JPH0717809A - Industrial mildewproofing composition - Google Patents

Abstract

PURPOSE:To obtain a mildewproofing composition for industrial raw materials and products of woods, pulps, papers, fibers, adhesives, films, etc. CONSTITUTION:This industrial mildewproofing composition contains diiodo- methylparatoluylsulfone and zinc salt of pyridinethiol-1-oxide as active ingredients.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an antifungal composition for industrial raw materials and products such as wood, pulp, paper, fibers, adhesives and films.

[0002]

2. Description of the Related Art Conventionally, halogenated phenol compounds and organotin compounds have been frequently used as industrial fungicides.
However, since these compounds have strong acute and chronic toxicity and are relatively difficult to decompose, there is concern about secondary pollution due to accumulation, and they are no longer suitable for use as fungicides in the future. Therefore, development of safer antifungal agents has been actively conducted, and various compounds have been provided.

[0003]

Diiodomethyl paratolyl sulfone has the structural formula (I)

[0004]

[Chemical 1]

It is often added in order to prevent the generation and decay of mold in various industrial fields such as wood, pulp, paper, fibers, adhesives and paints. However, the use of a single component of diiodomethyl paratolyl sulfone alone does not provide sufficient efficacy due to limited species of microorganisms that have efficacy, and often the amount of drug used increases and the cost also increases. Often. The zinc salt of pyridinethiol-1-oxide has the structural formula (II)

[0006]

[Chemical 2]

It is represented by the formula (1) and is useful as an industrial antiseptic and fungicide, but it needs to be added at a considerably high concentration in order to obtain a practical effect. In addition, resistance to microorganisms may occur, and sufficient efficacy may not be obtained. For this reason, various antifungal agents have been combined to stabilize the antibacterial spectrum and increase the action force.However, usually one of them only exhibits one effect or only an arithmetic average effect is obtained. The reality is that it cannot be done. For example, JP-A-63-196502 discloses that the metal salt of pyridinethiol-1-oxide and 2- (4
-A method of combining thiazolyl) benzimidazole,
Further, JP-A-5-58824 proposes a method of using a metal salt of pyridinethiol-1-oxide and iodopropargyl butyl carbamate as a mixture. Further, Japanese Patent Publication No. 57-16082 discloses a method in which the above-mentioned diiodomethylparatolyl sulfone and 1,2-dibromo-2,4-dicyanobutane are used as a mixture, and Japanese Patent Publication No. 3-72601.
The above-mentioned diiodomethyl paratolyl sulfone and 2-
Methods have been proposed in which methoxycarbonylaminobenzimidazole is used as a mixture, but these methods do not significantly improve the antifungal effect and are not sufficient.

[0008]

[Means for Solving the Problems] As a result of intensive studies conducted by the present inventors to supplement their antifungal efficacy, the inventors have found that zinc salts of diiodomethylparatolylsulfone and pyridinethiol-1-oxide are used as active ingredients. The present invention has been completed by finding that the industrial antifungal compositions characterized by containing each of them dramatically increase the antifungal effect as compared with the case where they are used alone. It is known that these diiodomethyl paratolyl sulfones are highly safe and do not accumulate, but as described above, they have poor antifungal spectrum selectivity and are not practically useful alone. Pyridinethiol-1-
The zinc salt of oxide has no accumulation property, and its synergistic effect with the above-mentioned diiodomethylparatolylsulfone can significantly reduce the amount used, so that it is possible to provide a practically harmless antifungal composition. Is.

The antifungal composition of the present invention can be applied directly or used in the form of oil, emulsion, paste, suspension and the like depending on the purpose of use. It is also possible to mix and use other fungicides, bactericides, insecticides, deterioration inhibitors and the like. The content ratio of the active ingredient in the composition of the present invention is not particularly limited, but the mixing ratio of the diiodomethylparatolylsulfone and the zinc salt of pyridinethiol-1-oxide is 1:19 to 1 by weight.
The ratio is preferably 9: 1, preferably 1: 4 to 4: 1. The antifungal composition of the present invention can be applied to various industrial materials and products. For example, wood and wood bamboo products, pulp, fibers, paints, adhesives, leather,
Examples include processed paper products, electronic components, wall coverings, and resin moldings.

[0010]

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. In the following description, compound names are abbreviated as follows.

Diiodomethylparatolylsulfone: DMTS Zinc salt of pyridinethiol-1-oxide: ZPT Further,% and parts are% by weight and parts by weight, respectively.

