KR100975374B1 - Isothiazolone composition and method for stabilizing isothiazolone - Google Patents

Abstract

The present invention relates to an isothiazolone composition and a method for stabilizing isothiazolone, and more particularly, (a) a 3-isothiazolone compound represented by the following formula (1); (b) alkali metal nitrates; (c) alkali metal chloride salts; (d) a compound selected from the group consisting of iodic acid, periodic acid, iodide and periodicate; (e) metal bromates; And (f) a isothiazolone composition comprising a solvent and a method for stabilizing isothiazolone.

   [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 isothiazolone composition of the present invention does not contain alkaline earth metal salts of divalent metals such as magnesium chloride which cause salt shock, so that the isothiazolone composition can be stably used as a disinfectant in an emulsion solution such as dispersion or paint acrylate or latex. In addition to effectively inhibiting growth, the sediment generation rate is low, and the storage stability is excellent.

Isothiazolone, alkali metal nitrate, alkali metal carbonate salt, alkali metal chloride salt, iodic acid, periodate, iodide, periodate, metal bromate

Description

Isothiazolone composition and the method of stabilization of isothiazolone {ISOTHIAZOLONE COMPOSITION AND METHOD FOR STABILIZING ISOTHIAZOLONE}

1 is a photograph showing the results of the salt shock of the isothiazolone composition samples of Example 1, Comparative Example 1 and the control in Test Example 1.

FIG. 2 is a photograph showing salt shock results of a sample obtained by diluting the isothiazolone compositions of Example 1 and Comparative Example 1 in Test Example 1 by 10 times.

FIG. 3 is a photograph showing salt shock results for the isothiazolone composition samples of Example 1 and Comparative Example 1 in Test Example 2 (paint acrylate emulsion). FIG.

Figure 4 is a photograph showing the results of the salt shock for the isothiazolone composition samples of Example 1 and Comparative Example 1 in Test Example 3 (latex emulsion).

[Industrial use]

The present invention relates to an isothiazolone composition and a method for stabilizing isothiazolone, and more particularly, it does not include an alkaline earth metal salt of a divalent metal such as magnesium chloride that causes salt shock, and thus a dispersion or paint acrylate or latex. The present invention relates to an isothiazolone composition and a method for stabilizing isothiazolone having excellent storage stability because it can be effectively used as a disinfectant in an emulsion solution of not only effectively inhibiting the growth of harmful microorganisms but also having a low sediment generation rate.

[Prior art]

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

However, isothiazolone is decomposed in polar organic solvents such as alcohol or water, and there is a problem in that biological activity decreases with time. Therefore, many studies have been conducted to increase the stability of the isothiazolone as described above in polar organic solvents or water.

In order to enhance the stability of isothiazolones in polar organic solvents or in water, US Pat. No. 3,870,795 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. U.S. Patent No. 4,824,957 also discloses a method of adding an organic hydroxyl group solvent as a stabilizer to an isothiazolone composition as a stabilizer.

However, in many cases using the isothiazolone compounds introduced in the methods described in the various U.S. patents, reducing the content of such stabilizers used to stabilize fungicides containing isothiazolone compounds is for various reasons. desirable.

For example, dispersions that require deterioration by microorganisms or emulsion solutions such as paint acrylates or latexes are sensitive to salts, especially when adding fungicides containing salts that are divalent ions. This is because it is easy to coagulate due to poor mixing.

Moreover, the sterilizing active ingredient may be entrapped in the coagulum, so that the sterilizing active ingredient may be reduced or eliminated when the product to be preserved is filtered.

Currently widely used stabilizers are metal nitrates, in particular magnesium chloride or magnesium nitrate, added to the 3-isothiazolone composition. Commonly used isothiazolone compositions comprise 1 to 20 wt% isothiazolone and 15 to 25 wt% nitrate.

In addition, isothiazolone compositions contain divalent metals, especially magnesium oxide, as pH neutralizing agents. However, isothiazolone compositions containing a large amount of divalent metal salts such as magnesium oxide have problems in use due to “salt shock” caused by bivalent metal salts and thus cannot be preferably used as fungicides.

