KR100324907B1 - Stabilized isothiazolone composition from water and ultraviolet rays and method for stabilizing isothiazolone - Google Patents

Abstract

PURPOSE: A stabilized isothiazolone composition and a method for stabilizing isothiazolone are provided. The decomposition of isothiazolone having improved antibiotic and antimicrobial activity is effectively inhibited by water and ultraviolet rays without using metal salts. CONSTITUTION: The stabilized isothiazolone composition comprises a 3-isothiazolone compound of free metal represented by the formula(I); a stabilizing agent selected from dioxane and trioxane; and a solvent selected from diethylene glycol, diethylene glycol methyl ether, diethylene glycol dimethyl ether and dipropylene glycol, wherein R1 and R2 are the same or different, and hydrogen, halogen or C1-C4 alkyl; and R3 is hydrogen, halogen atom, C1-C10 alkyl optionally substituted with hydroxy, C2-C10 alkenyl optionally substituted with halogen atom, C2 to C10 alkynyl optionally substituted with halogen atom, or aralkyl optionally substituted with halogen atom, C1-C10 alkyl or C2-C9 alkoxy. The method for stabilizing isothiazolone is characterized by mixing the solvent selected from diethylene glycol, diethylene glycol methyl ether, diethylene glycol dimethyl ether and dipropylene glycol with the 3-isothiazolone compound of free metal represented by the formula(I).

Description

Stabilized Isothiazolone Composition

The present invention relates to a stabilized isothiazolone composition, and more particularly to a stabilized 3-isothiazolone composition consisting of an isothiazolone compound represented by the following structural formula (I) and dioxane or trioxane.

In the above formula,

R ¹ and R ² are the same as or different from each other, and are a hydrogen atom; Halogen atom; Or a C ₁ to C ₄ alkyl group,

R ³ is a hydrogen atom; Halogen atom; Or a C ₁ to C ₁₀ alkyl group unsubstituted or substituted with a hydroxy group; C ₂ ~ C ₁₀ alkenyl group unsubstituted or substituted with a halogen atom; C ₂ ~ C ₁₀ alkynyl group unsubstituted or substituted with a halogen atom; Or an aralkyl group unsubstituted or substituted with a halogen atom, a C ₁ to C ₁₀ alkyl group or a C ₂ to C ₉ alkoxy group.

Since the isothiazolone compound was developed by Crow et al. In 1965, it has been widely used throughout the industry as an antimicrobial and antimicrobial agent such as disinfectants, paints, cosmetics, textiles or plastics. However, since the isothiazolone compound is very unstable and easily decomposed by moisture and ultraviolet light in the air, its effect may be reduced upon storage of the product to which the isothiazolone compound is added. Therefore, various methods for improving the stability of the isothiazolone compound have been researched and developed, and a typical method is to use a metal salt stabilizer.

For example, US Pat. Nos. 3,870,795 and 4,067,878 attempt to stabilize isothiazolone compounds by chemical decomposition by addition of metal nitrites or metal nitrates. Such metal salt stabilizers are latex emulsions in which polymers are dispersed. The removal of metal salts from these systems is essential because they can react with emulsion components in aqueous solutions and cause sedimentation. In some systems, chlorine ions bound to metal salts can cause corrosion of the system.

Therefore, the inventors of the present invention have solved all the problems according to the stabilization method of the conventional isothiazolone and provide a stabilized isothiazolone system without using a metal salt. As a result, dioxane or trioxane isothiazolone The present invention has been completed by focusing on the fact that the addition of S (a) may prevent decomposition of isothiazolone.

The present invention aims to provide a stabilized 3-isothiazolone composition as an antimicrobial agent.

Hereinafter, the present invention will be described in detail.

The present invention is characterized by an isothiazolone composition comprising a 3-isothiazolone compound represented by the following structural formula (I), dioxane or trioxane, and a solvent.

Wherein R ¹ , R ² and R ³ are as defined above.

The present invention will be described in more detail as follows.

The present invention relates to an isothiazolone composition in which dioxane or trioxane is mixed as a stabilizer to stabilize an unstable 3-isothiazolone compound in the atmosphere.

