KR20060070622A - Composition including isothiazolone compound - Google Patents

Abstract

The present invention relates to an isothiazolone composition, wherein the isothiazolone composition of the present invention comprising (a) a 3-isothiazolone compound of formula (1), (b) a polysaccharide, and (c) a solvent has excellent phase stability and thus an emulsion It can be used as a disinfectant stably in solution or creamy products.

 [Formula 1]

In Formula 1, the definitions of R ₁ , R _2, and R ₃ are the same as in the specification.

Isothiazolone, gum arabic, guar gum, xanthan gum, sodium alginate, propylene glycol alginate, carrageenan

Description

Isothiazolone composition {COMPOSITION INCLUDING ISOTHIAZOLONE COMPOUND}

The present invention relates to an improved isothiazolone composition comprising (a) a 3-isothiazolone compound of formula (1), (b) a polysaccharide and (c) a solvent.

Isothiazolone is a compound that has a wide range of bactericidal activity against many harmful organisms derived from plants and animals such as bacteria, fungi, algae, etc., and is used as an inhibitor for the growth of harmful microorganisms when added to cosmetics and paints.

In general, isothiazolone is decomposed in a polar organic solvent such as alcohol or water without adding a stabilizer, which causes a problem in that biological activity decreases with time. Therefore, many studies have been conducted to increase the stability of isothiazolone in polar organic solvent or in water.

In order to enhance the stability of isothiazolones in polar organic solvents or in water, US Pat. No. 3,870,785 discloses the addition of metal nitrates, nitrites, and the like as stabilizers to isothiazolone compositions. In addition, US Pat. No. 4,165,318 discloses a process for adding formaldehyde, formaldehyde eluting material to the isothiazolone composition as a stabilizer. In addition, US Pat. No. 4,824,957 discloses a method of adding an organic hydroxyl group solvent as a stabilizer to an isothiazolone composition as a stabilizer.

Therefore, metal nitrates, especially copper nitrate or magnesium nitrate, are added to the 3-isothiazolone composition as a stabilizer of isothiazolone which is currently widely used commercially. % Isothiazolone and 15-25 wt% nitrate.

However, according to the above methods, in many cases in which the isothiazolone composition is produced or used, the release of nitrogen oxide gas harmful to the human body or the environment is inevitable. In addition, the inorganic metal salt stabilizer is suitable for the stability effect of the disinfectant, but when added to dispersions or emulsion products such as latex, the viscosity of the product decreases, and coagulation occurs, which may impair the value of the product. There is a disadvantageous problem in maintaining stability.

In order to solve the above problems, the present invention does not destroy the active ingredient of the product during the manufacturing process or distribution of the disinfectant composition, and does not contain inorganic metal salts, which is beneficial to the water environment, and does not decrease the viscosity of the emulsion solution or the like when using the disinfectant. It is an object of the present invention to provide a novel isothiazolone composition which can not only effectively inhibit the growth of harmful microorganisms but also has excellent storage stability and does not generate precipitates.

In order to achieve the above object,                     

The present invention provides an isothiazolone composition comprising (a) a 3-isothiazolone compound represented by the following formula (1), (b) a polysaccharide, and (c) a solvent.

[Formula 1]

In Chemical Formula 1,

R ₁ and R ₂ are each a hydrogen atom, a halogen atom, an alkyl group of C ₁ to C ₄ , or a cyclized aryl group,

R ₃ is a hydrogen atom, C ₁ to C ₁₈ alkyl group, C ₂ to C ₁₈ alkenyl group, C ₂ to C ₁₈ alkynyl group, C ₃ to C ₁₂ cycloalkyl group having 3 to 8 octacyclic rings, C ₁₀ To C ₂₄ aralkyl group, or C ₁₀ to C ₂₄ aryl group.

In addition, the present invention (a) 0.1 to 60% by weight of 3-isothiazolone compound; (b) 0.01 to 10 weight percent of a polysaccharide; And (c) a solvent balance and the viscosity measured by a Brookfield viscometer is from 100 to 3000 centipoise at 25 ° C. to provide an isothiazolone composition.