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and an object of the present invention is not to include alkaline earth metal salts of divalent metals such as magnesium chloride, which cause salt shock, so that they are stable in dispersion or emulsion solution such as paint acrylate or latex. In addition, it can be used as a biocide inhibitor to effectively inhibit the growth of harmful microorganisms and to increase the stability of the isothiazolone solution by adding two synergistic stabilizers, the sediment generation rate is much lower than the conventional concentration. It is to provide an isothiazolone composition having low storage stability.

It is also an object of the present invention to provide a method for stabilizing isothiazolones.

In order to achieve the above object, the present invention (a) 3-isothiazolone compound of formula (1); (b) alkali metal nitrates; (c) alkali metal chloride salts; (d) a compound selected from the group consisting of iodic acid, periodic acid, iodide and periodicate; (e) metal bromates; And (f) provides an isothiazolone composition comprising 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.

The present invention also provides (i) 0.1 to 20% by weight of (iso) 3-isothiazolone compound represented by the following formula (1); (b) 0.1 to 25% by weight of alkali metal nitrate; (C) adding 0.001 to 20% by weight of an alkali metal carbonate salt to (f) the remainder of the solvent to prepare a mixed solution; And (ii) 0.0001 to 0.01% by weight of a compound selected from the group consisting of (d) iodic acid, periodic acid, iodide and periodicate and (e) 0.001 to 1.0% by weight of a metal bromate in step (iii). It provides a method for stabilizing isothiazolone comprising the step of adding to the mixed solution to prepare a 3-isothiazolone composition.

[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.

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

The isothiazolone composition of the present invention comprises (a) a 3-isothiazolone compound of formula (1); (b) alkali metal nitrates; (c) alkali metal chloride salts; (d) a compound selected from the group consisting of iodic acid, periodic acid, iodide and periodicate; (e) metal bromates; And (f) 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.

The 3-isothiazolone compound represented by the formula (1) of (a) is a compound having a wide range of bactericidal activity against many harmful organisms derived from animals and plants such as bacteria, fungi, algae, and the like. It is widely used as a growth inhibitor.

In the isothiazolone composition of the present invention, the content of 3-isothiazolone compound of the formula (1) of (a) is preferably 0.1 to 20% by weight. When the content of 3-isothiazolone compound of formula (1) of (a) is less than 0.1% by weight, the isothiazolone composition of the present invention is commercially preferable because the content of isothiazolone, which is a bactericide, is low in the isothiazolone composition of the present invention. There is a problem that can not be used. In addition, when the content of the 3-isothiazolone compound of the formula (1) of (a) exceeds 20% by weight, there is a problem that the stability is lowered.

As the 3-isothiazolone compound of the formula (1) of (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-isothia Zolone, benzisothiazolone or mixtures thereof and the like can be preferably used.

5-chloro-2-methyl-4-isothiazolin-3-one and 2-methyl-4-isothiazoline-3- when the 3-isothiazolone compound of formula 1 of (a) is used in a mixture A mixture of warm is preferable, and the mixed weight ratio is preferably 1:20 to 20: 1.

In addition, the isothiazolone composition of the present invention includes the above-mentioned (b) alkali metal nitrate as a stabilizer for preventing decomposition of isothiazolone.

In order to suppress the precipitation formation of the isothiazolone composition, metal nitrates, which are widely used in general, magnesium nitrate are generally used. If the amount of magnesium nitrate is less than 0.1 wt% with respect to the isothiazolone composition, there is no precipitation preventing effect. If the content exceeds 25% by weight, the solubility of magnesium nitrate decreases, and magnesium nitrate itself is precipitated, and more seriously, magnesium, a divalent metal, causes salt shock, thereby preventing stabilization of the aqueous dispersion of the polymer.

However, since the isothiazolone composition of the present invention contains alkali metal nitrate as a stabilizer instead of an alkali metal salt of a divalent metal such as magnesium nitrate which is mainly used as a stabilizer in the conventional isothiazolone composition, the isothiazolone composition of the present invention is salt shocked. The occurrence of is suppressed.

