseptic spectrum and enhance the antifungal effect, but usually either one of them is effective in expressing the effect. The reality is that they either stay or only get an additive effect. For example, JP-A-63-41405
JP-A-2-164803 describes a method of using sodium 1,4-bis- (2-ethylhexyl) sulfosuccinate as a stabilizer in the above-mentioned IPBC, and further discloses that the above-mentioned IPBC and a benzimidazole compound are used as a mixture. Although methods have been proposed, these methods did not remarkably improve the fungicidal effect and the control effect was not sufficient. In addition, JP-A-3
No. 251508 proposes a method in which a benzimidazole compound and an isothiazoline compound are used as a mixture, but fungi that cannot be controlled by these mixtures have appeared, and therefore a drug having further effects is desired. It was

[0004]

[Means for Solving the Problems] The inventors of the present invention have conducted extensive studies as to an industrial antifungal antiseptic composition for compensating for the lack of efficacy, and as a result, IPBC, MBTC and methyl 2-benzimidazole carbamate ( The present invention has been completed by finding that the antifungal effect is remarkably increased when three kinds of BCM (hereinafter abbreviated as BCM) are combined, as compared with the case where they are used alone or as a mixture of two kinds. That is, the present invention uses IPBC and MB
It is an antifungal composition for industrial use characterized by containing three kinds of TC and BCM as active ingredients.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The industrial antifungal composition of the present invention can be directly applied depending on the purpose of use, but it is generally used as a formulation such as an oil, emulsion, paste or suspension. use. The polar solvent used in the case of formulation, glycol solvents such as ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, hexylene glycol, polyethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono A glycol ether solvent such as butyl ether, an alcohol solvent such as isopropyl alcohol and 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.

Examples of the nonpolar solvent include plasticizers such as dioctyl phthalate and diisononyl phthalate, xylol,
Toluene, isophorone, phenylxylylethane, diethylene glycol monobutyl ether acetate, propylene carbonate, liquid paraffin, kerosene, palm oil,
Solvents such as rapeseed oil, cottonseed oil, 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, and when it is used, any of a nonionic surfactant, an anionic surfactant, a cationic surfactant and a zwitterionic surfactant may be used. Absent. 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. In the case of amphoteric surfactants, betaine-type surfactants,
Examples include, but are not limited to, aminocarboxylic acid salts.

These nonionic surfactants, anionic surfactants, cationic surfactants and amphoteric surfactants may be used alone or in combination of two or more. Good. The content ratio of the active ingredient in the composition of the present invention is not particularly limited, but the mixing ratio of IPBC and MBTC is 10: 1 to 1:10 by weight, preferably 5: 1.
˜1: 5, and the blending ratio of the total amount of IPBC and MBTC and BCM is 10: 1 to 1:10 by weight, preferably 5: 1.
~ 1: 5. The antifungal preservative composition of the present invention can be applied to various industrial materials and products. For example, wood, bamboo products and wood materials, pulp, fibers, paints, adhesives, leather,
Examples include paper and paper products, wallpaper materials, and resin molded products. It is also possible to mix and use other fungicides, bactericides, insecticides, rust preventives, deterioration inhibitors and the like.

[0008]

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

Table 1 shows the industrial antifungal compositions of Examples 1 to 3 and Comparative Examples 1 to 6. In Comparative Examples 1, 2 and 4, the antifungal agent compositions were obtained at the compounding ratio shown in Table 1 by ordinary stirring at room temperature. In addition, Examples 1 to 3 and Comparative Examples 3, 5, and 6
Was mixed with the composition shown in Table 1, mixed with glass beads having a diameter of 1 mm, pulverized for about 15 minutes and filtered with a wire net to obtain a fungicide-dispersed composition.