Example 1 DMTS 0.5%, ZPT
Emulsion was prepared by uniformly mixing 1.5%, dimethyl sulfoxide 83%, and emulsifier Sorpol 2852 (manufactured by Toho Kagaku) 15%.

(Example 2) DMTS 1.0%, ZPT
1.0%, dimethyl sulfoxide 83%, and emulsifier Sorpol 2852 (manufactured by Toho Kagaku Co.) 15% were uniformly mixed to obtain an emulsion.

(Example 3) DMTS 1.5%, ZPT
0.5%, dimethyl sulfoxide 83%, and emulsifier Solpol 2852 (manufactured by Toho Kagaku) 15% were uniformly mixed to obtain an emulsion.

(Example 4) DMTS 1.0%, ZPT
1.0%, polyoxyethylene nonyl phenyl ether 3.0%, polyoxyethylene alkyl phenyl ether sulfate 2.5%, white carbon 1.5%, xanthane gum 0.2%, water 90.8% And passed through a wet pulverizer to obtain a suspension.

Comparative Examples 1 and 2 A single agent containing 2% of each of DMTS and ZPT was prepared and used as a comparative example.

Test Example 1 Antifungal of Emulsion Paint A vinegar-acryl emulsion paint [ENBI # 60 manufactured by Shinto Paint Co., Ltd. (without addition of an antifungal agent)] was added with a prescribed amount of the chemical, and No. 1 was added. (5) A paint having the same weight as that of the filter paper was uniformly applied onto the qualitative filter paper and dried, and then the fungicidal efficacy after 3 days and 7 days was evaluated according to the test method of the paint described in JIS Z2911 "Test method for mold resistance". As a test strain, JI
In addition to the types described in S, strains that actually occurred on the paint wall surface (Pe
nicillium sp., Cladosporium sp.) was added and tested. The results are shown in Table 1. However, the indication of the degree of mold development was based on the following criteria.

-) No mold growth is observed on the test piece. ＋) The area of mold growth on the test piece is 1/100 of the total area
Do not exceed 10. ++) The area of mold growth on the test piece is 1 of the total area.
/ 10 to 1/3. ++) The area of mold growth on the test piece exceeds 1/3 of the total area. The results of Test Examples 2 and 3 are also shown based on the same criteria. As is clear from the results in Table 1, the composition of the present invention exhibited a remarkable antifungal effect as compared with the case where the composition of the present invention was used alone as in Comparative Example.

[0019]

[Table 1]

Test Example 2 Antifungal of wood Wood pine sapwood (length 2 cm × width 5 cm × thickness 0.3 cm) was mixed with 3 in a solution of chemicals diluted with water to a specified concentration.
Soak for 0 seconds and air dry. This test piece was placed on a potato dextrose agar plate, and a mixed mold spore suspension of 1 m
1 was sprinkled and cultured at 28 ° C. for 28 days and observed every 7 days. Chaetomium globosum, Trichode as test bacteria
rma viride, Penicillium funiculosum, and a wild strain (Fusarium sp.) that actually developed in Japanese red pine were used.
The results are shown in Table 2. As is clear from the results shown in Table 2, the composition of the present invention is
A remarkable antifungal effect was recognized.

[0021]

[Table 2]

Test Example 3 Anti-mold of cotton cloth with glue 5 parts of wheat starch, 2.5 parts of PVA, and 92 parts of water were mixed and heated to prepare a paste solution. After adding a specified amount of medicine to the paste solution,
Impregnate a # 40 broad cotton cloth with the same weight of glue as the cotton cloth,
After drying, it was cultured for 14 days based on the fiber product test method (wet method) described in JIS Z2911 "Mold resistance test method" to evaluate the antifungal effect. In addition to the types described in JIS as strains to be tested, strains actually generated on cotton cloth (Cladosporium
sp., Alternaria sp.) was also added and tested. The results are shown in Table 3. As is clear from the results in Table 3, the composition of the present invention exhibited a remarkable antifungal effect as compared with the case where the composition of the present invention was used alone as in Comparative Example. The composition of the present invention has a markedly improved efficacy as compared with the case where it is used as a single agent, and is suitable as a fungicide for various industrial materials and products.

[0023]

[Table 3]

[0024]

The composition of the present invention has remarkably improved efficacy as compared with the case where it is used alone, and is extremely excellent as an antifungal agent for various industrial materials and products.

Claims (1)

[Claims] 1. An industrial antifungal composition comprising a zinc salt of diiodomethylparatolylsulfone and pyridinethiol-1-oxide as an active ingredient.