JPH11171712A - Isothiazolone preparation and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject preparation excellent in stability of the product and scarcely having influence upon environment without using a metal salt and an organic solvent by including a specific compound, water or buffer aqueous solution, a specific derivative and a surfactant. SOLUTION: This preparation comprises (A) 0.5-40 wt.% isothiazolone compound (mixture) of formula I (X and Y are each H or a halogen; R is a 1-8C alkyl which may be straight chain or branched chain (e.g. 2-methylisothiazolin-3- one), (B) water or buffer aqueous solution in an amount enough to at least dissolve the component A, (C) 0.1-5 wt.% one or more kinds of 5-bromo-5- nitro-1,3-dioxane derivative of formula II (R1 and R2 are each H or a 1-5C lower alkyl) (e.g. 5-bromo-2-methyl-5-nitro-1,3-dioxane) and (D) a surfactant, preferably an anionic or nonionic surfactant in an amount enough to dissolve the component C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an isothiazolone preparation and a method for producing the same, and more particularly, to stabilization in water without containing a metal salt such as magnesium ion or calcium ion or an organic solvent which causes latex emulsion shock. Is an improvement.

[0002]

2. Description of the Related Art Conventionally, many compounds have been used as industrial fungicides. Among them, those having advantages such as a relatively simple treatment method and an excellent effect per cost include 5-chloro-2-methylisothiazolin-3-one and 2-methylisothiazoline-3. −
And other isothiazolone compounds. This isothiazolone compound is widely known as an industrial bactericide, preservative, and fungicide, particularly a slime control agent for paper pulp, a bactericidal agent for water treatment, a fungicide, a preservative for cutting oil, and a paint. It is useful and widely used as a fungicide, natural rubber latex, synthetic rubber latex, acrylic emulsion, vinyl acetate emulsion, and a preservative and fungicide for these polymer aqueous dispersions.

The isothiazolone compound is usually used as a liquid preparation because it can be easily added to a target system. However, it is known that isothiazolone compounds are very unstable in water and easily decompose in water.

Accordingly, a method for stabilizing an isothiazolone compound by dissolving it in water or a water-soluble solvent together with a magnesium salt, a calcium salt, or the like has been found and has been distributed on the market for many years.

However, when the above-mentioned preparation is used as a preservative or fungicide in latex emulsions and various resin emulsion phases which are part of the intended use, the emulsion phase is formed due to the presence of metal salts such as magnesium salts and calcium salts. There was a problem (so-called emulsion shock) that was broken and phase separation and solidification occurred.

As one method of stabilizing an isothiazolone compound of the type that does not cause such emulsion shock, a method of dissolving the compound in a hydrophilic organic solvent and preparing it has been invented and put to practical use.

However, in recent years, it remains in the final product,
Alternatively, the impact of volatile organic solvents on humans and the environment in manufacturing and formulation operations has been recognized, for example, Euro
It is also featured in pean Chemical News (Vol. 66, No. 1740, 11-17). Therefore, there is a need for a formulation that takes this point into account. So-called VOC (volatile organi)
c compound) This is a countermeasure problem.

[0008] In other words, the development of a stable isothiazolone preparation that does not cause so-called emulsion shock and is also taking measures against VOC has been a new subject.

In order to solve the above problems, there has been proposed a method for stabilizing an isothiazolone compound in water by adding a large amount of an anionic and nonionic surfactant to an aqueous solution of a metal salt-free isothiazolone compound. (JP-A-60-96652), but the stability of the preparation originally intended is not sufficient.

On the other hand, several methods using various organic compounds as stabilizers have been disclosed. For example, a method using a cyclic ester (JP-A-6-87705), a method using an orthoester (US Pat. No. 4,906,274), a method using hexamethylenetetramine (US Pat. No. 5,242,893), and the like are proposed. And still have the problem of the preparation containing an organic solvent described above.

Recently, as another stabilizer, a method for stabilizing an isothiazolone compound by combining 5-bromo-5-nitro-1,3-dioxane with hexamethylenetetramine as a second component has been disclosed. (EP
686347) Although this method has also achieved the purpose of stabilization, the use of a mixed solvent of dipropylene glycol and water as a solvent cannot avoid the use of an organic solvent.