The content of the alkali metal nitrate (b) is preferably 0.1 to 25% by weight based on the isothiazolone composition. When the content of the alkali metal nitrate is less than 0.1 wt% with respect to the isothiazolone composition, it is not possible to effectively prevent the isothiazolone from being precipitated, and the content of the alkali metal nitrate is relative to the isothiazolone composition. If it exceeds 25% by weight, the solubility is lowered, there is a problem that the manufacturing cost rises and is not commercially economical.

As the alkali metal nitrate (b), lithium nitrate, sodium nitrate, potassium nitrate or a mixture thereof may be preferably used. Among them, sodium nitrate may be most preferably used.

In addition, the isothiazolone composition of the present invention includes (c) an alkali metal chloride salt produced by reaction of an alkali metal carbonate salt introduced with a pH neutralizer with hydrochloric acid.

Magnesium oxide, which is widely used as a pH neutralizer of isothiazolone composition, is present in the form of MgCl ₂ (magnesium chloride) by reacting in the composition.If the content exceeds 9% by weight of the composition, the solubility of magnesium chloride is poor. Magnesium chloride itself is not only precipitated, but more seriously, there is a problem that magnesium, which is a divalent metal, cannot cause salt shock to stabilize the aqueous dispersion of the polymer.

However, in the isothiazolone composition of the present invention, alkali metal carbonate salts are used as the pH neutralizing agent instead of magnesium oxide which is mainly used as a pH neutralizing agent of the conventional isothiazolone composition, so that the occurrence of salt shock is suppressed in the isothiazolone composition of the present invention.

The content of the alkali metal chloride salt (c) is preferably 0.001 to 20% by weight, more preferably 0.01 to 15% by weight and more preferably 0.1 to 10% by weight based on the isothiazolone composition.

(C) If the content of the alkali metal chloride salt is less than 0.001% by weight relative to the isothiazolone composition, the concentration of the alkali metal carbonate salt introduced into the pH neutralizer is too low to adjust the pH of the isothiazolone composition to a commercially available range. When the content of the alkali metal chloride salt (c) exceeds 20% by weight with respect to the isothiazolone composition, the stability of the composition is lowered and the manufacturing cost is increased, which is not commercially economical.                     

The alkali metal chloride salt (c) is preferably sodium chloride, potassium chloride or a mixture thereof produced by the addition of an alkali metal carbonate salt. The alkali metal carbonate salt added as a pH neutralizer may be preferably sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, or a mixture thereof.

In addition, the isothiazolone composition of the present invention is a stabilizer that prevents decomposition of isothiazolone, and (d) a compound selected from the group consisting of iodic acid, periodic acid, iodide and periodicate and (e) metal bromate Include.

Isothiazolone compositions form traces of precipitate during storage. This is a different form of precipitation than salt shock, in which by-products produced in the manufacturing process, compounds produced during storage, and fine precipitation by decomposition of isothiazolones occur. The precipitate is undesirable from a commercial point of view as it damages the appearance of the product.

However, the isothiazolone composition of the present invention has an advantage that the precipitate can be effectively suppressed by mixing two small amounts of additives having an excellent effect of inhibiting precipitate formation. (D) iodic acid by mixing (d) iodic acid, periodic acid, iodide, periodicate, or a mixture thereof and (e) metal bromate in appropriate proportions and concentrations. It is possible to stabilize the isothiazolone compound much more effectively than using periodic acid, iodide, periodic acid salt or a mixture thereof alone.

The content of the compound selected from the group consisting of (d) iodic acid, periodic acid, iodide and periodic acid salt is preferably 0.0001 to 0.01% by weight, more preferably 0.001 to 0.005% by weight based on the isothiazolone composition. .

(D) Problems in which the isothiazolone cannot be effectively prevented when the content of the compound selected from the group consisting of iodic acid, periodic acid, iodide and periodic acid salt is less than 0.0001% by weight relative to the isothiazolone composition If there is more than 0.01% by weight, there is a problem that the manufacturing cost rises and is not economical.

