JPH08165206A - Germicidal agent composition - Google Patents

Abstract

PURPOSE: To obtain a germicidal agent composition improved in storage stability in water of a clathrate compound of 5-chloro-2-methyl-4-isothiazoline-3-one by adding a halogenated aliphatic nitroalcohol to the clathrate compound of 5-chloro-2-methyl-4-isothiazoline-3-one. CONSTITUTION: This germicidal agent composition (slime control agent composition) is obtained by treating 5-chloro-2-methyl-4-isothiazoline-3-one of formula I as a germicide with a host compound to form a clathrate compound and adding a halogenated aliphatic nitroalcohol to the clathrate compound to improve storage stability in water, especially in high-temperature water. Furthermore, since skin stimulating property of the halogenated aliphatic nitroalcohol is remarkably small compared with that of 5-chloro-2-methyl-4-isothiazoline-3-one, the skin stimulating property as the germicidal agent is almost unchanged by blending the compound. A compound such a bisphenol-based compound of formula II (R<1> is methylene or an alkylidene) is preferably used as a host compound including the compound of formula I.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a fungicide composition, and more particularly to 5-chloro-2-methyl-4-isothiazoline-3.
The present invention relates to a fungicide composition having improved storage stability of an on-inclusion compound in water.

[0002]

2. Description of the Related Art Conventionally, in order to prevent damage due to slime or the like in cooling water systems of various factory facilities or water systems such as paper pulp making systems, and to prevent spoilage of paints, adhesives, etc.
Because the treatment method is relatively simple and inexpensive,
Bactericides (slime control agents) are commonly used. Therefore, 5-chloro-2-methyl-4-isothiazoline-3 represented by the following formula (I) is used as a bactericide.
-ON (hereinafter abbreviated as "Cl-MIT") is excellent in bactericidal activity, and therefore slime control agents for various water systems such as cooling water systems, paper pulp, swimming pools, bactericides, algaecides, Widely used as a fungicide.

[0003]

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However, although Cl-MIT has an excellent bactericidal activity, it is extremely irritating to the skin and requires great care in handling.

Cl-MIT is extremely unstable,
In particular, it is a compound that is easily decomposed at high temperatures.

In order to solve such a problem, the present applicant has previously proposed that a water-soluble bactericidal agent such as Cl-MIT be formed into an inclusion compound with a host compound such as a bisphenol compound (Japanese Patent Laid-Open No. 1-1999). No. 190602, Japanese Patent Application No. 5-24
6888).

[0007]

By using Cl-MIT as the clathrate compound, the handling and stability of Cl-MIT are improved, but there are still the following problems.

That is, since the Cl-MIT clathrate compound is a crystalline powder, when it is used as a bactericide, it is usually added to the system to be sterilized as an aqueous suspension. In this case, Cl-MIT is used. As an inclusion compound, the stability is still insufficient in water, especially in high temperature water at a temperature of 60 ° C., and a satisfactory bactericidal effect cannot be obtained due to early decomposition.

The present invention solves the above-mentioned conventional problems, and
-An object of the present invention is to provide a bactericide composition having improved storage stability of MIT inclusion compound in water, especially in high temperature water.

[0010]

The fungicide composition of the present invention is characterized by containing a Cl-MIT inclusion compound and a halogenated aliphatic nitro alcohol.

In the present invention, as the host compound including Cl-MIT, the following I to IV are preferable.

[0012]

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Specific examples of the bisphenol compound of the above I include 4,4'-ethylidene bisphenol,
2,4'-isopropylidene bisphenol, 4,4 '
-Isobutylidene bisphenol and the like. Specific examples of the halogenated bisphenol compound of II include 2,2'-methylenebis (4-chlorophenol) and bis (2-hydroxy-5-chlorophenyl) sulfide. Specific examples of the monophenol compound of III include 2,4-dipropylphenol and 2,4-di-t-butylphenol.

The clathrate compound consisting of Cl-MIT and the above-mentioned host compound can be easily produced by a reaction in an organic solvent or in water.