On the other hand, as an example in which an organic solvent is not used, a 5-bromo-5-nitro-1,3-dioxane derivative or the like and an amide or potassium hydrogen phthalate are used.
A method for stabilizing an isothiazolone compound in water or a mixed solvent of water and an organic solvent soluble in water has been proposed.
According to this method, storage stability at 50 ° C. for 60 days is exhibited, and from the viewpoint of stability, this method is sufficiently practical.

However, 5-bromo-5-nitro-
In the case where a 1,3-dioxane derivative is used, there is no description of an example in which stabilization was performed using only water.

A method of stabilization in water using only 5-bromo-5-nitro-1,3-dioxane (JP-A-4-9
No. 305) has also been proposed, but there is no description of an example using no organic solvent.

[0015]

As described above, although various methods for stabilizing isothiazolone compounds have been proposed, metal salts such as magnesium ion and calcium ion and organic solvents which cause emulsion shock are used. A method for stabilizing an isothiazolone compound in water in a wide concentration range without using it has not been completed.

The present invention has been made under such circumstances, and has been used to convert an isothiazolone compound into a metal salt such as magnesium ion or calcium ion or an organic solvent which causes latex emulsion shock in a wide concentration range which has not been achieved so far. An object of the present invention is to provide an isothiazolone preparation which is excellent in product stability over a long period of time and has little effect on the environment, without using the compound.

Another object of the present invention is to provide a method for producing this isothiazolone preparation.

[0018]

Means for Solving the Problems From the above-mentioned viewpoints, the present inventors have conducted intensive studies and as a result, have found that aqueous solutions of unstable isothiazolone compounds can be treated with 5-bromo-5-nitro-1,3
-By adding a dioxane derivative and a surfactant in an amount small enough to solubilize or disperse the same in a solution, stability without practical problems is obtained without substantially using an organic solvent. I have found the facts that can be obtained.

The organic solvent is a liquid organic compound used when a solute is dissolved to form a solution. In the present invention, acetic acid may be used to prepare a buffered aqueous solution, but it does not correspond to an organic solvent because the amount of addition is extremely small. Also stabilizers,
The same applies to the surfactant. Therefore, in the present invention, although the preparation contains an organic compound, it can be said that substantially no organic solvent is used.

Thus, the isothiazolone preparation according to the present invention comprises (A) the general formula (1)

[0021]

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(Where X and Y in the formula are the same or different and each represent a hydrogen atom or a halogen atom, R represents an alkyl group having 1 to 8 carbon atoms, and the alkyl group may be linear or branched. Good)) or an isothiazolone compound represented by the formula
(B) water or a buffered aqueous solution in an amount sufficient to at least dissolve the compound of the above general formula (1), and (C) the following general formula (2) blended as a stabilizing component:

[0023]

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(Wherein R ₁ and R ₂ are the same or different and represent a hydrogen atom or a lower alkyl group having 1 to 5 carbon atoms).
At least one of 1,3-dioxane derivatives, and
(D) a surfactant in an amount sufficient to dissolve the dioxane derivative, which is characterized by comprising four components.

The substituents X and Y of the isothiazolone compound of the formula (1) used in the present invention are the same or different and represent a hydrogen atom or a halogen atom. Examples of the halogen atom include a chlorine atom, a bromine atom and an iodine atom, and a chlorine atom is preferable. R represents an alkyl group having 1 to 8 carbon atoms, which may be linear or branched. Further, a mixture irrespective of these ratios may be used.

Specific examples of the isothiazolone compounds of the formula (1) include 5-chloro-2-methylisothiazolin-3-one, 2-methylisothiazolin-3-one,
2-n-octylisothiazolin-3-one, 4,5-
Dichloro-2-n-octylisothiazolin-3-one, 2-ethylisothiazolin-3-one and 5-chloro-2-ethylisothiazolin-3-one; and preferably 5-chloro-2-methylisothiazoline-3. −
On, 2-methylisothiazolin-3-one, 2-n-
Octylisothiazolin-3-one and 4,5-dichloro-2-n-octylisothiazolin-3-one; and more preferably, 2-methylisothiazolin-3-one.
On, 5-chloro-2-methylisothiazolin-3-one. These isothiazolone compounds may be used as a mixture in any ratio. These isothiazolone compounds are described, for example, in G. A. It can be synthesized according to the method of Miller et al. (J. Heterocyclic Chem., 8, 581-586 (1971)).

