JPH07196409A - Stabilized antimicrobial agent composition - Google Patents

Abstract

PURPOSE:To obtain a composition by combining a nitrilopropionamide compound which is an antimicrobial agent with a triol-based compound, further an isothiazolone compound or, as desired, adding a glycolic compound to the resultant combination. CONSTITUTION:This stabilized antimicrobial agent composition is obtained by combining a nitrilopropionamide compound expressed by formula I (R<1> is a halogen; R<2> is H or a halogen; R<3> is H or an alkyl) with a triol-based compound expressed by formula II (R<4> is H or an alkyl; R<5> is OH or methylol) or, as desired, further adding a glycolic compound thereto. Furthermore, the stabilized antimicrobial composition is prepared by combining the nitrilopropionamide compound expressed by formula I with an isothiazolone- based compound expressed by formula III (R<6> is H or a hydrocarbon; R<7> and R<8> each is H or a halogen) and the triol-based compound expressed by formula II or, as desired, further comprising the glycolic compound therein. Glycerol, trimethylolpropane and 1,1,1-tris(hydroxymethyl)ethane are preferred as the triol-based compound expressed by formula II.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fungicide composition comprising a nitrilopropionamide compound or an isothiazolone compound and a triol compound or, if necessary, a glycol compound, which is stabilized.

[0002]

2. Description of the Related Art Conventionally, general formula

[Chemical 11] It is known that a nitrilopropionamide compound represented by the formula (R ¹ is a halogen atom, R ² is a hydrogen atom or a halogen atom, and R ³ is a hydrogen atom or an alkyl group) is effective as an antimicrobial agent. There is
No. 0386). Furthermore, the general formula

[Chemical 12] (In the formula, R ⁶ is a hydrogen atom or a hydrocarbon group, R ⁷ and R ⁸ are a hydrogen atom or a halogen atom, and these may be the same or different from each other). There has been proposed a bactericide which utilizes an isothiazolone compound used in combination with the component (A) and utilizes its synergistic effect (JP-A-3-184904).

Each of these active ingredients is used in various industrial systems such as water systems in the pulp and paper industry, for example, so-called white water discharged from the paper making process and circulating cooling water in various industrial fields. Aqueous paint, paper coating liquid, latex, polymer emulsion, prepared by
It has a wide range of application as a metalworking oil such as cutting oil, leather, textile paste, adhesives, and other antibacterial / bactericidal agents, and exhibits excellent antibacterial / bactericidal effects.

However, in order to use these compounds alone or in combination of two or more as a bacteriostatic agent, it is required that they are stable agents during production, storage and use, but often the quality is high. In some cases, it may not be possible to exert sufficient antibacterial / bactericidal action during use due to changes, especially due to remarkable decomposition of the active ingredient.

Therefore, many years of research have been conducted on a method for stabilizing a fungicide composition containing a nitrilopropionamide compound alone or a combination of this compound and an isothiazolone compound. For example, a method of incorporating a nitrilopropionamide compound into a liquid such as polyethylene glycol or its mono- or dimethyl, ethyl, n-propyl or n-butyl ethers (Japanese Patent Publication No. 53-53).
No. 75), a method of dissolving a nitrilopropionamide compound in a liquid in which ethylene glycol and water are mixed in a ratio of 1: 1/7 to 5 (Japanese Patent Publication No. 5-59881), and a 3-isothiazolone compound is added to dibromonitrilo. There is a method of stabilizing with propionamide, ethylene glycol and water (JP-A-3-176407).

[0006] However, in the above method, when a composition containing a nitrilopropionamide compound is produced, contact with a metal is unavoidable. For example, when a stainless steel filter is used in the production process, the active ingredient is produced during production. Decomposes significantly and it is not possible to obtain the desired quality liquid composition. Further, when using this composition, for example, a cooling water circulation step, a metal working oil agent, when contact with a metal occurs even at a low concentration such as a metal can-containing waterborne coating, the effect of decomposing the nitrilopropionamide compound is high. Corrosion of the metal surface occurs as the durability decreases.

