JPH08119810A - Industrial mildewproofing agent - Google Patents

Abstract

PURPOSE: To obtain an industrial mildewproofing agent exhibiting excellent antimicrobial action on mould and a wide antimicrobial spectrum through synergistic effect, and capable of effectively inhibiting the propagation of mould by combining an isothiazolone compound with a specific thiophene compound. CONSTITUTION: This industrial mildewproofing agent is obtained by combining 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide of formula I with 4,5-dichloro-2- n-octylisothiazolin-3-one of formula II. The mixing weight ratio of the compound of formula I to the compound of formula II is pref. (40:1)-(1:10). In general, this industrial mildewproofing agent is pref. used in the form of solvent solution or an emulsified dispersion. This industrial mildewproofing agent is useful as a slime-controlling agent esp. in the paper and pulp industry.

Description

Detailed Description of the Invention

[0001]

The present invention relates to a novel industrial fungicide,
More specifically, the present invention relates to an industrial fungicide containing two kinds of agents as active ingredients, which exert excellent antibacterial activity against filamentous fungi by a synergistic effect and can effectively suppress the growth of filamentous fungi.

[0002]

2. Description of the Related Art Conventionally, water-based paints, paper coating liquids, and latexes prepared by using water systems for papermaking processes in the pulp and paper industry, water systems such as circulating cooling water in various industrial fields, or industrial water. In printing paste, leather, etc., harmful microorganisms are easily propagated, which causes a decrease in productivity and a decrease in quality.

Particularly, in the papermaking process of the pulp and paper industry, slime adheres to the wall surface of the place where the pulp slurry flows, chests, flow boxes, transportation pipes, etc., which are detached and mixed in the paper pulp products to be variously mixed. It causes unfavorable situations such as staining spots and stains on paper, contamination of paper and pulp products, paper breakage, and reduction of work efficiency, which is a major obstacle to the production of paper and pulp.

Since such slime disorders have been mainly caused by bacteria, it has been attempted to suppress the production of slime by adding a compound having an antibacterial action. Conventionally, as such an antibacterial agent, an isothiazolone compound is used alone or in combination with another antibacterial agent (Japanese Patent Laid-Open No. 62-70301, Japanese Patent Laid-Open No. 3301/1987).
No. 184904 and Japanese Patent Publication No. 6-21043).

[0005] By the way, most of the slime disorders so far have been caused by bacteria, but in recent years, due to the closure of industrial water, or the increase of the mixing ratio of waste paper in the raw materials for papermaking, etc., they are caused by filamentous fungi. The number of cases has increased. However, with respect to such filamentous fungi, antibacterial agents composed of isothiazolone-based compounds up to now have a low effect of suppressing the reproduction thereof, and cannot sufficiently control slime.

[0006]

Under these circumstances, the present invention is capable of effectively suppressing the growth of filamentous fungi, and is particularly useful for industrial fungicide for slime control in the pulp and paper industry. It was made for the purpose of providing an agent.

[0007]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies to develop an industrial fungicide capable of effectively suppressing the reproduction of filamentous fungi, and as a result, have identified a thiophene-based compound specific to an isothiazolone-based compound. By combining the compounds, the synergistic effect shows excellent antibacterial activity and broad antibacterial spectrum against filamentous fungi, and it was found that the reproduction of filamentous fungi can be effectively suppressed, and the present invention is completed based on this finding. I arrived.

That is, the present invention uses 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide and 4,5-dichloro-2-n-octylisothiazolin-3-one as active ingredients. The present invention provides an industrial antifungal agent.

In the industrial fungicide of the present invention, 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide used as an active ingredient is represented by the formula:

Embedded image It is a known compound having a structure represented by 4,5-dichloro-2-n-octylisothiazoline-
3-on is the formula

Embedded image It is a known compound having a structure represented by: Each of these compounds has an excellent antibacterial activity against a certain type of microorganism, but when used alone, it has a narrow antibacterial spectrum against filamentous fungi, and its antibacterial activity is low. Cannot be suppressed sufficiently.

In the present invention, the above 3,3,4,4-
By combining tetrachlorotetrahydrothiophene-1,1-dioxide and 4,5-dichloro-2-n-octylisothiazolin-3-one, its synergistic effect makes filamentous fungi superior to those used alone. It has antibacterial activity and is effective against a wide range of filamentous fungi.

In the industrial fungicide of the present invention, the 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide and 4,5-dichloro-2-n-octylisothiazolin-3-one are used. It is desirable that the mixing ratio by weight is in the range of 40: 1 to 1:10, preferably 10: 1 to 1: 2. If the content ratio deviates from the above range, the desired synergistic effect is not exhibited, and the object of the present invention cannot be sufficiently achieved.

The industrial fungicide of the present invention is basically prepared by uniformly mixing the above-mentioned two components, but it is generally used as a solvent solution or an emulsion dispersion.

Examples of the solvent that can be used here include alcohol solvents, ketone solvents, ether solvents, hydrocarbon solvents and the like. Among them, triol solvents such as glycerin and trimethylolpropane,
Glycol-based solvents such as alkylene glycol, dialkylene glycol and dialkylene glycol monoalkyl ether are preferred, and glycerin, trimethylolpropane, ethylene glycol, propylene glycol, diethylene glycol, diethylene glycol monobutyl ether, diethylene glycol monomethyl ether or dipropylene glycol are particularly preferred. Further, propylene carbonate, ethylene carbonate, γ-butyrolactone, N-methylpyrrolidone, tetrahydrofurfuryl alcohol and the like may be used. These solvents may be used alone or in combination of two or more.