In the present invention, the 5-bromo-5-nitro-1,3-dioxane derivative of the formula (2) is used as a stabilizer (C) for a preparation. In this compound (2), R ₁ and R ₂ are the same or different and represent a hydrogen atom or a lower alkyl group. The lower alkyl group refers to an alkyl group having 1 to 5 carbon atoms, which may be linear or branched, such as methyl, ethyl, normal propyl, isopropyl, normal butyl, isobutyl, and tertiary butyl. And a normal pentyl group.

Specific examples of the compound of the above formula (2) include 5-bromo-5-nitro-1,3-dioxane,
Bromo-2-methyl-5-nitro-1,3-dioxane, 5-bromo-2,2-dimethyl-5-nitro-1,
3-dioxane, 5-bromo-2-ethyl-5-nitro-1,3-dioxane, 5-bromo-5-nitro-2-
Normal propyl-1,3-dioxane, 5-bromo-
2,2-diethyl-5-nitro-1,3-dioxane,
5-bromo-2-ethyl-2-methyl-5-nitro-
1,3-dioxane and the like. These may be used alone or in combination of two or more.

These compounds have the formula (3)

[0030]

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2-bromo-2-nitro-1, represented by the formula:
3-propanediol and general formula (4)

[0032]

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(Wherein R ₁ and R ₂ have the same meanings as in the above formula (2)). Method (J. Soc.
According to Cosmet. Chem., 35, 73-93 (1984)), it can be easily obtained both in the laboratory and industrially.

Among the thus obtained stabilizers, 5-bromo-5 is preferred from the viewpoint of solubility in aqueous solution and economy.
-Nitro-1,3-dioxane, 5-bromo-2-methyl-5-nitro-1,3-dioxane are particularly preferred.
These compounds are known to be bactericidal but have very little irritation to the human body and the environment, and also meet the purpose of the present invention.

Further, in the present invention, a surfactant is used for solubilizing or dispersing the stabilizing component (C) which is hardly soluble in the aqueous solution of the isothiazolone compound to obtain a predetermined concentration of the stabilizing agent in the preparation. As the surfactant, anionic, cationic, or nonionic surfactants can be used, and among them, anionic or nonionic surfactants are preferable in terms of economy and stability of the preparation.
As anionic surfactants, alkylbenzene sulfonic acid and salts thereof, alkyl (phenyl) ether sulfate, α-olefin sulfonate, and the like can be used. As nonionic surfactants, higher alcohol surfactants, alkyl phenol surfactants Surfactants can be used. Particularly, sodium tetradecenesulfonic acid salt is preferred from the viewpoint of the stability of the preparation. The surfactant is also used as a raw material for cosmetics, and is a surfactant that is less irritating to the human body.

In the isothiazolone preparation provided by the present invention, in addition to water, a buffer aqueous solution in an amount necessary for maintaining the liquid property at pH 2 to 6 can be used.

The stability of the isothiazolone compound is also affected by the pH. At a pH of 2 or less, the stability becomes very poor and decomposition proceeds. When the isothiazolone compound is decomposed, hydrochloric acid is generated.
Decomposition is further accelerated below.

The isothiazolone compound is stable in the present preparation using water, but a decrease in pH cannot be avoided. The present inventors have found that the use of various buffered aqueous solutions alleviates a decrease in pH as compared with in water and improves the stability of the isothiazolone preparation.

The kind of the buffer aqueous solution used here is acetic acid.
Sodium acetate, phthalic acid / potassium hydrogen phthalate, phosphoric acid / sodium phosphate, and the like can be used. In particular, an aqueous solution of acetic acid / sodium acetate buffer is most preferable from the viewpoint of the stability of the preparation and economy.

The concentration of the aqueous buffer solution may be an amount sufficient to maintain the pH within a predetermined range. Specifically, 0.1
N to 2.0N is preferred. When the concentration is higher than this, not only is there no economic merit but also the stability of the preparation may be impaired.