Further, in the above method, when the content of the nitrilopropionamide compound is less than 5% by weight or 26% by weight or more, a composition containing this compound as an active ingredient does not have sufficiently satisfactory stability. .

In the method (1), although the isothiazolone compound is stabilized, there is no suggestion about the stability of dibromonitrilopropionamide, which is an active ingredient of the antibacterial agent.

[0009]

Under the circumstances, the present invention has been made for the purpose of providing a stabilized antibacterial agent composition having improved stability of the active ingredient of the antibacterial agent. is there.

[0010]

Means for Solving the Problems As a result of various studies to develop a bactericidal composition having improved stability, the present inventors have found that a composition containing a nitrilopropionamide compound or an isothiazolone compound and the same. It was found that the objective can be achieved by adding a triol-based compound and a glycol-based compound used as desired to the above, and the present invention has been completed based on this finding.

That is, the present invention provides (A) general formula (I)

[Chemical 13] (Wherein R ¹ represents a halogen atom, R ² represents a hydrogen atom or a halogen atom, and R ³ represents a hydrogen atom or an alkyl group), and (B) the general formula (II)

[Chemical 14] (Wherein R ⁴ represents a hydrogen atom or an alkyl group, and R ⁵ represents a hydroxyl group or a methylol group), or a (A) nitrilopropionamide compound of the general formula (I) Or (B) a triol compound of general formula (II) and (C) a glycol compound, or (A) a nitrilopropionamide compound of general formula (I), and (D) a general formula of (III)

[Chemical 15] (In the formula, R ⁶ is a hydrogen atom or a hydrocarbon group, R ⁷ and R ⁸ are a hydrogen atom or a halogen atom, and these may be the same or different from each other). And an isothiazolone compound represented by the general formula (I)
I) a triol-based compound, or (A) a nitrilopropionamide compound of the general formula (I), (D) an isothiazolone-based compound of the general formula (III), and (B) a general formula ( II) a triol compound,
The present invention provides a stabilized antibacterial agent composition containing (C) a glycol compound.

The nitrilopropionamide compound used as the component (A) of the present invention is represented by the general formula (I):
Examples of the halogen atom of R ¹ and R ^{2 in} this formula include Cl and Br, and examples of the alkyl group of R ³ include a methyl group, an ethyl group, a propyl group and a butyl group. , Especially when both R ¹ and R ² are Br
2,2-dibromo-3-nitrilopropionamide is preferable because it has excellent bactericidal activity. In addition, examples of the nitrilopropionamide compound of the general formula (I) include 2-chloro-3-nitrilopropionamide, 2-bromo-3-nitrilopropionamide, 2,
Examples thereof include 2-dichloro-3-nitrilopropionamide and N-methyl-2,2-dibromo-3-nitrilopropionamide. These may be used alone,
Moreover, you may use it in combination of 2 or more type.

Next, the triol compound used as the component (B) of the present invention is represented by the general formula (II), and the alkyl group of R ^{4 in} this formula is, for example, a methyl group, an ethyl group, Examples include propyl group and butyl group,
In particular, glycerin in which R ⁴ is a hydrogen atom and R ⁵ is a hydroxyl group is preferable because it has good compatibility with the preparation and excellent stability of the active ingredient. In addition, examples of the compound represented by the general formula (II) include trimethylolpropane and 1,1,1-tris (hydroxymethyl) ethane. These may be used alone or in combination of two or more.

Next, examples of the glycol compound used as the component (C) of the present invention include ethylene glycol, diethylene glycol, triethylene glycol,
In addition to alkylene glycols and polyalkylene glycols such as polyethylene glycol, propylene glycol, dipropylene glycol and polypropylene glycol, alkylenes such as ethylene glycol mono (or di) alkyl ether, diethylene glycol mono (or di) alkyl ether, ethylene glycol monoalkyl ester Examples thereof include alkyl ethers or alkyl ester derivatives of glycols and polyalkylene glycols, and it is particularly preferable to use ethylene glycol and diethylene glycol monomethyl ether in combination because the concentration of the antibacterial active ingredient such as nitrilopropionamide compound can be adjusted at a high concentration.