The compound (d) selected from the group consisting of iodic acid, periodic acid, iodide and periodic acid salt is lithium iodate, sodium iodate, sodium iodate, potassium iodate, or iodide Ammonium iodate, lithium periodate, sodium periodate, potassium periodate, ammonium periodate, iodide, periodic acid dihydrate Or mixtures thereof and the like are preferable, and iodic acid, periodate dihydrate, sodium iodide, potassium iodide, or a mixture thereof is more preferable.

In addition, the content of the (e) metal bromate is preferably 0.001 to 1.0% by weight, more preferably 0.001 to 0.2% by weight, still more preferably 0.001 to 0.05% by weight based on the isothiazoron composition.

If the content of the metal bromate (e) is less than 0.001% by weight with respect to the isothiazolone composition, there is a problem in that the isothiazolone may not be effectively prevented from being precipitated. There is a problem that is not.

The metal bromate (e) is preferably sodium bromate, potassium bromate or a mixture thereof.

In addition, the isothiazolone composition of the present invention comprises (f) a solvent. 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. Preferably used.

As mentioned above, preferred isothiazolone compositions of the present invention comprise (a) 0.1 to 20% by weight of 3-isothiazolone compounds; (b) 0.1 to 25% by weight of alkali metal nitrate; (c) 0.001 to 20% by weight of alkali metal chloride salt; (d) 0.0001 to 0.01 weight percent of a compound selected from the group consisting of iodic acid, periodic acid, iodide and periodicate; (e) 0.001 to 1.0 weight percent of metal bromate; And (f) the remainder of the solvent.

The present invention also provides (i) 0.1 to 20% by weight of (a) 3-isothiazolone compound of formula (1); (b) 0.1 to 25% by weight of alkali metal nitrate; (C) adding 0.001 to 20% by weight of an alkali metal carbonate salt to (f) the remainder of the solvent to prepare a mixed solution; And (ii) 0.0001 to 0.01 weight percent of a compound selected from the group consisting of (d) iodic acid, periodic acid, iodide and periodate; And (e) adding 0.001% to 1.0% by weight of a metal bromate to the mixed solution of step (iii) to prepare a 3-isothiazolone composition.

[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.

As the 3-isothiazolone compound of the formula (1) of (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-isothia Zolon, benzisothiazolone, mixtures thereof, and the like can be preferably used.

Moreover, in the stabilization method of the isothiazolone of this invention, (c) alkali metal carbonate salt is added as a pH neutralizing agent. The (c) alkali metal carbonate salt added at this time is present in the form of an alkali metal chloride salt by reacting with hydrochloric acid in the isothiazolone composition.

The amount of the (c) alkali metal carbonate salt added is preferably 0.01 to 15% by weight, more preferably 0.1 to 10% by weight based on the isothiazolone composition.

The alkali metal carbonate salt (c) is preferably sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, or a mixture thereof.

In addition, in the stabilization method of isothiazolone of the present invention, as a precipitation stabilizer, (d) a compound selected from the group consisting of iodic acid, periodic acid, iodide and periodicate is added.

The content of the compound selected from the group consisting of (d) iodic acid, periodic acid, iodide and periodic acid salt is preferably 0.0001 to 0.01% by weight, more preferably 0.001 to 0.005% by weight based on the isothiazolone composition. .

(D) Problems in which the isothiazolone cannot be effectively prevented when the content of the compound selected from the group consisting of iodic acid, periodic acid, iodide and periodic acid salt is less than 0.0001% by weight relative to the isothiazolone composition There is a problem that, if it exceeds 0.01% by weight, the color changes over time and the manufacturing cost rises, so it is not economical.

The compound (d) selected from the group consisting of iodic acid, periodic acid, iodide and periodic acid salt is lithium iodate, sodium iodate, sodium iodate, potassium iodate, or iodide Ammonium iodate, lithium periodate, sodium periodate, potassium periodate, ammonium periodate, iodide, periodic acid dihydrate Or mixtures thereof and the like are preferable, and iodic acid, periodate dihydrate, sodium iodide, potassium iodide, or a mixture thereof is more preferable.

In addition, the content of the (e) metal bromate is preferably 0.001 to 1.0% by weight, more preferably 0.001 to 0.2% by weight, still more preferably 0.001 to 0.05% by weight based on the isothiazoron composition.