The isothiazolone composition of the present invention increases the stability without destroying the active material of the disinfectant by using polysaccharide as a stabilizer of isothiazolone, and destroys the stability of the phase stability due to the decrease in the viscosity of the emulsifier and the dispersion system that are inevitably added when the disinfectant is added. In particular, it can be used as a disinfectant stably without deteriorating the properties of the product, especially in emulsion solutions or creamy products such as latex paint products or cosmetics.

Hereinafter, the present invention will be described in more detail.

The 3-isothiazolone compound represented by Formula (a) 1 is preferably included in an amount of 0.1 to 60 wt%. If the content of 3-isothiazolone compound is less than 0.1% by weight, the content of isothiazolone, a fungicide, in the isothiazolone composition of the present invention is low and cannot be used commercially preferably. There is a problem that cannot be dissolved.

As the 3-isothiazolone compound of the formula (a), 5-chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, 4,5 -Dichloro-2-methyl-4-isothiazolin-3-one, 5-chloro-2-n-octyl-3-isothiazolone, 4,5-dichloro-2-n-octyl-3-isothiazolone , Benzisothiazolone alone or a mixture thereof may be preferably used.

The 3-isothiazolone compound of formula (a) is generally added to the composition as a solid in the form of hydrochloride during the preparation process. When used as a mixture, a mixture of 5-chloro-2-methyl-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one is preferable, and the mixing weight ratio thereof is 1:20 to 20: 1 is preferred.

The polysaccharide (b) includes etherified derivatives of cellulose, synthetic or natural. Hydroxyl groups of polysaccharides induce hydrogen bonds in aqueous solution to decrease the activity of water, thereby reducing the reaction rate between isothiazolone and aqueous solution, and thus can be stably present in aqueous solution without decreasing the concentration. Polysaccharides include, for example, hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose, hydroxypropyl methyl cellulose, hydroxyethyl methyl cellulose, hydroxyethyl carboxymethyl cellulose and the like. In addition, natural polysaccharides may include gums such as gum arabia, guar gum, xantangum, cellulose ether, sodium alginate, propylene glycol alginate, carrageenan, and the like. Ether substituents suitable for use in the present invention preferably consist of ethers having from 2 to 4 carbon atoms per molecule.

The polysaccharide is prepared as a 1 to 30% aqueous phase concentrate and then added with a fungicide or mixed in the fungicide solution, it is preferably included in an amount of 0.01 to 10% by weight relative to the entire fungicide composition. When used at less than 0.01% by weight, the isothiazolone stabilization effect by the polysaccharide is reduced, and when it is more than 10% by weight, it is economically disadvantageous. Stabilizing effect of isothiazolone by polysaccharides can be evaluated by quantitatively analyzing the decrease in active ingredient concentration of the fungicide composition. In this case, the stabilizing effect varies depending on the molecular weight of the polysaccharide, and the molecular weight is generally 10,000-5 × 10 ⁶ grams / gram mole, preferably 50,000-1 × 10 ⁶ grams / gram mole. As used herein, the term "molecular weight" means a weight average molecular weight.

The viscosity of the fungicide composition to which the polysaccharide is added is generally 5-6000 cp (centipoise), preferably in the range of 100-3000 cp. Unless stated otherwise, the term "viscosity" as used herein refers to the viscosity of aqueous solution of fungicide, measured at 25 ° C. with a Brookfield viscometer. Such viscosity measurement methods are common knowledge in the art and are represented by ASTM D 2364-89.

The average particle size of the polysaccharide itself affects the agitation efficiency in the preparation of the composition so that it is preferably 0.01-1000 microns, more preferably 50-400 microns, in order to be an economical manufacturing process.

The solvent may be water, ethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, diethylene glycol, triethylene glycol, 1,5-pentanediol, 2,4-pentanediol, benzyl alcohol or mixtures thereof. It can be used preferably.

Hereinafter, preferred examples and comparative examples of the present invention are described. The following examples and comparative examples are described for the purpose of more clearly expressing the present invention, but the contents of the present invention are not limited to the following examples and comparative examples.

