JPH0930909A - Harmful microorganism eradicator containing isothiazolone-based clathrate compounds and stabilization of the eradicator - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject compounds that effectively prevent damage to paper, pulp and other industrial products by deleterious microorganisms and excels in sustainability of their effects as well as in storage stability by adding specific two kinds of stabilizers to an isothiazolone-based clathrate compound preparation. SOLUTION: With an isothiazolone-based clathrate compound preparation (A), hexamethylenetetramine (B) and a bromine-containing compound are mixed. It is preferable for the preparation to contain components (B) and (C) at wt. ratio within the range of (100:1) to (1:100). Furthermore, it is preferable for the total of contents of the components (B) and (C) to be within the range of 0.5-10wt.% to weight of the component (A). As the component (C), a compound of formula 1 (X is nitro or cyano group; Y and Z are Br, nitro group, cyano group, etc.; Y and Z are dioxane ring, etc.) is preferable. The component (A) is obtained by including a isothiazolone-based compound of formula II as a guest compound in a host compound (e.g. cyclodextrin, etc.).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel isothiazolone inclusion compound-containing harmful microorganism erasing agent and a stabilizing method. More specifically, the present invention is an isothiazolone inclusion compound-containing harmful microorganism that can effectively prevent damages caused by harmful microorganisms such as bacteria, fungi, and algae, and that has excellent sustainability of the effect and storage stability. The present invention relates to an eradication agent and a method for effectively stabilizing a harmful microorganism eradication agent containing an isothiazolone inclusion compound as an active ingredient.

[0002]

2. Description of the Related Art Conventionally, water-based paints and paper coatings prepared by using water-based systems in the papermaking process in the pulp and paper industry, metalworking oils, circulating cooling water in various industrial fields, or industrial water. Working fluid, latex emulsion,
In starch slurries, printing pastes, leather, etc., harmful microorganisms are easily propagated, which causes a decrease in productivity and quality. For example, 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., and it is released and mixed into the paper pulp product, causing various colored spots. It causes stains, stains of paper and pulp products, paper breakage, and reduction of work efficiency, which is a serious obstacle to the production of paper and pulp.
Further, in water systems such as circulating cooling water in various industrial fields, slime composed of bacteria, filamentous fungi, algae, etc. adheres to water passage pipes, etc., causing pipe closure, corrosion of metal materials, and deterioration of thermal efficiency. It is known that.

In order to prevent such damage caused by microorganisms, treatment with a compound having an antibacterial action has hitherto been carried out, and in recent years, particularly the skin and eyes are less irritating and the antibacterial effect is also present. The isothiazolone-based clathrate compounds have come to be used because of their excellent durability (JP-B-2-34356, JP-A-63-295568, JP-A-1-316301).

However, when this isothiazolone inclusion compound is slurried for formulation and the like, the storage stability is poor, and the pH at the initial preparation during storage of the slurry is
Since it decreases with the lapse of the storage period and causes aggregation and solidification, product management is difficult and it is difficult to stably supply the product.

In the paper and pulp industry, the antibacterial agent is often added to the papermaking system intentionally by an automatic addition device. In this case, the above isothiazolone inclusion compound preparation is used as the antibacterial agent. As described above, aggregation occurs as described above, and as a result, it becomes difficult to drop an appropriate amount of the antibacterial agent into the papermaking system, which causes generation of microorganisms. Furthermore, when an isothiazolone-type clathrate compound is used in a synthetic polymer emulsion, if the pH is lowered as described above, an emulsion shock occurs, and the emulsion phase is broken, causing phase separation and coagulation.

In order to improve such drawbacks, acids such as sulfuric acid, phosphoric acid, citric acid, maleic acid and succinic acid and salts thereof are blended as a pH adjuster, and ethylene glycol as a freezing point depressant is added. Propylene glycol,
Attempts have been made to blend glycerin and the like. However, it cannot be said that these techniques have sufficiently improved the above drawbacks.