If the content of the metal bromate (e) is less than 0.001% by weight with respect to the isothiazolone composition, there is a problem in that the isothiazolone may not be effectively prevented from being precipitated. There is a problem.

The metal bromate (e) is preferably sodium bromate, potassium bromate or a mixture thereof.

In addition, as the solvent (f), water, ethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, diethylene glycol, triethylene glycol, 1,5-pentanediol, 2,4-pentanediol, benzyl alcohol or Mixtures thereof and the like can be preferably used.

Cooling towers, air washers, boilers, mineral slurries, wastewater treatment units, decorative fountains, reverse osmosis filtration systems, ultrafiltration systems, ballast water, evaporative condensers, heat exchangers, pulp and paper processing oils, plastics, emulsions and dispersants, paints, When the isothiazolone composition of the present invention is used as a biocide in a microbial habitat such as latex, a coating agent, a metal working oil, etc., it is possible to effectively inhibit or kill the growth of harmful microorganisms such as bacteria, fungi, algae and the like.

As described above, the isothiazolone composition of the present invention does not include alkaline earth metal salts of divalent metals such as magnesium chloride, which cause salt shock, so that the isothiazolone composition may be used as a disinfectant in a dispersion solution or an emulsion solution such as paint acrylate or latex. It can be effectively inhibit the growth of harmful microorganisms.

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.

(Examples 1 to 3 and Comparative Example 1)

To prepare a 3-isothiazolone concentrated solution in the composition and content as shown in Table 1, respectively. 3-isothiazolone compounds include 5-chloro-2-methyl-4-isothiazolin-3-one (CMI) and 2-methyl-4-isothiazolin-3-one (MI) as about 3: 1. What was mixed by the weight ratio of was used. Samples of Examples 1 to 3 and Comparative Example 1 are 3-isothiazolone compounds, sodium nitrate, sodium carbonate, magnesium nitrate (comparative), magnesium oxide (comparative) and water, as shown in Table 1 below. The mixture was prepared by adding KIO ₃ and NaBrO ₃ for the purpose of preventing precipitation.

                                                          (Unit: weight%) sample Isothiazolone Compound Mg (NO ₃ ) ₂ MgCl ₂ NaNO ₃ NaCl KIO ₃ NaBrO ₃ Example 1 13.84 - - 17.0 5.7 0.005 0.025 Example 2 13.84 - - 17.0 5.7 0.005 0.05 Example 3 13.84 - - 17.0 5.7 0.01 0.1 Comparative Example 1 13.84 18.2 4.9 - - - -

Alkali metal carbonate salts (sodium chloride, potassium chloride) and magnesium chloride in the samples of Examples 1 to 3 and Comparative Example 1 were produced in the composition by sodium carbonate, potassium carbonate, magnesium nitrate and magnesium oxide which are added for pH neutralization. will be.

That is, alkali metal carbonate salts (sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate) which are added as pH adjusters are present in the form of alkali metal chloride salts (NaCl, KCl) in the composition of the present invention.

(Test Example 1)

Salt Shock Generation Test

The samples prepared by the methods of Examples 1 to 3 and Comparative Example 1 were examined to determine whether the samples caused salt shock, and the results are shown in Table 2 below.

In general, a salt shock type isothiazolone composition which causes salt shock contains a large amount of magnesium ions as a stabilizer, and SiO ₂ forms a poorly soluble salt with magnesium ions under acidic conditions of pH 4 to 5. Focusing on the theory of scale formation, the samples prepared by the methods of Examples 1 to 3 and Comparative Example 1 are used as disinfectants in emulsions such as paint acrylates or latexes, which are solidified by reacting sensitively to divalent ions. It was confirmed whether this is possible, i.e., the polymer aqueous dispersion can be stabilized.

As a test method, a detection reagent was added dropwise at a rate of 5 ml to 10 ml of the isothiazolone composition solution to be tested, and then white or gray precipitates were examined. In addition, salt-type shock detection reagent was used as the aqueous solution of sodium metasilicate _{(Na 2 SiO 3 · 9H 2} O) in 5%.

sample Presence of sediment by salt shock Example 1 No precipitation after 5 ml dropping Example 2 No precipitation after 5 ml dropping Example 3 No precipitation after 5 ml dropping Comparative Example 1 Precipitate from 1 ml dropwise

As shown in Table 2, precipitation is formed in the case of the salt shock type, and precipitation is not formed in the case of the non salt shock type.