<Example 1>

100 g of an aqueous isothiazolone solution composition was prepared by dissolving 21 g of solid in 2-methyl-4-isothiazolin-3-one (MI) hydrochloride in a 300 ml flask volume with water so that the active ingredient weight was 16%. As a polysaccharide, 1 g of solid xanthan gum having an average molecular weight of 1000000 was added and stirred sufficiently. A small amount of sodium bicarbonate was added as a pH adjuster of the composition to bring the pH of the solution to 4. In order to evaluate the stability of the solution, it was stored at 65 ° C. for 7 days and the change of the active ingredient content was measured by HPLC.

In order to evaluate the stability during emulsion application of the prepared sterilant composition, 1 g of the sterilant composition prepared in 100 g of the latex paint standard product shown in Table 1 was added thereto, stirred vigorously, and after removing the foam generated under vacuum heating conditions, the viscosity of the latex paint was measured. It was measured at 25 degreeC with the Brookfield viscometer.

Material content Anionic Polymer Dispersant 4.2g Potassium Triphosphate 0.25g Nonionic surfactant 1.0 g Silicone Defoamer 1.0 g Vinylacrylic latex 50 g Propylene glycol 10 g Monoisobutylate 10 g Aluminum silicate 60 g Titanium oxide 70 g Calcium carbonate 100 g water 230 g

<Example 2>

To prepare 100 g of isothiazolone aqueous solution composition, 5-chloro-2-methyl-4-isothiazolin-3-one (CMI) and 2-methyl-4-isothiazoline-3 as 3-isothiazolone compounds The same procedure as in Example 1 was conducted except that a solid hydrochloride mixture having a 1: 3 weight ratio of -MI was used.

<Example 3>

Example 1 was the same as in Example 1 except that 1g of gum arabic gum instead of 1g xanthan gum was added.

<Example 4>

Example 2 was carried out in the same manner as in Example 2, except that 1 g of gum arabic was added instead of 1 g of xanthan gum.                     

Comparative Example 1

100 g of an aqueous isothiazolone solution composition was prepared by dissolving 21 g of solid in 2-methyl-4-isothiazolin-3-one (MI) hydrochloride in a 300 ml flask volume with water so that the active ingredient weight was 16%. A small amount of sodium bicarbonate was added to bring the pH of the solution to 4. In order to evaluate the stability of the composition solution was stored for 7 days at 65 ℃ to measure the change in the active ingredient content by HPLC.

In order to evaluate the stability during emulsion application of the prepared sterilant composition, 1 g of the sterilant composition prepared in 100 g of the latex paint standard product shown in Table 1 was added thereto, stirred vigorously, and after removing the foam generated under vacuum heating conditions, the viscosity of the latex paint was measured. It was measured at 25 degreeC with the Brookfield viscometer.

Comparative Example 2

To prepare 100 g of isothiazolone aqueous solution composition, 5-chloro-2-methyl-4-isothiazolin-3-one (CMI) and 2-methyl-4-isothiazoline-3 as 3-isothiazolone compounds The same procedure as in Comparative Example 1 was carried out except that a solid hydrochloride mixture having a 1: 3 weight ratio of -MI was used.

The aqueous solution compositions prepared in Examples 1 to 4 and Comparative Examples 1 and 2 are 5-chloro-2-methyl-4-isothiazolin-3-one (CMI), methyl-4-, as shown in Table 2 below. Isothiazolin-3-one (MI), Xantangum, Arabic gum, Sodium chloride (NaCl) and water balance.                     

sample MI (% by weight) CMI (% by weight) Xanthan Gum (% by weight) Arabian gum (% by weight) NaCl (% by weight) Example 1 16 0 One 0 7.5 Example 2 4 12 One 0 7.5 Example 3 15 0 0 One 7.5 Example 4 4 12 0 One 7.5 Comparative Example 1 16 0 0 0 7.5 Comparative Example 2 4 12 0 0 7.5

Experimental Example 1 Stability Measurement Test

The composition prepared by the above Examples and Comparative Examples was taken and stored for 7 days at 65 ° C. incubator to quantify the active ingredient concentration by HPLC instrument. In the quantitative analysis, the column was microbondapak C18 reverse and the developing solvent was diluted with water and methanol at a ratio of 6: 4 and separated at a flow rate of 1 ml per minute. At this time, MI and CMI were separated and detected within 10 minutes of retention time. Verification is possible with a mass spectrometer (MASS) and quantitation is measured relative to the standard. The measurement results are shown in Table 3 below.