The 3-isothiazolone compound which can be used in the present invention is a single or a mixture of two or more selected from the compounds represented by the above formula (I), preferably 5-chloro-2-methyl-3-isothiazolone, 2 -Methyl-3-isothiazolone, 2-n-octyl-3-isothiazolone, 4,5-dichloro-2-cyclohexyl-3-isothiazolone and 4,5-dichloro-2-n-octyl- Single or a mixture of two or more selected from 3-isothiazolones. Most preferred of these are 5-chloro-2-methyl-3-isothiazolone or a mixture of 5-chloro-2-methyl-3-isothiazolone and 2-methyl-3-isothiazolone. In the case of the 5-chloro-2-methyl-3-isothiazolone and 2-methyl-3-isothiazolone mixtures, the preferred mixing ratio is about 70:30 to 85:15 wt%, and more preferred mixing ratio is about 70:30 80: 20 weight%. On the other hand, a mixture of 2-methyl-3-isothiazolone as a main component and a small amount of 5-chloro-2-methyl-3-isothiazolone is also very desirable. In this case, the preferred mixing ratio is about 98: 2 to 96: 4. % By weight, and a particularly preferred mixing ratio is about 97: 3% by weight.

The amount of dioxane or trioxane used as a stabilizer in the present invention can be changed depending on the conditions of use and the concentration of isothiazolone in the mixture, and the effective amount is 1: 100 to 1000: 1 weight ratio In a concentrated solution, a weight ratio of 1:50 to 50: 1 is common, and more stabilizers may be used, but this is uneconomical. In a highly diluted 3-isothiazolone solution (such as about 1 to 10000 ppm isothiazolone in the solvent), the ratio of stabilizer to isothiazolone is about 1: 10 to 20: 1 weight ratio, preferably 1: 5 20: 1 weight ratio.

3-isothiazolone composition according to the present invention is prepared in the form of a solution, the composition ratio is about 0.01 to 99% by weight of a single or a mixture of two or more selected from the 3-isothiazolone compound represented by the formula (I) 0.01 to 99% by weight of dioxane or trioxane and 99.98% by weight of solvent; Preferably 0.01 to 15% by weight of a single or two or more mixtures selected from 3-isothiazolone compounds represented by the above formula (I), 0.01 to 15% by weight of dioxane or trioxane, and 90 to 99.98% by weight of a solvent. ; Most preferably, 0.01 to 1% by weight of a single or two or more mixtures selected from 3-isothiazolone compounds represented by the above formula (I), 0.01 to 1% by weight of dioxane or trioxane, and 98 to 99.98% by weight of a solvent to be.

The composition of the present invention as described above is prepared in the form of a solution, depending on the use of the solution is prepared in concentrated or dilute solution, in the case of specific use, such as bulk shipping, a more concentrated solution can be used.

The solvent that can be used in the present invention can be used as long as it is an organic solvent that can dissolve and stabilize the isothiazolone compound. Hydroxyl solvents such as, for example, glycols or alcohols may also be used, and the greater the ratio of the amount of isothiazolone to dioxane or trioxane, and the higher the dilution conditions, the more effective the use of glycol. In addition, aliphatic or aromatic hydrocarbons are useful in a series of compositions. In addition, preferred solvents are polyols in which free hydroxy is substituted with an ether or ester functional group, with ethylene glycol methyl ether or ethylene glycol dimethyl ether being particularly preferred.

In the present invention, only a small amount of dioxane or trioxane can be used to achieve stabilization of isothiazolones, so that the amount of dioxane or trioxane in the system to be treated is very small and in a system requiring protection. Other components or protection systems do not interfere with the system to which they are applied.

The isothiazolone composition according to the present invention as described above is very stable in the air, and even after being stored for a relatively long time, its medicinal effect persists and can be used in any area contaminated by bacteria, fungi, yeast or algae.

Ie disinfectants, sanitizers, detergents, deodorants, liquid and powdered soaps, oil and grease removers, food processing chemicals, daily chemicals, food preservatives, animal feed preservatives, wood preservatives, paints, lazures, dyeing Liquids, flavoring agents, hospital and medical preservatives, metal working agents, cooling water, air fresheners, petroleum manufacturing, paper processing, paper mill slime inhibitors, petroleum products, adhesives, textiles, pigment slurry, latex, leather and leather treatment, petroleum Fuel, laundry detergent, agricultural compound feed, ink, mining, non-woven fabric, oil storage, good materials, rubber, sugar, tobacco, swimming pool, cosmetics, toiletries, glue, plastic, card board, pharmaceuticals, chemical toilet paper, household laundry, diesel fuel Use anywhere in areas of organics and moisture that come into contact with the environment where additives, waxes, cokes, lubricants, building supplies, concrete blends or polishes and other undesirable microorganisms can grow. Neunghada.