[0007]

The present invention overcomes various drawbacks of such isothiazolone clathrate compound preparations, maintains the pH during preparation of the preparations during storage, and does not cause aggregation. Moreover, an isothiazolone-based clathrate-containing harmful microbe eradication agent and an isothiazolone-based clathrate-based harmful microbe eradication agent that can effectively prevent damage caused by harmful microbes such as bacteria, mold, and algae over a long period of time are effective. It was made for the purpose of providing a stabilizing method.

[0008]

Means for Solving the Problems The inventors of the present invention have conducted various investigations on a harmful microorganism eradicating agent containing an isothiazolone-based clathrate compound, and as a result, have found that an isothiazolone-based clathrate compound, hexamethylenetetramine, and a bromine-containing organic compound. By using a harmful microbial eradication agent containing a combination of, in this case, to the isothiazolone-based clathrate compound, by adding a predetermined amount of a mixture of hexamethylenetetramine and a bromine-containing organic compound in a specific ratio, They have found that they can be effectively stabilized, and have completed the present invention based on this finding.

[0009] That is, the present invention comprises a isothiazolone-based clathrate compound-containing harmful microorganism erasing agent, which comprises (A) an isothiazolone-based clathrate compound, (B) hexamethylenetetramine and (C) a bromine-containing organic compound. And a harmful microbial eradication agent containing an isothiazolone inclusion compound as an active ingredient, a mixture of hexamethylenetetramine and a bromine-containing organic compound in a weight ratio of 100: 1 to 1: 100 is added to the weight of the isothiazolone inclusion compound. The present invention provides a stabilizing method characterized by adding 0.01 to 10% by weight based on the above.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The isothiazolone-type clathrate compound used in the present invention is a compound in which an isothiazolone-type compound is used as a guest compound and which is clathrated with a host compound capable of being clathrated. The isothiazolone compound used as the guest compound has a general formula

Embedded image (R ¹ in the formula is a hydrogen atom, an alkyl group, an alkenyl group,
The alkynyl group or aralkyl group, R ² and R ³ are each a hydrogen atom or a halogen atom, and they may be the same or different, or they are condensed with each other to form a benzene ring. You may form. )
It is a compound represented by these.

In the general formula (I), among the groups represented by R ¹ , the alkyl group is, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group or a sec-group. A butyl group, a tert-butyl group, etc., an alkenyl group, for example, a vinyl group, an allyl group, a propenyl group, an isopropenyl group, a butenyl group, an isobutenyl group, etc., an alkynyl group, for example, an ethynyl (acetylenyl) group, Examples of the aralkyl group include propynyl group and propargyl group, and examples of the aralkyl group include benzyl group and phenethyl group. Moreover, examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom. Further, among the groups represented by R ² and R ³ , examples of the halogen atom include the same ones as described above.

Examples of such isothiazolone compounds include 5-chloro-2-methyl-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one.
On, 2-octyl-4-isothiazolin-3-one,
4,5-dichloro-4-isothiazolin-3-one,
Examples thereof include 1,2-benzisothiazolin-3-one, and among them, 5-chloro-2-methyl-4-isothiazolin-3-one is particularly preferable because it has excellent bactericidal properties.

The host compound used in the present invention is not particularly limited as long as it is capable of forming an inclusion compound by including an isothiazolone compound as the guest compound. Examples of such compounds include cyclodextrin, 1,1,6,6-tetraphenyl-2,4-
Hexadiyne-1,6-diol, 1,1-bis (2,2
4-dimethylphenyl) -2-propyn-1-ol,
1,1,4,4-tetraphenyl-2-butyne-1,4
-Diol, 1,1-bi-2-naphthol, 1,1,
6,6-Tetrakis (2,4-dimethylphenyl)-
2,4-hexadiyne-1,6-diol, 9,10-
Bis (4-methylphenyl) -9,10-dihydroanthracene-9,10-diol, 1,1-bis (4-hydroxyphenyl) cyclohexane, N, N, N ',
N '-(tetracyclohexyl)-[1,1-biphenyl] -2,2'-dicarboxamide, 5,5'-dichloro-2,2'-dihydroxydiphenylmethane, deoxycholic acid, 2,5-di- t-butylhydroquinone,
2,2'-methylenebis (4-chlorophenol), and further tetrakisphenol compounds are used.