sample MI% before treatment CMI% before treatment MI% after treatment CMI% after treatment 65 ℃ stability Example 1 16 0 14.9 0 99% Example 2 4 12 4 10.8 92.5% Example 3 16 0 14.8 0 98% Example 4 4 12 3.9 10.5 90% Comparative Example 1 16 0 12 0 80% Comparative Example 2 4 12 3.1 5.2 52%

Experimental Example 2 Latex Stability Test

100 g of the standard latex sample described in Table 1 was added to each of the sterilant composition prepared in Examples and Comparative Examples and stirred vigorously, and subjected to vacuum degassing under heated conditions of about 50 ℃ to remove bubbles. The viscosity of the latex was then measured at 25 ° C. with a Brookfield viscometer. The measurement results are shown in Table 4 below.                     

sample CP before treatment Properties before disinfectant treatment Post Treatment Viscosity CP After treatment Stability Example 1 3000 Gel 3000 Gel No change Example 2 3000 Gel 3000 Gel No change Example 3 3000 Gel 3000 Gel No change Example 4 3000 Gel 3000 Gel No change Comparative Example 1 3000 Gel 2500 Liquid layer generation Change Comparative Example 2 3000 Gel 2500 Liquid layer generation Change

In the present invention, polysaccharide is used as a stabilizer of the isothiazolone composition, and by minimizing or excluding an amount of inorganic metal salt, which is a widely used stabilizer, the generation of nitrogen oxide gas harmful to the human body during the production, distribution, and use of a disinfectant is fundamentally eliminated. It is possible to increase the safety of the human body and increase the stability of the sterilizer products due to low storage stability.It can be used as a disinfectant in emulsion solution because it does not destroy the dispersing or emulsifying system when applied to the disinfectant products. It can be suppressed.

Claims (6)

(a) 3-isothiazolone compound represented by the following formula (1); (b) polysaccharides; And (c) solvent Isothiazolone composition comprising: [Formula 1]

In Chemical Formula 1, R ₁ and R ₂ are each a hydrogen atom, a halogen atom, an alkyl group of C ₁ to C ₄ or a cyclized aryl group, R ₃ is a hydrogen atom, C ₁ to C ₁₈ alkyl group, C ₂ to C ₁₈ alkenyl group, C ₂ to C ₁₈ alkynyl group, C ₃ to C ₁₂ cycloalkyl group having 3 to 8 octacyclic rings, C ₁₀ To C ₂₄ aralkyl group or C ₁₀ to C ₂₄ aryl group. The method of claim 1, The isothiazolone composition is (a) 0.1 to 60 weight percent of 3-isothiazolone compound; (b) 0.01 to 10 weight percent of a polysaccharide; And (c) solvent balance Isothiazolone composition comprising a and the viscosity measured by a Brookfield viscometer is 100 to 3000 centipoise at 25 ℃. The method according to claim 1 or 2, The 3-isothiazolone compound is 5-chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, 4,5-dichloro-2-methyl- 4-isothiazolin-3-one, 5-chloro-2-n-octyl-3-isothiazolone, 4,5-dichloro-2-n-octyl-3-isothiazolone, benzisothiazolone and these Isothiazolone composition, characterized in that selected from the group consisting of. The method according to claim 1 or 2, The polysaccharide is isothiazolone composition, characterized in that the solid having a weight average molecular weight of 10000 to 5000000. The method according to claim 1 or 2, The polysaccharide is hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose, hydroxypropyl methyl cellulose, hydroxyethyl methyl cellulose, hydroxyethyl carboxymethyl cellulose gum arabic, guagum, xanthan gum ( Xantangum), cellulose ether, sodium alginate, propylene glycol alginate and carrageenan is one or more selected from the group consisting of isothiazolone composition. The method according to claim 1 or 2, The solvent is selected from the group consisting of water, ethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, diethylene glycol, triethylene glycol, 1,5-pentanediol, 2,4-pentanediol and benzyl alcohol Isothiazolone composition.