The preparation of the present invention is prepared by diluting the isothiazolone compound represented by the formula (1) with water or a buffered aqueous solution so as to obtain a desired concentration, and preparing this aqueous solution. It can be prepared by adding a surfactant (D) in an amount sufficient to solubilize (C) and its stabilizing component in a solution. When the stabilizing component (C) is hardly soluble, the stabilizing component (C) can be solubilized by heating for a short time without impairing the stability of the preparation.

The compounding amount of the compound of the general formula (1) in the preparation of the present invention is preferably 0.5 to 40% by weight from the viewpoint of storage stability, preferably 0.5 to 30% by weight, more preferably 1 to 40% by weight. It is particularly preferable that the content be 20% by weight or less from the viewpoints of economic advantages in storage and transportation and storage stability.

The amount of the 5-bromo-5-nitro-1,3-dioxane derivative represented by the general formula (2) as the stabilizing component (C) is 0.1 to 5% by weight of the preparation in storage stability. The amount is preferably 0.5 to 2% by weight from the viewpoint of stabilizing effect and economical aspect.

When both the stabilizing component (C) and the surfactant (D) are contained, the preparation can be stably maintained for a longer period of time than when only the stabilizing component (C) (dioxane derivative) is used. When the surfactant (D) is not added, the stabilizing component (C) is difficult to dissolve or disperse in the aqueous solution of isothiazolone, and it is difficult to add a predetermined concentration. In addition, it has been confirmed that the surfactant (D) alone cannot stabilize the aqueous solution presented in the present invention in a predetermined concentration range so as to be practically usable. Therefore, the remarkable stabilizing effect of the preparation presented by the present invention is due to the combined use of the stabilizing component (C) and the surfactant (D).

[0045]

EFFECT OF THE INVENTION The preparation of the present invention does not contain metal salts such as calcium salts and magnesium salts which have been conventionally used for stabilizing isothiazolone compounds in an aqueous solution, and contains substantially an organic solvent. And has excellent formulation stability. In addition, since the present formulation substantially imparts stability without using an organic solvent, there is little environmental pollution and adverse effects on the human body due to the organic solvent. Further, it is economically inexpensive and has excellent characteristics as a preparation.

[0046]

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

(A) Preparation of Formulation (1): A bactericidal composition corresponding to Examples 1 to 6 was prepared. One example of the preparation method is shown below.

Hereinafter, 2-methylisothiazoline-
3-one is referred to as MT, and 5-chloro-2-methylisothiazolin-3-one is referred to as CMT.

Stabilizer, 5-bromo-2-methyl-5
1.00 g of nitro-1,3-dioxane and a surfactant,
2.00 g of Triton X was placed in the container. Separately, 550.0 g of a buffer solution obtained by mixing a 0.2N aqueous acetic acid solution and a 0.2N aqueous sodium acetate solution in a volume ratio of 4: 1 was mixed with 9 MT CMT.
89.57 g of a mixture of two kinds of isothiazolone compounds consisting of 1.53% by weight and MT of 8.47% by weight was added to prepare an aqueous solution of isothiazolone. 100.03 g of this aqueous solution was added to the above-mentioned container, and the mixture was stirred until it became uniform, whereby Preparation 1 was prepared. Similarly, Formulations 2 to 6 were prepared as shown in Table 1.

[0050]

[Table 1]

Numerical values are all percentages by weight.

The stabilizer (1) is 5-bromo-5-nitro-1,3-dioxane, and (2) is 5-bromo-2-
Shows methyl-5-nitro-1,3-dioxane.

In Examples 1 to 6, the surfactant was UCC
As a buffer aqueous solution, a solution of 0.2N acetic acid aqueous solution and 0.2N sodium acetate aqueous solution mixed at a volume ratio of 4: 1 to pH 4.1 was used.

(B) Result of thermal stability test of preparation (1);
Examples 7 to 12 The six preparations prepared in (A) were left in a thermostat at 55 ° C., and the content of the isothiazolone compound was analyzed at regular intervals by using high performance liquid chromatography. The results are shown in Table 2.

[0055]

[Table 2]

Numerical values indicate the residual ratio (%) determined from the results of analysis using high performance liquid chromatography.

The upper row shows the CMT residual ratio, the middle row shows the MT residual rate, and the lower row shows the appearance observed visually.