Specific examples of the above tetrakisphenol compound include 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane and 1,1,2,2-tetrakis (3-methyl-4-hydroxyphenyl). Ethane 1,
1,2,2-tetrakis (3-bromo-4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3,3
5-dimethyl-4-hydroxyphenyl) ethane, 1,
1,2,2-tetrakis (3-t-butyl-4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3-chloro-4-hydroxyphenyl) ethane, 1,
1,2,2-tetrakis (3,5-dichloro-4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3-fluoro-4-hydroxyphenyl) ethane,
1,1,2,2-tetrakis (3,5-difluoro-4
-Hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3-methoxy-4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3,5-dimethoxy-4-hydroxyphenyl) ethane, 1,1,2,2-
Tetrakis (3-chloro-5-methyl-4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3-
Chloro-5-phenyl-4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3-phenyl-4-
Hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -2,2-bis (3-methyl-4-hydroxyphenyl) ethane, 1,1,3,3-tetrakis (4-hydroxyphenyl) propane , 1, 1, 3,
3-tetrakis (3-methyl-4-hydroxyphenyl) propane, 1,1,3,3-tetrakis (3-chloro-4-hydroxyphenyl) propane, 1,1,4
4-tetrakis (4-hydroxyphenyl) butane,
1,1,4,4-tetrakis (3-methyl-4-hydroxyphenyl) butane, 1,1,4,4-tetrakis (3-chloro-4-hydroxyphenyl) butane, 1,
1,5,5-tetrakis (4-hydroxyphenyl) pentane and the like can be mentioned.

The inclusion compound using these host compounds and the isothiazolone compound as a guest compound is
At least one of the above-mentioned host components is dissolved or suspended in a conventionally known method, for example, water, a lower alcohol such as methanol or ethanol, acetone, or a mixture thereof, and then the above-mentioned is added thereto. It is produced by a method of adding an isothiazolone compound and stirring the mixture at a temperature of usually 0 to 100 ° C., preferably 10 to 50 ° C. for about 10 minutes to 24 hours, preferably for about 30 minutes to 10 hours. You can

Since the isothiazolone-based clathrate compound thus formed is usually in a solid state, it is taken out from the reaction-terminated liquid by a known means such as filtration, and dried by vacuum drying or the like to form a powdery encapsulating compound. A clathrate is obtained.

The harmful microbial eradication agent of the present invention contains the isothiazolone inclusion compound obtained as described above as the component (A), and in this eradication agent, the isothiazolone inclusion compound is usually used. In order to suspend and make a slurry, water, an organic solvent, a mixed solvent of water and a hydrophilic solvent, or the like is used as a dispersion medium. As the organic solvent, ethylene glycol, propylene glycol, glycerin, polyol such as polyglycerin, diethylene glycol monomethyl ether, glycol ethers such as ethylene glycol monobutyl ether, liquid paraffin, further xylene, alkylbenzenes such as toluene, castor oil, Examples include vegetable oils such as soybean oil and olive oil, and terpenes such as cypress oil. These solvents may be used alone or in combination of two or more.

In the harmful microorganism eradicating agent of the present invention, the isothiazolone inclusion compound of the above-mentioned component (A),
Hexamethylenetetramine as component (B) and (C)
It is necessary to contain a bromine-containing organic compound as a component.

Examples of the bromine-containing organic compound as the component (C) include those represented by the general formula

Embedded image (In the formula, X is a nitro group or a cyano group, Y and Z are a bromine atom, a nitro group, a cyano group, a hydroxyl group,
Aminocarbonyl group, alkyl group, hydroxyalkyl group, acyloxyalkyl group, halogenated alkyl group,
A cyanoalkyl group, an aralkyl group or a halogenated aralkyl group, which may be the same or different from each other, and both Y and Z form a dioxane ring or a benzylidene group. , Or N-bromosuccinimide.