[0010]

【table 1】 * 1: Polyoxyethylene styryl phenyl ether * 2: Propylene glycol

Test Example 1 Beech sapwood (2 cm × 5 cm) was added to a solution of the industrial antifungal preservative composition of Examples and Comparative Examples, which was prepared by diluting wood with antifungal water to a specified concentration.
(cm × 0.3 cm) is soaked for 30 seconds and then air dried. This test piece was placed on a potato dextrose agar medium and sprinkled with 1 ml of a mixed spore suspension of mold, and the temperature was 26 ° C and the humidity was 95%.
The cells were cultured for 28 days. As the test bacteria, Aspergillus ni
ger, Penicillium funiculosum, Aureobasidium pullul
ans, Gliocladium virens, Cladosporium cladosporioi
des and Neurospora sp. were used. The results are shown in Table 2. However, the indication of the degree of mold growth was based on the following criteria.

-: No mold growth is observed on the test piece. +: Mold growth is recognized on the side surface of the test piece. ++: The area of mold growth on the test piece is 1 / of the total area
It is less than 3. ++: The area of mold growth on the test piece is 1 of the total area
/ 3 or more.

Test Example 2 A paste solution was prepared by mixing 5 parts of mildewproof wheat starch, 2.5 parts of PVA and 92 parts of water in a sizing cotton cloth and heating. After adding the specified amount of medicine to the paste, 4
A No. 0 broad cotton cloth is impregnated with a glue solution in an amount equal to that of the cotton cloth, dried, and then cultured at 28 ° C. for 14 days based on the textile product test method (wet method) described in JIS Z 2911 “Mold resistance test method”. The antifungal efficacy was evaluated. The test bacteria are Aspergillus niger, P
enicillium citrinum, Chaetomium globosum and Myrot
hecium verrucaria was used. The results are shown in Table 2. However, the indication of the degree of mold growth was based on the following criteria.

0: Growth of mycelia is not observed in the inoculated portion of the sample or test piece. 1: The area of the growing part of hyphae observed in the inoculated part of the sample or test piece does not exceed 1/3 of the total area. 2: The area of the growing part of hyphae observed in the inoculated part of the sample or test piece exceeds 1/3 of the total area.

Test Example 3 Saturated pine sapwood (2 cm x 5 cm x 0.3 cm) was added to a solution of the industrial antifungal antiseptic composition of Examples and Comparative Examples, which was prepared by diluting wood with antiseptic water to a specified concentration. Is soaked for 30 seconds and then air dried. A potato dextrose agar medium was solidified in a petri dish, and then a rotting fungus was inoculated, followed by culturing at 26 ° C. After the rotten fungus grew on the entire surface of the petri dish, a test piece was placed on this and cultured at 26 ° C. for 28 days. The test bacteria are Fomitopsis p
alustris and Trametes versicolor were used. The results are shown in Table 2. However, the indication of the degree of mold growth was based on the following criteria.

-: No growth of decay fungi is observed on the test piece. +: Growth of decay fungi is observed on the side surface of the test piece. ++: Area of growing portion of decay fungus on test piece is 1 of the total area
It is less than / 3. +++: The area of the growing portion of the decay fungus on the test piece is 1/3 or more of the total area.

[0017]

[Table 2] As is clear from the results in Table 2, the composition of the present invention had a remarkable antifungal effect as compared with the comparative example.

[0018]

EFFECTS OF THE INVENTION The composition of the present invention has remarkably improved efficacy as compared with the case where it is used alone or as a mixture of two kinds, and is suitable as an industrial antifungal preservative.

Claims (2)

[Claims] 1. An industrial antifungal preservative composition comprising 3-iodo-2-propynylbutyl carbamate, methylenebisthiocyanate and methyl 2-benzimidazole carbamate. 2. The compounding ratio of 3-iodo-2-propynylbutylcarbamate to methylenebisthiocyanate in the weight ratio of 10: 1 to 1:10, 3-iodo-2-
An industrial fungicidal preservative composition comprising a total amount of propynyl butyl carbamate and methylenebis thiocyanate and a compounding ratio of methyl 2-benzimidazole carbamate in a weight ratio of 10: 1 to 1:10.