In the antibacterial composition of the present invention, the content of 100 parts by weight of the component (A) alone or the combination of the components (A) and (D) as the active ingredient of the antibacterial agent is 100 parts by weight. The content of the component (B) alone or the combination of the components (B) and (C) is in the range of 100 to 20,000 parts by weight, preferably 500 to 10,000 parts by weight.

If the amount is too small, the stability of the antibacterial composition is lowered and the active ingredient is decomposed, so that a sufficient antibacterial action cannot be obtained at the time of use. Since it becomes small, sufficient antibacterial action cannot be obtained at the time of use.

When the component (B) and the component (C) are used in combination, the mixing ratio of the triol compound of the component (B) and the glycol compound of the component (C) is 1 to 10 by weight.
It is preferable to select in the range of 0: 100 to 1, preferably 30 to 70:70 to 30 because sufficient stability can be obtained.

Next, the isothiazolone compound used as the component (D) of the present invention is represented by the general formula (III), and the hydrocarbon group of R ^{6 in} the formula is a methyl group or an ethyl group. , A propyl group, a butyl group, an octyl group and other alkyl groups, a cyclohexyl group, a cyclopentyl group and other cycloalkyl groups, and R ⁷ and R ⁸ include halogen atoms such as Cl and Br.
R ⁷ and R ⁸ may be the same as or different from each other, but it is particularly preferable that R ⁷ is a hydrogen atom and R ⁸ is Cl because the antibacterial effect is excellent. General formula (II
Examples of the isothiazolone compound of I) include 5-chloro-2-methyl-4-isothiazolin-3-one and 2
-Methyl-4-isothiazolin-3-one, 2-n-octyl-4-isothiazolin-3-one, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, 2-ethyl-4 -Isothiazolin-3-one, 4,
5-dichloro-2-cyclohexyl-4-isothiazolin-3-one, 5-chloro-2-ethyl-4-isothiazolin-3-one, 5-chloro-2-t-octyl-4
-Isothiazolin-3-one and the like. These may be used alone or in combination of two or more.

When the component (D) is blended in the antibacterial agent of the present invention, the content ratio is in the range of 1 to 1500 parts by weight, preferably 1 to 500 parts by weight per 100 parts by weight of the component (A). It is preferable to select If this proportion is too low, the bactericidal activity against mold will be reduced, and if it is too high, the bactericidal activity against bacteria will be reduced.

[0020]

The stabilized antibacterial composition of the present invention contains a nitrilopropionamide compound or an isothiazolone compound by using a triol compound and optionally a glycol compound in addition to the triol compound. The decomposition of the composition can be remarkably suppressed, the stability is greatly enhanced, and the storage stability and transportability are excellent. Furthermore, the content of the nitrilopropionamide compound can be adjusted to a desired amount, and since the stability is high, the content of the nitrilopropionamide compound and the isothiazolone compound used as desired can be adjusted depending on the use environment. Antibacterial agents can be prepared. In addition, since the stability of the nitrilopropionamide compound is significantly improved even in the presence of metal, the active ingredient is decomposed even in the case of contact with metal such as cooling water circulation process, metalworking oil agent or aqueous paint enclosed in metal can. There is also an advantage that it can be used without doing.

[0021]

EXAMPLES Next, further details will be described with reference to Examples and Comparative Examples. Examples 1 to 13 and Comparative Examples 1 to 4 A bacteriostatic agent was prepared from each composition shown in Table 1 and the composition having the blending amount (parts by weight).