In the general formula (II), among the groups represented by Y and Z, the alkyl group is, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a butyl group, a pentyl group or a hexyl group. An alkyl group having 1 to 10 carbon atoms is preferable. Examples of the hydroxyalkyl group, acyloxyalkyl group, halogenated alkyl group and cyanoalkyl group include those in which one or more of a hydroxyl group, an acyloxy group, a halogen atom and a cyano group are introduced into the above alkyl group, respectively. Here, examples of the acyloxy group include an acetoxy group and a formyloxy group. Examples of the aralkyl group and halogenated aralkyl group include a benzyl group, a phenethyl group, a halogenobenzyl group, and a halogenophenethyl group. Further, the dioxane ring or benzylidene group formed by both Y and Z has a suitable substituent, for example, a lower alkyl group, a nitro group,
A halogen atom or the like may be introduced.

Examples of the compound represented by the general formula (II) include tribromonitromethane, 2,2-dibromo-2-nitroethanol, 1,2-dibromo-1-
Nitropropanol, 2,2-dibromo-3-nitrilopropionamide, 2-bromo-2-nitropropane-
1,3-diol, 1,1-dibromo-1-nitro-2
-Acetoxyethane, 1,1-dibromo-1-nitro-
2-acetoxypropane, 2-bromo-2-nitro-
1,3-diacetoxypropane, 1,2-dibromo-
2,4-dicyanobutane, 2-bromo-2-nitro-
1,3-Diformyloxypropane, 2,2-Dibromopropionnitrile, 2-Bromo-2-nitropropane, 5-Bromo-2-methyl-5-nitro-1,3-dioxane, 5-Bromo-5- Nitro-1,3-dioxane, β-bromo-β-nitrostyrene, β-bromo-4
-Chloro-β-nitrostyrene, β-bromo-β, p-
Dinitrostyrene, β-bromo-4-methyl-β-nitrostyrene, (1,2-dibromo-2-nitroethenyl) benzene, 1- (1,2-dibromo-2-nitroethenyl) -4-chlorobenzene, etc. .

In the present invention, as the bromine-containing organic compound as the component (C), one type of the compound represented by the general formula (II) may be used, or two or more types may be used in combination. N-bromosuccinimide may be used. Further, the compound 1 represented by the general formula (II)
One or more species and N-bromosuccinimide may be used in combination. Preferred components (C) include 5-bromo-5-nitro-1,3-dioxane, 2,2-dibromo-2-nitroethanol, 2-bromo-2-nitropropane-1,3-diol and 2, 2-dibromo-3-nitrilopropionamide can be mentioned, but among these, 5-
Bromo-5-nitro-1,3-dioxane is preferred.

In the harmful microbial eradication agent of the present invention, the content ratio of the component (B) and the component (C) is usually selected in the range of 100: 1 to 1: 100 by weight.
If the amount of component (B) is less than this range, a synergistic effect with the bromine-containing organic compound of component (C) cannot be expected, and if it is more than this range, the eradication agent causes aggregation and solidification, which is not preferable. From the viewpoint of exhibiting a good synergistic effect and effectively preventing aggregation and solidification, the content ratio of the component (B) and the component (C) is preferably in the range of 50: 1 to 1:50, particularly 10 A range of: 1 to 1:10 is preferred.

Further, in the harmful microorganism erasing agent of the present invention, in order to suppress the decrease in pH and prevent the occurrence of aggregation and solidification, the total content of the component (B) and the component (C) is , (A) based on the weight of the isothiazolone-based clathrate compound, it is preferably in the range of 0.5 to 10% by weight, and particularly preferably in the range of 1 to 6% by weight.

The harmful microorganism eradicating agent of the present invention may contain, if desired, other antibacterial agents, dispersants, diluents, and surfactants at the time of its preparation, as long as the object of the present invention is not impaired. , Thickener, specific gravity adjusting agent, defoaming agent, metal corrosion inhibitor,
A freezing point depressant and the like can be added.

The dispersants are used especially when preparing aqueous suspensions. Examples of the dispersant include alkyl sulfates, dialkyl sulfosuccinates, formalin condensates of naphthalene sulfonates, lignin sulfonates, anionic surfactants such as polycarboxylates, polyoxyethylene alkyl ethers, and polyoxyethylene alkyl ethers. Nonionic surfactants such as oxyethylene alkyl aryl ethers and polyoxyethylene polyoxypropylene block copolymers are used. Of these, formalin condensates of naphthalene sulfonates and lignin sulfonates are particularly preferable because they have excellent dispersibility. These dispersants are 1
Seeds may be used, or two or more types may be used in combination.