When 10 ml of the sample of Comparative Example 1 was added dropwise at 5 ml, a white or gray precipitate was formed. In contrast, no precipitation was generated even when the detection reagent was added dropwise to the sample of Example 1.

Therefore, it was confirmed that the sample of Comparative Example 1 was of the salt shock type, but the sample of Example 1 was of the non salt shock type.

In Test Example 1, a salt free type isothiazolone solution stabilized with a glycol solvent was used as a control.

1 is a photograph showing the results of the salt shock of the isothiazolone composition samples of Example 1, Comparative Example 1 and the control in Test Example 1.

2 is a photograph showing the results of the salt shock obtained by diluting the isothiazolone composition samples of Example 1 and Comparative Example 1 in Test Example 1.

As shown in FIG. 1, white or gray precipitation occurred in the sample of Comparative Example 1, and no precipitation occurred in the sample of Example 1. In addition, as shown in FIG. 2, the same experimental results were obtained even when the samples of Example 1 and Comparative Example 1 were diluted 10 times.

Therefore, it was confirmed that the isothiazolone composition which does not contain alkaline earth metal salts of divalent metals such as magnesium chloride, that is, the isothiazolone composition stabilized with alkali metal nitrates, can stabilize the aqueous dispersion of the polymer even at high concentrations. .

(Test Example 2)

Salt Shock Generation Test in Paint Acrylate Emulsions

Examine whether the samples of Examples 1 to 3 and Comparative Example 1 cause salt shock in the same manner as in Test Example 1, but in this Test Example 2 to confirm the presence of salt shock in practice, 10 ml of paint acrylate Samples of Examples 1 to 3 and Comparative Example 1 were added dropwise to the emulsion at a rate of 5 ml, and then the presence or absence of agglomeration (precipitation) due to salt shock was examined and the results are shown in Table 3 below.                     

sample Presence of tangles due to salt shock Example 1 No tangling even after 5 ml dropping Example 2 No tangling even after 5 ml dropping Example 3 No tangling even after 5 ml dropping Comparative Example 1 Tangle (precipitation) from 1 ml dropping

As shown in Table 3, in the case of the salt shock type (sedimentation) precipitates are formed, in the case of the non-salt shock type (non-salt shock type) is not formed.

In the case of Comparative Example 1, entanglement (sedimentation) due to salt shock occurred when introduced into the paint acrylate emulsion, which is an aqueous dispersion of the polymer. In contrast, in Examples 1 and 2, no agglomeration occurred.

Therefore, it was confirmed that the sample of Comparative Example 1 was of the shock shock type, but the samples of Examples 1 to 3 were of the non salt shock type.

FIG. 3 is a photograph showing salt shock results of the isothiazolone composition samples of Example 1 and Comparative Example 1 in Experimental Example 2. FIG.

As shown in FIG. 3, the paint acrylate emulsion to which the isothiazolone composition of Comparative Example 1 was heavily entangled, and the paint acrylate emulsion to which the isothiazolone composition of Example 1 was added was maintained in a solution state without entanglement. .

As can be seen in Test Example 2, the isothiazolone composition which does not contain an alkaline earth metal salt of a divalent metal such as magnesium chloride, that is, an isothiazolone composition stabilized with an alkali metal nitrate, can be used to obtain an aqueous dispersion of a polymer even at high concentrations. As it can be stabilized, it can be confirmed that it is not applicable to conventional commercial products, that is, it can be used in a process such as a down process for manufacturing a paint.