When an organic solvent is used, methanol,
A solution prepared by dissolving the above-mentioned host compound in an ordinary organic solvent such as ethanol or acetone is mixed with Cl-MIT or a mixture thereof containing impurities, and the mixture is reacted.
As a result, the clathrate compound precipitates as a solid,
This is filtered and separated by a conventional method to obtain the target inclusion compound.

When the reaction is performed in water, the above host compound is directly added to an aqueous solution in which a guest compound, Cl-MIT, is dissolved, mixed and stirred. The aqueous solution used is
It does not necessarily need to contain only Cl-MIT, and may contain Cl-MIT and impurities as in the case of the organic solvent reaction. That is, Cl-MIT
And the above host compound reacts extremely selectively,
In the production of the clathrate compound, even if the raw material Cl-MIT containing impurities such as by-products is used as it is, the clathrate compound selectively encapsulating only the target Cl-MIT can be obtained. .

The reaction temperature may be arbitrary in the range of 0 to 100 ° C., but usually it is set to about 10 to 30 ° C.
A reaction time of about 0.5 to 24 hours is sufficient.

After the completion of the reaction, the clathrate compound is usually obtained as a solid, and this can be separated from the aqueous layer, washed with water and dried to obtain the target clathrate compound.

Cl-MIT which constitutes the inclusion compound
And the molar ratio of the host compound is usually Cl
-MIT: host compound = 1: 0.2-5.

On the other hand, the halogenated aliphatic nitro alcohol used in the present invention includes 2-chloro-2-nitroethanol, 1-chloro-1-nitro-2-propanol,
3-chloro-3-nitro-2-butanol, 2-chloro-2-nitro-1,3-butanediol, 1-chloro-
1-nitro-2-butanol, 2-chloro-2-nitrobutanol, 2-chloro-2-nitro-3-pentanol, 2,2'-dichloro-2-nitroethanol, 2-
Bromo-2-chloro-2-nitroethanol, 3-chloro-3-nitro-2,4-pentanediol, 4-chloro-4-nitro-3-hexanol, 2-bromo-2-
Nitroethanol, 2-bromo-2-nitro-3-propanol, 2-bromo-2-nitro-1,3-butanediol, 3-bromo-3-nitro-2,4-pentanediol, 2,2'- Dibromo-2-nitroethanol,
1,1'-dibromo-1-nitro-2-propanol,
4-bromo-4-nitro-3-hexanol, 2-fluoro-2-nitroethanol, 2-fluoro-2-nitro-1,3-butanediol, 3-iodo-3-nitro-2-butanol, 2- Chloro-2-fluoro-2-nitroethanol, 2-bromo-2-iodo-2-nitroethanol, 2-chloro-2-nitro-1,3-propanediol, 2-bromo-2-nitro-1,3 -Propanediol and the like.

Incidentally, the Cl-MIT clathrate compound is usually used as an aqueous suspension containing 0.1 to 15% by weight, preferably 0.5 to 5% by weight, of Cl-MIT.

In the present invention, a halogenated aliphatic nitroalcohol is blended in order to improve the storage stability of the Cl-MIT clathrate compound used in this way. The halogenated aliphatic nitroalcohol is blended. The proportion is preferably 0.1 to 5% by weight, and more preferably 0.3 to 3.0% by weight based on the Cl-MIT inclusion compound. If this ratio is less than 0.1% by weight, a sufficient stabilizing effect cannot be obtained, and if it is added in excess of 5% by weight, there is no difference in the stability improving effect, which is uneconomical.

Therefore, the bactericidal composition of the present invention generally comprises 0.1 to 15% by weight, preferably 0.5 to 5% by weight, of Cl-MIT inclusion compound in terms of Cl-MIT and the inclusion compound. 0.1 to 8% by weight based on Cl-MIT in the contact compound
And a halogenated aliphatic nitro alcohol. In addition, in order to prevent sedimentation of suspended particles, an appropriate dispersant or thickener may be used in combination with this aqueous suspension.