In this dispersant, the weight ratio of the isothiazolone clathrate compound (A) to the dispersant is 1:10 to 2.
It is advantageous to mix them in a ratio of 00: 1, preferably 1: 5 to 50: 1 because a good dispersion state can be obtained.

Examples of the thickener include carboxymethyl cellulose, polyvinylpyrrolidone, polyvinyl alcohol, sodium alginate, guar gum, xanthan gum, lanzan gum, sodium polyacrylate, polyacrylamide, methacrylate / diethylaminoethyl methacrylate copolymer, alkyl methacrylate / N-vinyl-2-pyrrolidone acrylate copolymer, alkyl methacrylate / polyethylene glycol methacrylate copolymer, dodecyl fumarate / diethylaminoethyl methacrylate copolymer, styrene /
Maleic acid copolymer, sodium montmorillonite,
Examples thereof include silica.

Further, the defoaming agent is mainly added to prevent bubbles during wet pulverization, and silicone type is useful. As the specific gravity adjusting agent, when the dispersion medium is water, a soluble compound such as urea can be added.

The amount of the harmful microbial eradication agent of the present invention to be added, which varies depending on the concentration of microorganisms, is generally about 0.01 to 100 ppm in terms of solid content in the case of a water system in the field of paper pulp and the like. In the case of water-based paints, pastes, leather, etc., the amount is about 1 to 500 ppm, and in this range, damages by harmful microorganisms can be effectively prevented.

On the other hand, according to the stabilizing method of the present invention, in the harmful microorganism eradicating agent containing the isothiazolone inclusion compound as an active ingredient, the weight ratio of hexamethylenetetramine and bromine-containing organic compound is from 100: 1 to 1:10.
By adding the mixture of 0 at a ratio of 0.01 to 10% by weight based on the weight of the isothiazolone inclusion compound, the storage stability of the harmful microbial eradication agent can be improved.

As the isothiazolone inclusion compound and the bromine-containing organic compound in this method, the same compounds as those used as the components (A) and (C) of the harmful microorganism eradicating agent can be mentioned. Further, in order to improve the storage stability, the ratio of hexamethylenetetramine and the bromine-containing organic compound used is preferably in the range of 50: 1 to 1:50 by weight, particularly 1
The range of 0: 1 to 1:10 is preferable, and the addition amount of the mixture of hexamethylenetetramine and the bromine-containing organic compound is 0.1 to 5% by weight based on the weight of the isothiazolone inclusion compound. Ranges are preferred.

Due to this stabilization, the harmful microorganism eradication agent containing the isothiazolone inclusion compound as an active ingredient is
Even during storage, there is almost no decrease in pH, aggregation and solidification are suppressed, and storage stability is excellent.

[0034]

The harmful microbial eradication agent of the present invention is capable of effectively preventing damages caused by harmful microorganisms such as bacteria, fungi, and algae, has excellent sustainability of the effect, and lowers the pH during storage. There is almost no occurrence, and aggregation and solidification are suppressed, and storage stability is excellent.

Further, according to the method of the present invention, a harmful microbial eradication agent containing an isothiazolone inclusion compound as an active ingredient can be stabilized extremely effectively.

[0036]

Next, 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 88.94 parts by weight of water, 40% by weight of 5-chloro-2-methyl-4-isothiazolin-3-one as a guest compound and 1,1,2,2-tetrakis (as a host compound) 8 parts by weight of an isothiazolone inclusion compound composed of 60% by weight of 4-hydroxyphenyl) ethane, 0.7 parts by weight of a mixture of xanthan gum and polyvinylpyrrolidone in a weight ratio of 1: 5, 1 part by weight of ligninsulfonic acid sodium salt and silicone A slurry was prepared by thoroughly mixing and stirring 1 part by weight of the system antifoaming agent.

Next, 0.06 part by weight of hexamethylenetetramine and 0.3 part by weight of 2,2-dibromo-2-nitroethanol were added to this slurry to prepare a harmful microorganism erasing agent.

