JPH04356404A - Moldproof agent for industrial use - Google Patents

Abstract

PURPOSE:To provide the title low toxic agent having excellent moldproof effects on a wide variety of molds, comprising a combination of a specific quaternary ammonium compound with methyl 2-benzimidazolyl carbamate. CONSTITUTION:The objective moldproof agent which comprises a combination of (A) a quaternary ammonium compound of formula I (R1 to R4 are each chain hydrocarbon; one or two of them being of >=8C; X is halogen) (e.g. dioctyl dimethylammonium chloride, didecyl dimethylammonium chloride) with (B) methyl 2-benzimixazolyl carbamate of formula II. The weight ratio of A/B is (10:1) to (1:10), pref. (5:1) to (1:5). The level of the present agent at ca.1-1000 ppm gives a favorable mold proof effect.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a new antifungal agent.

0002

[Prior art and its problems] Conventionally, inorganic or organic compounds of heavy metals such as mercury, tin, copper, etc. and halogenated phenols have been used as industrial fungicides.
Since these compounds have high toxicity to humans and fish, they significantly deteriorate working and living environments, and their use is subject to significant restrictions. In general, industrial products such as wood, pulp, paints, pastes, leathers, textiles, and plastics often have the problem of mold growth and propagation, which impairs product value. Antifungal agents have been proposed to solve these problems. Quaternary ammonium salts (hereinafter abbreviated as QAC) are known as relatively excellent low toxicity fungicides. However, in the case of this antifungal agent, there are problems in that the antifungal effect is still insufficient, such as the effect being limited to a specific type of mold, and that the antifungal effect lacks sustainability. In addition, methyl 2-benzimidazolylcarbamate (hereinafter abbreviated as BICM) is known as another fungicide, but although this agent is effective against a wide range of fungi, its antifungal effect is weak at practical concentrations. There was a problem.

0003

[Problems to be Solved by the Invention] The present invention solves the above-mentioned problems found in conventional fungicides, and provides a fungicidal agent that is excellent in low toxicity and exhibits excellent fungal effects against a wide range of molds. The task is to do so.

0004

[Means for Solving the Problems] As a result of intensive research aimed at solving the above problems, the present inventors surprisingly found that
The inventors have discovered that the problem can be solved by combining BICM with QAC, and have completed the present invention.

That is, according to the present invention, there is provided an industrial fungicide characterized by containing a quaternary ammonium salt compound represented by the following general formula and 2-benzimidazoline methyl carbamate.

[0006]

[Chemical formula 1]

In the above formula, R1, R2, R3, and R4 are hydrocarbon groups, and one or two of them are long-chain hydrocarbon groups having 8 or more carbon atoms. This long-chain hydrocarbon group includes an alkyl group and an alkenyl group. Moreover, this long-chain hydrocarbon group can be linear or branched. The other hydrocarbon group may be any hydrocarbon group such as a lower alkyl group having 7 or less carbon atoms, a cycloalkyl group, or an aralkyl group. A preferred quaternary ammonium salt compound is, in the general formula, R1 is an alkyl group or alkenyl group having 8 to 18 carbon atoms, R2 is an alkyl group having 7 or less carbon atoms, or an alkyl group or alkenyl group having 8 to 18 carbon atoms, R3 and R4 are each represented by an alkyl group having 7 or less carbon atoms or a benzyl group. As the halogen, chlorine, bromine or iodine is generally used. Further, the BICM used in the present invention is expressed by the following formula.

[0008]

[Chemical 2]

The antifungal agent of the present invention is composed of a combination of two different types of antifungal agents as described above, and has extremely excellent antifungal properties that could not be expected from each component alone. It exhibits a mold effect and has a wide range of application against mold, regardless of its type.

[0010] Specific examples of QAC used in the present invention include:
Long chain alkyltrimethylammonium halides such as octyltrimethylammonium chloride, decyltrimethylammonium chloride, dodecyltrimethylammonium chloride, hexadecyltrimethylammonium chloride, stearyltrimethylammonium chloride; octyldecyldimethylammonium chloride, dioctyldimethylammonium chloride,
Di-long chain alkyl dimethyl ammonium halides such as didecyl dimethyl ammonium chloride, dihexadecyl dimethyl ammonium chloride, dioctadecyl dimethyl ammonium chloride; Examples include chain alkyldimethylbenzylammonium halides. Of course, these may be a mixture, or a mixture having mixed long-chain alkyl groups derived from common fats and oils. Among these, dioctyldimethylammonium chloride, didecyldimethylammonium chloride,
Preference is given to using dodecyldimethylbenzylammonium chloride, hexadecyldimethylbenzylammonium chloride or octadecyldimethylbenzylammonium chloride.