As is evident from Table 2, the residual amount of isothiazolone in the preparation and the appearance of the aqueous solution are correlated. This preparation was colorless and transparent at the time of preparation, but gradually turned yellow when heated. At that time, isothiazolone is 95%
The above remained. Thereafter, the color gradually increased in color, and at a certain point, a large amount of precipitate was generated. At this time, the isothiazolone remaining in the solution portion was 40% or less, and it was determined that the isothiazolone was decomposed at this time.

(C) Preparation of Formulation (2); Examples 13 to 1
Eight corresponding germicidal compositions were prepared.

[0060]

[Table 3]

The isothiazolone compounds include CMT, 9
Using a mixture of 1.5% by weight, MT and 8.5% by weight, the concentration in the preparation was adjusted to 11.6% by weight and 1.1% by weight, respectively.

The concentration of all stabilizers was 1.0% by weight, and the surfactant used was Triton X-100 manufactured by UCC.
The concentration was 2.0% by weight.

(1) 5-bromo-5-nitro-1,3-dioxane, (2) 5-bromo-2-
Methyl-5-nitro-1,3-dioxane.

The buffer aqueous solution is 0.2M acetic acid aqueous solution and 0.1M aqueous solution.
2M sodium acetate aqueous solution was mixed at a volume ratio of 4: 1
H4.1 was used.

In Example 17, 4.6% by weight of sodium chloride was added.

In Example 18, Formulation 11 of Example 17 was diluted 100-fold with water.

(D) Coagulation test: Examples 19 to 24 Using the preparations 7 to 12 shown in Table 3, an emulsion shock test was performed on the synthetic polymer aqueous dispersion styrene-butadiene polymer latex.

The test was carried out as follows. Synthetic polymer aqueous dispersion styrene butadiene polymer latex, about 5
of the formulation shown in Table 3
5 drops and stirred well with a spoon. As a comparative example, Zonen C manufactured by Ichikawa Gosei Chemical Co., Ltd. was similarly tested.

[0069]

[Table 4]

In this table, ○ indicates that no aggregation occurred, X indicates that a small amount of aggregation occurred, and XX
Indicates that the particles aggregated violently.

Zonene C, shown as a comparative example, is widely used as a bactericide but contains a magnesium salt for stabilizing isothiazolone. Normally, it is used after being diluted to a concentration of several hundred ppm, but in this comparative example, the stock solution was used as it was. The result was that flocculation occurred in all dispersions. In contrast, this formulation did not cause any aggregation even when a buffer solution was used as in Examples 19 to 22.

In Example 23, to examine the effect of the addition of sodium chloride, the composition 7 was tested with a composition in which 4.6% by weight of a salt was added. Adding salt will result in mixed results, SB
A small amount of aggregation occurred at 1341 and NBR1561. However, no aggregation was observed in the composition of Example 24 using Formulation 12, which was diluted 100-fold to a practical concentration. It is clear that the addition of salt has no practical problem.

(E) Preparation of Formulation (3); Examples 25 to 5
4 Preparations 13 to 42 shown in Table 5 were prepared.

AI in Table 5 represents the total concentration of 5-chloro-2-methylisothiazolin-3-one (CMT) and 2-methylisothiazolin-3-one (MT), and CMT: MT Is 9: 1. A thermal stability test at 55 ° C. was performed using this formulation.

[0075]

[Table 5]

The type of the stabilizer is (1) is 5-bromo-5
-Nitro-1,3-dioxane, (2) being 5-bromo-
2-methyl-5-nitro-1,3-dioxane, (3)
Is 5-bromo-2,2-dimethyl-5-nitro-1,3
-Stands for dioxane, the concentration is% by weight.

The types of surfactants are as follows: A is Triton X-100 manufactured by UCC, and B is Lipolan LB-44 manufactured by Lion.
0 and all others use Lion surfactants. Concentrations are% by weight.

The solvent is (A) 0.2M, (b) 2
M, (c) is an aqueous solution of acetic acid / sodium acetate of 0.02M, and (d) is 0.2M potassium hydrogen phosphate and 0.2M.
Caustic soda aqueous solution is mixed at a volume ratio of 20: 1.