The bactericidal composition of the present invention containing the Cl-MIT inclusion compound and the halogenated aliphatic nitroalcohol in such a ratio may be, for example, the following Cl- depending on the purpose.
It is added and used so as to have the MIT concentration.

For the purpose of preventing slime of paper / pulp paper making system and cooling water: the Cl-MIT concentration is 0.1 to 25 g /
m ³ Synthetic resin emulsion, starch paste, starch slurry, paint, preservative for metal working oil, etc. Purpose: Cl-MIT concentration is 1 to 5000 g / m ³

[0026]

[Action] Cl-MIT becomes a solid state by being made into an inclusion compound by a host compound, the handling property is greatly improved, its solubility in water is suppressed, its toxicity,
Skin irritation and the like are reduced. Moreover, in addition to preventing the bactericidal activity from decreasing by reacting with other substances during use,
Thermal stability is also enhanced. Therefore, this clathrate compound can also be effectively used as a sustained-release bactericide capable of maintaining bactericidal activity for a long time.

By the way, as described above, Cl-MIT is
Although the inclusion compound enhances the stability, it cannot be said that its storage stability, especially in water, particularly in hot water, is sufficient.

However, in accordance with the present invention, the use of a halogenated aliphatic nitroalcohol in combination with Cl
-The storage stability of the MIT inclusion compound can be significantly enhanced. Since the skin irritation of halogenated aliphatic nitroalcohol is remarkably smaller than that of Cl-MIT, there is almost no change in skin irritation as a bactericide even if a halogenated aliphatic nitroalcohol is added.

[0029]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded.

Example 1 Production of Cl-MIT Inclusion Compound (Methanol Solvent Method) 75 g of methanol and 4,4'-ethylidene bisphenol (host compound) were placed in a 1-liter separable flask.
50 g was added and stirred with a meniscus stirring blade (length 5 cm) to completely dissolve the host compound. Keep this separable flask at 20 ° C and spin the contents at 500 rpm.
While stirring at 300g, 300 g of Caisson WT (registered trademark: manufactured by Rohm and Haas Co., an aqueous solution containing 10 to 12 wt% of Cl-MIT) was continuously added over 30 minutes to precipitate a host compound. After the addition was completed, stirring was continued for 1 hour to sufficiently precipitate the host compound. The precipitate is filtered,
It was washed 3 times with 75 ml of demineralized water and then air dried.

As a result, 79.8 g of Cl-MIT / 4,4'-ethylidene bisphenol inclusion compound was obtained. The Cl-MIT content in this clathrate is 35.7.
% By weight.

Evaluation of Stability of Cl-MIT Clathrate Compound The clathrate compound obtained above was used at a Cl-MIT concentration of about 1
It was added to water so that the concentration of the inclusion compound in water (concentration of inclusion compound in water was 2.81% by weight), and 2-bromo-2-nitro-
1,3-Propanediol was added at a ratio shown in Table 1 and suspended.

This suspension was left in a constant temperature bath at 60 ° C., and the change with time of the Cl-MIT concentration in the sample was measured. The results are shown in Table 1 (Nos. 1 to 4). For comparison, 2
The same measurement was performed in the case where -bromo-2-nitro-1,3-propanediol was not added, and the results are shown in Table 1.
(No. 5).

From Table 1, 2-bromo-2-nitro-1,
It is clear that the stability of Cl-MIT in water is enhanced by adding 3-propanediol.

[0035]

[Table 1]

[0036]

As described above in detail, according to the fungicide composition of the present invention, the storage stability of the Cl-MIT clathrate compound in water can be improved, so that Cl-MIT is used as an active ingredient. The practicality of the disinfectant is greatly increased.

Claims (1)

[Claims] 1. A bactericide composition comprising an inclusion compound of 5-chloro-2-methyl-4-isothiazolin-3-one and a halogenated aliphatic nitroalcohol.