Hereinafter, the present invention will be described in detail with reference to the following Examples, but the present invention is not limited by the Examples.

All percentages are by weight and all reagents used are industrial grade reagents in good condition.

In addition, the isothiazolone solution prepared in Examples 1 to 13 and Comparative Examples 1 to 9 was measured for thermal stability after being left in a 65 ° C. thermostatic chamber, respectively, and the degree of decomposition by thermal stability measurement was high performance liquid chromatography (HPLC). , High Performance Liquid Chromatography). Residual content (%) measurement results are shown in the following Tables 1,2 and 3.

Example 1

4.5% by weight isothiazolone mixture with 5-chloro-2-methyl-3-isothiazolone and 2-methyl-3-isothiazolone in a 3: 1 weight ratio, 9% by weight of dioxane and 86.5% by weight of diethylene glycol Mix% to prepare an isothiazolone solution.

Example 2

An isothiazolone solution was prepared in the same composition as in Example 1, except that 86.5 wt% of diethylene glycol methyl ether was used instead of 86.5 wt% of diethylhen glycol as a solvent.

Example 3

An isothiazolone solution was prepared in the same composition as in Example 1, except that 86.5 wt% of diethylene glycol dimethyl ether was used instead of 86.5 wt% of diethylene glycol as a solvent.

Comparative Example 1

Isothia by mixing 4.5% by weight of an isothiazolone mixture containing 5-chloro-2-methyl-3-isothiazolone and 2-methyl-3-isothiazolone in a 3: 1 weight ratio and 95.5% by weight of diethylene glycol. A jolon solution was prepared.

Comparative Example 2

An isothiazolone solution was prepared in the same composition as Comparative Example 1, except that 95.5% by weight of ethylene glycol methyl ether was used instead of 95.5% by weight of diethylene glycol.

Comparative Example 3

An isothiazolone solution was prepared in the same composition as Comparative Example 1, except that 95.5% by weight of ethylene glycol dimethyl ether was used instead of 95.5% by weight of diethylene glycol.

Table 1

Example 4

2.5% by weight mixture of 5-chloro-2-methyl-3-isothiazolone and 2-methyl-3-isothiazolone in a 1: 5 weight ratio, 10% by weight of trioxane and 87.5% by weight of diethylene glycol Mix% to prepare an isothiazolone solution.

Example 5

An isothiazolone solution was prepared in the same composition as in Example 4, except that 87.5 wt% of diethylene glycol methyl ether was used instead of 87.5 wt% of diethylene glycol as a solvent.

Example 6

An isothiazolone solution was prepared in the same composition as in Example 4, except that 87.5 wt% of diethylene glycol dimethyl ether was used instead of 87.5 wt% of diethylene glycol as a solvent.

Example 7

An isothiazolone solution was prepared in the same composition as in Example 4 except using 45% by weight of diethylene glycol methyl ether and 42.5% by weight of dipropylene glycol instead of 87.5% by weight of diethylene glycol.

Example 8

An isothiazolone solution was prepared in the same composition as in Example 4, except that 45% by weight of diethylene glycol dimethyl ether and 42.5% by weight of dipropyllan glycol were used instead of 87.5% by weight of diethylhen glycol.

Comparative Example 4

Isothia by mixing 2.5% by weight of an isothiazolone mixture containing 5-chloro-2-methyl-3-isothiazolone and 2-methyl-3-isothiazolone in a 1: 5 weight ratio and 97.5% by weight of diethylene glycol. A jolon solution was prepared.

Comparative Example 5

An isothiazolone solution was prepared in the same composition as Comparative Example 4 except using 97.5 wt% of ethylene glycol methyl ether instead of 97.5 wt% of diethylene glycol as a solvent.

Comparative Example 6

An isothiazolone solution was prepared in the same composition as Comparative Example 4, except that 97.5 wt% of ethylene glycol dimethyl ether was used instead of 97.5 wt% of diethylene glycol as a solvent.