[0022]

[Table 1]

* 1 to * 6 in the table have the following meanings. * 1 2,2-Dibromo-3-nitrilopropionamide * 2 5-Chloro-2-methyl-4-isothiazoline-
3: 1 mixture of 3-one and 2-methyl-4-isothiazolin-3-one * 3 Glycerin * 4 Trimethylolpropane * 5 Ethylene glycol * 6 Diethylene glycol monomethyl ether

Reference Example The following tests were conducted on the antibacterial composition obtained in each Example and Comparative Example. A sample of each antibacterial composition is stored in a thermostatic chamber at 40 ° C, a part of each sample is collected daily, and the residual concentration of the nitrilopropionamide compound and optionally the isothiazolone compound is measured by liquid chromatography. did. Table 2 shows their residual rates. The residual rate was calculated by the following formula. Residual rate (%) = (X ′ / X) × 100 (where X is the initial concentration of the nitrilopropionamide compound or isothiazolone compound, X ′ is the nitrilopropionamide compound or isothiazolone compound after 10 days or 30 days) Indicates the concentration)

[0025]

[Table 2]

From these results, the antibacterial composition of each Example of the present invention is more stable than that of each Comparative Example, and the nitrilopropionamide compound or the isothiazolone-based compound used as desired. It will be appreciated that a stabilized antimicrobial composition can be prepared regardless of compound content.

Claims (7)

[Claims] 1. (A) General formula: (Wherein R ¹ represents a halogen atom, R ² represents a hydrogen atom or a halogen atom, R ³ represents a hydrogen atom or an alkyl group), and (B) a general formula: A stabilized antibacterial composition comprising a triol compound represented by the formula (R ⁴ represents a hydrogen atom or an alkyl group, and R ⁵ represents a hydroxyl group or a methylol group). 2. (A) General formula: (Wherein R ¹ represents a halogen atom, R ² represents a hydrogen atom or a halogen atom, and R ³ represents a hydrogen atom or an alkyl group), and (B) the general formula: Stabilized antibacterial agent composition comprising a triol compound represented by the formula (R ⁴ in the formula represents a hydrogen atom or an alkyl group, R ⁵ represents a hydroxyl group or a methylol group) and (C) a glycol compound . 3. (A) General formula: (Wherein R ¹ represents a halogen atom, R ² represents a hydrogen atom or a halogen atom, and R ³ represents a hydrogen atom or an alkyl group), and (D) a general formula: (In the formula, R ⁶ is a hydrogen atom or a hydrocarbon group, R ⁷ and R ⁸ are a hydrogen atom or a halogen atom, and these may be the same or different from each other). An isothiazolone compound, and (B) a general formula: A stabilized antibacterial composition comprising a triol compound represented by the formula (R ⁴ represents a hydrogen atom or an alkyl group, and R ⁵ represents a hydroxyl group or a methylol group). 4. (A) General formula: (Wherein R ¹ represents a halogen atom, R ² represents a hydrogen atom or a halogen atom, and R ³ represents a hydrogen atom or an alkyl group), and (D) a general formula: (In the formula, R ⁶ is a hydrogen atom or a hydrocarbon group, R ⁷ and R ⁸ are a hydrogen atom or a halogen atom, and these may be the same or different from each other). And an isothiazolone compound (B) having the general formula: Stabilized antibacterial agent composition comprising a triol compound represented by the formula (R ⁴ in the formula represents a hydrogen atom or an alkyl group, R ⁵ represents a hydroxyl group or a methylol group) and a (C) glycol compound . 5. The blending ratio of the component (B) and the component (C) is 1
-100: 100-1. The stabilized antibacterial composition according to claim 2 or 4. 6. The stabilized antibacterial composition according to any one of claims 1 to 5, wherein the component (B) is glycerin, trimethylolpropane or 1,1,1-tris (hydroxymethyl) ethane. 7. The stabilized antibacterial composition according to claim 3, wherein 0.01 to 15 parts by weight of the component (D) is mixed with 1 part by weight of the component (A).