About this product, immediately after preparation and after preparation 40
PH and anti-aggregation / coagulability at the time of storage for 1 week at 40 ° C. and storage at 40 ° C. for 2 weeks after preparation,
The storage stability was evaluated by measuring or judging by the method described below.

(1) pH: Determined using a pH meter manufactured by Horiba. (2) Anti-aggregation and coagulation: Slurry (harmful microbial eradication agent)
Was placed in a container with a lid, stored at 40 ° C., and after a lapse of a predetermined period of time, the state when the slurry was transferred from the container to a beaker was visually observed and judged according to the following criteria. ◯: Flows easily and solids such as lumps cannot be confirmed. B: Flows only when the container is shaken. Solids can be confirmed. X: It did not flow and solidified. Table 3 shows the results.

Examples 2 to 5 In Example 1, except that 2,1-dibromo-2-nitroethanol was used as the bromine compound instead of the compounds shown in Tables 1 and 2 in the amounts shown in Tables 1 and 2. Was prepared in the same manner as in Example 1, and the storage stability was evaluated. Table 3 shows the results. However, Example 4
The amount of water used was 89.04 parts by weight.

Comparative Example In Example 1, hexamethylenetetramine and 2,
A harmful microorganism eradication agent was prepared in the same manner as in Example 1 except that 2-dibromo-2-nitroethanol was not added and the amount of water used was 89.3 parts by weight, and the storage stability was evaluated. . Table 3 shows the results.

[0043]

[Table 1]

[0044]

[Table 2]

Note 1) isothiazolone inclusion compound: 40% by weight of 5-chloro-2-methyl-4-isothiazolin-3-one as a guest compound and 1,1,2,2-tetrakis (4) as a host compound. -Hydroxyphenyl) ethane 60% by weight

[0046]

[Table 3]

Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display area A01N 33:20 37:18 43:32)

Claims (6)

[Claims] 1. An (A) isothiazolone-based clathrate compound,
(B) Hexamethylenetetramine and (C) a bromine-containing organic compound, and an isothiazolone inclusion compound-containing harmful microorganism eradication agent. 2. The weight ratio of component (B) and component (C) is 1
The composition according to claim 1, which is contained in a ratio of 00: 1 to 1: 100.
A harmful microorganism eradicating agent containing the isothiazolone-based clathrate compound described. 3. The isothiazolone encapsulation according to claim 1, wherein the total content of the component (B) and the component (C) is in the range of 0.5 to 10% by weight based on the weight of the component (A). A harmful microbial eradication agent containing contact compounds. 4. The component (C) has the general formula: (In the formula, X is a nitro group or a cyano group, Y and Z are a bromine atom, a nitro group, a cyano group, a hydroxyl group,
Aminocarbonyl group, alkyl group, hydroxyalkyl group, acyloxyalkyl group, halogenated alkyl group,
A cyanoalkyl group, an aralkyl group or a halogenated aralkyl group, which may be the same or different from each other, and both Y and Z form a dioxane ring or a benzylidene group. 4. The isothiazolone clathrate-containing harmful microorganism eradicating agent according to claim 1, 2 or 3, which is at least one selected from the group consisting of the compound represented by (4) and N-bromosuccinimide. 5. A harmful microbial eradication agent containing an isothiazolone inclusion compound as an active ingredient, wherein a weight ratio of hexamethylenetetramine to a bromine-containing organic compound is 10
A stabilizing method, characterized in that a mixture of 0: 1 to 1: 100 is added in a proportion of 0.01 to 10% by weight based on the weight of the isothiazolone inclusion compound. 6. The bromine-containing organic compound has the general formula: (In the formula, X is a nitro group or a cyano group, Y and Z are a bromine atom, a nitro group, a cyano group, a hydroxyl group,
Aminocarbonyl group, alkyl group, hydroxyalkyl group, acyloxyalkyl group, halogenated alkyl group,
A cyanoalkyl group, an aralkyl group or a halogenated aralkyl group, which may be the same or different from each other, and both Y and Z form a dioxane ring or a benzylidene group. 6. The stabilization method according to claim 5, wherein the stabilization method is at least one selected from the group consisting of compounds represented by the formula) and N-bromosuccinimide.