TABLE 2

Example 9

14.5% by weight mixture of 5-chloro-2-methyl-3-isothiazolone and 2-methyl-3-isothiazolone in a 3: 1 weight ratio, 15% by weight of dioxane and 70.5% by weight of diethylene glycol Mix% to prepare an isothiazolone solution.

Example 10

An isothiazolone solution was prepared in the same manner as in Example 9, except that 70.5 wt% of diethylene glycol methyl ether was used instead of 70.5 wt% of diethylene glycol as a solvent.

Example 11

An isothiazolone solution was prepared in the same composition as Example 9, except that 70.5 wt% of diethylene glycol dimethyl ether was used instead of 70.5 wt% of diethylene glycol as a solvent.

Example 12

An isothiazolone solution was prepared in the same composition as Example 9, except that 35 wt% diethylene glycol methyl ether and 35.5 wt% dipropylene glycol were used instead of 70.5 wt% of diethylene glycol as a solvent.

Example 13

An isothiazolone solution was prepared in the same composition as Example 9, except that 35 wt% diethylene glycol dimethyl ether and 35.5 wt% dipropylene glycol were used instead of 70.5 wt% of diethylene glycol as a solvent.

Comparative Example 7

Isothia by mixing 14.5 wt% of an isothiazolone mixture containing 5-chloro-2-methyl-3-isothiazolone and 2-methyl-3-isothiazolone in a 3: 1 weight ratio and 85.5 wt% of diethylene glycol A jolon solution was prepared.

Comparative Example 8

An isothiazolone solution was prepared in the same composition as Comparative Example 7, except that 85.5% by weight of ethylene glycol methyl ether was used instead of 85.5% by weight of diethylene glycol.

Comparative Example 9

An isothiazolone solution was prepared in the same composition as Comparative Example 7, except that 85.5% by weight of ethylene glycol dimethyl ether was used instead of 85.5% by weight of diethylene glycol.

TABLE 3

Claims (7)

3-isothiazolone compound of the free metal represented by the following structural formula (I); Stabilizers selected from dioxane and trioxane; And isothiazolone composition, characterized in that consisting of a solvent selected from diethylene glycol, diethylene glycol methyl ether, diethylene glycol dimethyl ether and dipropylene glycol. In the above formula, R ¹ and R ² are the same as or different from each other, and a hydrogen atom; Halogen atom; Or a C ₁ to C ₄ alkyl group, R ³ is a hydrogen atom; Halogen atom; Or a C ₁ to C ₁₀ alkyl group unsubstituted or substituted with a hydroxy group: a C ₂ to C ₁₀ alkenyl group unsubstituted or substituted with a halogen atom; C ₂ -C ₁₀ alkynyl groups which are unsubstituted or substituted with halogen atoms; Or an aralkyl group unsubstituted or substituted with a halogen atom, a C ₁ to C ₁₀ alkyl group, or a C ₂ to C ₉ alkoxy group. The method of claim 1, wherein the 3-isothiazolone compound is 5-chloro-2-methyl-3-isothiazolone, 2-methyl-3-isothiazolone, 2-n-octyl-3-isothiazolone, An isothiazolone composition, characterized in that at least one selected from 4,5-dichloro-2-cyclohexyl-3-isothiazolone and 4,5-dichloro-2-n-octyl-3-isothiazolone. The isothiazolone composition according to claim 1, wherein the mixing ratio of dioxane or trioxane and 3-isothiazolone is 1: 50-20: 1 by weight. According to claim 1, wherein the composition is composed of 0.01 to 99% by weight of the 3-isothiazolone compound represented by the formula (I), 0.01 to 99% by weight of dioxane or trioxane, and 99.98% by weight or less of the solvent. Isothiazolone composition. A stabilized effective amount of dioxane or trioxane, and a solvent selected from diethylene glycol, diethylene glycol methyl ether, diethylene glycol dimethyl ether, and dipropylene glycol are selected from 3- of the free metal represented by the following structural formula (I): A method for stabilizing isothiazolones, which is mixed with an isothiazolone compound. Wherein R ¹ , R ² and R ³ are as defined in claim 1 above. The method of claim 5, wherein the mixing ratio of the dioxane or trioxane and 3-isothiazolone is 1: 100 to 1000: 1 by weight ratio. Antimicrobial agent, characterized in that the isothiazolone composition of claim 1 contained as an active ingredient.