(F) Result of thermal stability test of preparation (2);
Examples 55 to 84

[0080]

[Table 6]

The evaluation of the stability of the aqueous isothiazolone preparation of the present invention was visually confirmed in the same manner as in the heat stability test result (1) of the preparation (B). That is,
は indicates that the aqueous isothiazolone aqueous preparation was colorless and transparent to pale yellow and transparent, △ indicates that a very small amount of turbidity occurred, and x indicates that a large amount of precipitation occurred and the isothiazolone was considered to be completely decomposed.

(G) Preparation of Formulation (4); Examples 85-9
2 Preparations 43 to 50 shown in Table 7 were prepared.

Note that AI in Table 7 has the same meaning as in the previous table. A thermal stability test at 55 ° C. was performed using this formulation.

[0084]

[Table 7]

The stabilizers are all 5-bromo-2 of (2)
-Methyl-5-nitro-1,3-dioxane was used.

All figures in the table are% by weight.

-Lipolan LB-440 is a surfactant from Lion Corporation.

(H) Result of thermal stability test of preparation (3);
Examples 93 to 100

[0089]

[Table 8]

The meanings of ○, Δ, and × in the table are the same as in Table 6 above.

(I) Preparation of Formulation (5);
102

[0092]

[Table 9]

CMT, 7 in the isothiazolone compound
Using a mixture of 8.5% by weight, MT, 21.5% by weight,
The concentrations in the preparation were 11.0% by weight and 3.0% by weight, respectively.
And a thermal stability test at 55 ° C. was performed using this formulation. The AI in Table 9 is CMT and M
The total concentration with T is shown.

(1) 5-bromo-5-nitro-1,3-dioxane, (2) 5-bromo-2-stabilizer
Shows methyl-5-nitro-1,3-dioxane. Each concentration is 1.0% by weight in the preparation.

The surfactant is Lion Corporation's Lipolan LB
-440 was used.

All contain 6.3% by weight of salt in the preparation.

(J) Result of thermal stability test of preparation (4);
Examples 103 and 104

[0098]

[Table 10]

In the table, ○, Δ, and × have the same meanings as in Table 6 above.

(K) Preparation of Formulation (6);
106

[0101]

[Table 11]

The isothiazolone compounds include CMT, 9
A mixture of 1.5% by weight, MT, 8.5% by weight was used.
Note that AI in Table 11 indicates the total concentration of CMT and MT. A thermal stability test at 55 ° C. was performed using this formulation.

(L) Result of thermal stability test of preparation (5);
Examples 107 and 108

[0104]

[Table 12]

In the table, ○, Δ, and X have the same meanings as in Table 6 above.

(M) Preparation of Formulation (7);
115

[0107]

[Table 13]

The isothiazolone compounds include CMT, 9
A mixture of 1.5% by weight, MT, 8.5% by weight was used.
It should be noted that AI in Table 13 indicates the total concentration of CMT and MT. A thermal stability test at 55 ° C. was performed using this formulation.

(N) Result of thermal stability test of preparation (5);
Examples 116 to 122

[0110]

[Table 14]

○, ○, and × in the table have the same meanings as in Table 6 above.

(P) Comparative Examples; Comparative Examples 2 to 6 As comparative examples, the compositions shown in Table 15 below were prepared and subjected to a stability test at 55 ° C. The results are shown in Table 16.

[0113]

[Table 15]

[0114]

[Table 16]

In the table, ○, Δ, and × have the same meanings as in Table 6 above.

────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI A01N 43/32 A01N 43/32 C07D 275/03 C07D 319/06 319/06 275/02 (72) Inventor Masayuki Morita Iwaki, Fukushima 1-133 Shimokawa-shi, Ishiizumi-cho Ichikawa Gosei Chemical Co., Ltd. (72) Inventor Kazuyoshi Tsuchiya 1-133 Shimokawa-shi, Iwaki-shi, Iwaki-shi

Claims (18)