Further, the industrial antifungal agent of the present invention may be used by supporting it on any carrier, and the use mode is not particularly limited, and various methods can be adopted. Further, other antibacterial and antifungal active ingredients, stabilizers, surfactants and the like can be added, if desired, within a range that does not impair the object of the present invention.

The amount of the fungicide added when used is
Although it depends on the concentration of microorganisms, etc., it is generally about 0.01 to 100 ppm based on the total amount of the two components in the case of a water system in the field of paper pulp, etc. It is about 500 ppm, and a good antifungal effect can be obtained in this range.

[0016]

The industrial antifungal agent of the present invention is 3,3.
4,4-tetrachlorotetrahydrothiophene-1,1
-Dioxide and 4,5-dichloro-2-n-octylisothiazolin-3-one are combined to show excellent antibacterial activity against filamentous fungi and broad antibacterial spectrum by synergistic effect, and to promote the reproduction of filamentous fungi. It can be effectively suppressed and is particularly useful as a slime control agent in the pulp and paper industry.

[0017]

EXAMPLES The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

Example 1 10 parts by weight of 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide, 4,5-dichloro-
2-n-octylisothiazolin-3-one 25% by weight
An industrial antifungal agent was prepared consisting of 10 parts by weight of a phenylxylylethane solution having a concentration and 80 parts by weight of propylene carbonate.

Example 2 5 parts by weight of 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide, 4,5-dichloro-2
-N-octylisothiazolin-3-one 25% by weight
An industrial antifungal agent was prepared consisting of 5 parts by weight of a phenylxylylethane solution at a concentration and 90 parts by weight of propylene carbonate.

Comparative Example 1 An industrial fungicide was prepared consisting of 10 parts by weight of 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide and 90 parts by weight of propylene carbonate.

Comparative Example 2 4,5-Dichloro-2-n-octylisothiazoline-
An industrial antifungal agent was prepared consisting of 10 parts by weight of a 3-one 25% by weight phenylxylylethane solution and 90 parts by weight of propylene carbonate. With respect to the industrial antifungal agents prepared in Examples 1 and 2 and Comparative Examples 1 and 2, the bacterial growth inhibitory effect and slime generation inhibitory effect were examined by the test methods shown below.

Test Example 1 Inhibition test A part of an Aspergillus niger colony was taken, suspended in physiological saline, divided into test tubes in equal amounts, and Waxman's medium was added to each of the fungicides. The agent was added so that the concentration of the bactericidal component was a predetermined value, and the mixture was shake-cultured at 32 ° C. After 24 hours, the growth inhibitory concentration of the microorganism was determined by the degree of reproduction of the microorganism. The results are shown in Table 1.
Shown in

[0023]

[Table 1]

In the table, "++" indicates that the microorganism was clearly grown, "+" indicates that the microorganism was observed, and "±" indicates that the culture was slightly turbid and the growth of the microorganism was observed. , "-" Means that the culture solution is transparent and growth of microorganisms is not observed.

Test Example 2 Inhibition Test A test was carried out in the same manner as in Test Example 1 by removing a part of a colony of filamentous fungus of the genus Geotricum. Table 2 shows the results.

[0026]

[Table 2]

The symbols in the table are the same as in Table 1.

Test Example 3 Sterilization test A part of an Aspergillus niger colony was taken, suspended in physiological saline, and divided into test tubes in equal amounts. Add it to the specified concentration, leave it for 15 minutes, dilute it with a large volume of physiological saline, mix 1 ml of this solution with the heat-dissolved Waxman agar medium, solidify, and incubate at 32 ° C. went. Four
After 8 hours, the bactericidal concentration of the microorganism was determined by the degree of reproduction of the microorganism. The results are shown in Table 3.

[0029]

[Table 3]

In the table, "++" indicates that 100 or more colonies were observed, "+" indicates that 10 or more and less than 100 colonies were observed, and "±" indicates 1 or more and less than 10 colonies. Colonies were observed, and "-" indicates that no microbial growth was observed.

Test Example 4 Sterilization Test A test was carried out in the same manner as in Test Example 3 by taking a part of a colony of filamentous fungus of the genus Geotricum. The results are shown in Table 4.

[0032]

[Table 4]

The symbols in the table are the same as in Table 3.

From the results of Test Examples 1 to 4 described above, 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide and 4,5-dichloro were found to have the effect of inhibiting the growth and bactericidal effect of filamentous fungi. The synergistic effect of the combination with the 2-n-octylisothiazolin-3-one is clear.

Test Example 5 A white paper produced by a paper manufacturing company was used to carry out a sterilizing effect test of each of the antifungal agents. The filamentous fungi isolated from white water were of the genus Psilomyces, genus Acremonium, and genus Geotricum. The results are shown in Table 5.

[0036]

[Table 5]

The symbols in the table are the same as in Table 3.

From Table 5, the effect of the present invention was clarified also on filamentous fungi in white water of a paper manufacturing company.

Claims (2)

[Claims] 1. An active ingredient comprising 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide and 4,5-dichloro-2-n-octylisothiazolin-3-one. Industrial fungicide. 2. A mixing ratio of 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide and 4,5-dichloro-2-n-octylisothiazolin-3-one in a weight ratio of 40: The industrial antifungal agent according to claim 1, which is 1 to 1:10.