[0011] Blending ratio (weight ratio) of QAC and BICM
is (10:1) to (1:10), preferably (
5:1) to (1:5). The antifungal agent of the present invention is basically prepared by uniformly mixing the two components described above, but it is generally used as a dispersion solvent solution, an emulsified dispersion, etc. with a surfactant, etc. Ru. In this case, examples of the surfactant include general nonionic and anionic surfactants. Examples of the solvent include alcohol solvents, ketone solvents, ether solvents, hydrocarbon solvents, and the like. The antifungal agent of the present invention may be used in the liquid form as well as in the form of a solid carrier.
The mode of use thereof is not particularly limited, and it can be used in various modes. The amount added when using the fungicide of the present invention varies depending on the microorganism concentration, but in general, 1
A good antibacterial effect can be obtained at about 1000 ppm. There is no problem in adding stabilizers, surfactants, etc. to the antifungal agent of the present invention as long as they do not particularly impede the purpose of the present invention.

0012

EXAMPLES Next, the present invention will be explained in more detail with reference to examples. Note that all parts shown below are based on weight.

Examples (Preparation of antifungal agents) Various antifungal agents having the following component compositions were prepared. Invention product (I) BICM: 5 parts DDAC: 5 parts Invention product (II) BICM: 5 parts Berzalkonium chloride: 5 parts Invention product (III) BICM: 7.5 parts DDAC: 2.5 parts Invention product (IV) BICM: 2.5 parts DDAC: 7.5 parts Comparative product (I) BICM: 10 parts Comparative product (II) DDCA: 10 parts Comparative product (III) Berzalkonium chloride: 10 parts In addition, the above-mentioned DDAC and chloride The content of benzalkonium is as follows. (1) DDAC didecyldimethylammonium chloride (2) Benzalkonium chloride dodecyldimethylbenzylammonium chloride

0
(Mold-proofing test) Next, the mold-inhibiting concentration, mold-proofing effect on wood, and mold-proofing effect on pulp slurry were tested using the following test methods for the mold-proofing agents of the present invention and comparative products shown above. Examined. (1) Mold Growth Inhibitory Concentration Test A test bacterial species is inoculated into Waxman liquid medium supplemented with 50 μg/ml of streptomycin, each test fungicide is added at a specified concentration to this fixed amount, and cultured with shaking at 32°C. . After 7 days, the growth of mold was investigated, and the growth-inhibiting concentration of each test fungicide was determined. The results are shown in Table 1. The bacterial species used in the test are as follows. ■ Aspergillus niger ATCC
6275(A.n) ■ Trichoderma T-
1 ATCC 9545 (T.t)■ Penicil
lium luteum ATCC 9644 (P.l
) ■ Rhizopus nigricans S. N
．． 32 (R.n)

[0015]

[Table 1] (Note) ++ indicates complete growth of the test bacteria.

(2) Antifungal test for pulp slurry The antifungal agents of the present invention and comparative products were added to a 1% slurry of pulp (BLKP) at a concentration of 300 ppm. This was filtered to create a pulp sheet, and after storing this sheet in a thermostat at 32° C. for 7 days, the growth of mold on the surface was observed. The results are shown in Table 2. The growth status of mold was determined based on the following criteria. -: No signs of mold growth ±: No obvious growth, but signs of growth +: Obviously growth ++: Vigorous growth

[0017]

[Table 2]

(3) Wood mold test Sapwood pieces (20 x 3 x 50 m/m) of tropical wood containing 0.03%, 0.06%, and 0.12% of the present invention product and comparative product. It is immersed in an aqueous solution for 30 minutes under reduced pressure of about 60 mmHg. Thereafter, after air-drying for one day and storing in a thermostat at 32° C. for 7 days, the growth of mold on the surface of the sapwood was observed, and the results are shown in Table 3. The growth status of mold was determined based on the following criteria. −: No signs of mold growth ±: No obvious growth, but signs of growth +: Obviously growth ++: Vigorous growth

[0019]

[Table 3]

[0020]

Effects of the Invention: As can be seen from the results shown in Tables 2 and 3 above, each component constituting the antifungal agent of the present invention alone does not provide a particular antifungal effect, but when both components are used in combination. This makes it possible to obtain a significantly superior anti-mold effect.

Claims (1)

[Claims] Claim 1: General formula: An industrial fungicidal agent characterized by containing a quaternary ammonium compound represented by the following formula (wherein X represents a halogen atom) and methyl 2-benzimidazolylcarbamate.