[Claims] 1. A compound of the general formula (1) (However, X and Y in the formula are the same or different and represent hydrogen or a halogen atom, R represents an alkyl group having 1 to 8 carbon atoms, and the alkyl group may be linear or branched.) And an isothiazolone compound represented by the general formula (2) (Wherein R ₁ and R ₂ in the formula are the same or different and each represent a hydrogen atom or a lower alkyl group having 1 to 5 carbon atoms) of a 5-bromo-5-nitro-1,3-dioxane derivative represented by An isothiazolone preparation comprising at least one kind, a surfactant necessary for dissolving or dispersing the dioxane derivative, and water or a buffered aqueous solution, and containing substantially no organic solvent. 2. The isothiazolone compound of the general formula (1), wherein R is a methyl group, X is a hydrogen atom, and Y is a chlorine atom, or 5-chloro-2-methylisothiazolin-3-one or R is methyl. Group wherein X and Y are hydrogen atoms
2. The isothiazolone preparation according to claim 1, which is -methylisothiazolin-3-one or a mixture of any kind thereof. 3. The method according to claim 1, wherein the dioxane derivative is contained in an amount of 0.1 to 10.
The isothiazolone preparation according to claim 1, which is contained in an amount of 1 to 5% by weight. 4. The isothiazolone preparation according to claim 1, wherein the surfactant is an anionic surfactant or a nonionic surfactant. 5. The isothiazolone preparation according to claim 1, further comprising an aqueous buffer solution in an amount necessary to maintain the pH of the solution at pH 2 to 6. 6. The isothiazolone preparation according to claim 5, wherein the buffer aqueous solution is an acetic acid / sodium acetate aqueous solution. 7. The preparation according to claim 1, wherein the isothiazolone compound of the general formula (1) is contained in the preparation in an amount of 0.5 to 40% by weight.
7. The isothiazolone preparation according to any one of claims 6 to 6. 8. The isothiazolone preparation according to claim 1, wherein the dioxane derivative of the general formula (2) is 5-bromo-2-methyl-5-nitro-1,3-dioxane. 9. The isothiazolone preparation according to claim 1, wherein the dioxane derivative of the general formula (2) is 5-bromo-5-nitro-1,3-dioxane. 10. The general formula (1) (However, X and Y in the formula are the same or different and represent hydrogen or a halogen atom, R represents an alkyl group having 1 to 8 carbon atoms, and the alkyl group may be linear or branched.) And an isothiazolone compound represented by the formula (I) or a mixture thereof in any ratio, and a compound represented by the general formula (2): (Wherein R ₁ and R ₂ in the formula are the same or different and each represent a hydrogen atom or a lower alkyl group having 1 to 5 carbon atoms) of a 5-bromo-5-nitro-1,3-dioxane derivative represented by A method for producing an isothiazolone preparation, comprising dissolving at least one kind and a surfactant necessary for dissolving or dispersing the dioxane derivative in water or a buffered aqueous solution. 11. The isothiazolone compound of the general formula (1), wherein R is a methyl group, X is a hydrogen atom, Y is a chlorine atom, or 5-chloro-2-methylisothiazolin-3-one or R is methyl. Group wherein X and Y are hydrogen atoms
The method for producing an isothiazolone preparation according to claim 10, which is -methylisothiazolin-3-one or a mixture of any kind thereof. 12. The amount of the dioxane derivative of the general formula (2) dissolved in water or an aqueous buffer solution is 0.1 to 5% by weight of the isothiazolone preparation to be produced. A method for producing an isothiazolone preparation. 13. The method for producing an isothiazolone preparation according to claim 10, wherein an anionic surfactant or a nonionic surfactant is used as the surfactant. 14. The method according to claim 10, wherein an amount of a buffered aqueous solution necessary for maintaining the pH of the solution at pH 2 to 6 is used.
14. The method for producing an isothiazolone preparation according to any one of claims 13 to 13. 15. The method for producing an isothiazolone preparation according to claim 14, wherein an acetic acid / sodium acetate aqueous solution is used as the buffer aqueous solution. 16. The method according to claim 10, wherein the amount of the isothiazolone compound represented by the general formula (1), which is dissolved in the water or the aqueous buffer solution, is 0.5 to 40% by weight of the isothiazolone preparation to be produced. A method for producing an isothiazolone preparation. 17. The isothiazolone preparation according to claim 10, wherein the dioxane derivative of the general formula (2) is 5-bromo-2-methyl-5-nitro-1,3-dioxane. Production method. 18. The method for producing an isothiazolone preparation according to claim 10, wherein the dioxane derivative of the general formula (2) is 5-bromo-5-nitro-1,3-dioxane.