(Test Example 3)

Salt Shock Generation Test in Latex Emulsions

Examine whether the samples of Examples 1 to 3 and Comparative Example 1 cause salt shock in the same manner as in Test Example 1, but in this Test Example 3, in order to confirm whether or not the salt shock induced, 10 ml of latex emulsion Samples of Examples 1 to 3 and Comparative Example 1 were added dropwise at a rate of 5 ml, and the presence or absence of agglomeration (precipitation) due to salt shock was examined and the results are shown in Table 4 below.

sample Presence of tangles due to salt shock Example 1 No tangling even after 5 ml dropping Example 2 No tangling even after 5 ml dropping Example 3 No tangling even after 5 ml dropping Comparative Example 1 Tangle (precipitation) from 1 ml dropping

As shown in Table 4, in the case of the salt shock type (precipitation) precipitates are formed, in the case of the non-salt shock type (Non Salt shock type) is not formed.

In the case of Comparative Example 1, entanglement (settling) due to salt shock occurred when introduced into the latex emulsion, which is an aqueous dispersion of the polymer. In contrast, in Examples 1 to 3, no agglomeration occurred.

Therefore, it was confirmed that the sample of Comparative Example 1 was of the shock shock type, but the samples of Examples 1 to 3 were of the non salt shock type.

FIG. 4 is a photograph showing salt shock results of the isothiazolone composition samples of Example 1 and Comparative Example 1 in Test Example 3.

As shown in FIG. 4, the latex emulsion containing the isothiazolone composition of Comparative Example 1 was heavily entangled, and the latex emulsion into which the isothiazolone composition of Example 1 was added was maintained in solution without entanglement.

(Test Example 4)

Sediment Generation Test

Storage stability experiments were performed on the samples prepared by the methods of Examples 1 to 3 and Comparative Example 1, and the results are shown in Table 5 below.

In order to confirm the low stability, the concentration of active ingredients (MIT, CMIT) remaining in the composition was analyzed by HLPC while the isothiazolone composition (samples of Examples 1 to 3 and Comparative Example 1) was allowed to stand in an oven at 65 ° C. for 28 days. The results are shown in Table 5 below.

sample Storage days Changes in Contents of Active Ingredients at 65 ℃ MIT CMIT Sum
(CMI + MI) ratio
(CMI / MI) % Example 1 Early 3.43 10.41 13.84 3.04 100 Day 28 3.34 10.05 13.39 3.01 99 Example 2 Early 3.43 10.41 13.84 3.04 100 Day 28 3.32 10.07 13.39 3.03 100 Example 3 Early 3.43 10.41 13.84 3.04 100 Day 28 3.37 10.23 13.60 3.04 100 Comparative Example 1 Early 3.46 10.44 13.90 3.01 100 Day 28 3.10 7.30 10.39 2.36 78

As shown in Table 5, in the case of the sample of Comparative Example 1, the concentration change of the main component is large after 28 days storage at 65 ℃, accordingly the ratio of CMI / MI decreases and precipitation occurs. Among the two active ingredients of isothiazolone solution, CMIT and MIT, the stability of CMIT is lower than that of MIT, so that the ratio falls below that at initial ratio 3: 1, indicating that CMI is inactivated and precipitated.

On the other hand, the samples of Examples 1 to 3 prepared by adding KIO ₃ and NaBrO ₃ as precipitation stabilizers were significantly less changed in concentrations of the main components even after 28 days of storage, and in particular, almost no precipitate was formed due to the large CMI / MI ratio. To stabilized isothiazolone compositions.

Therefore, even if the isothiazolone composition from which the divalent metal is excluded from the experiment, a small amount of stabilized 3-isothiazolone composition can be obtained by adding a small amount of potassium iodide and metal bromate at an appropriate ratio and concentration. I could confirm it.

The isothiazolone composition of the present invention does not contain alkaline earth metal salts of divalent metals such as magnesium chloride which cause salt shock, so that the isothiazolone composition can be stably used as a disinfectant in an emulsion solution such as dispersion or paint acrylate or latex. In addition to effectively inhibiting growth, the sediment generation rate is low, and the storage stability is excellent.

Claims (14)

(a) 3-isothiazolone compound of formula 1; (b) alkali metal nitrates; (c) alkali metal chloride salts; (d) lithium iodate, sodium iodate, sodium iodate, potassium iodate, ammonium iodate, lithium periodate, sodium periodate periodate), potassium periodate, ammonium periodate, iodic acid, periodate dihydrate, or mixtures thereof, iodide, periodate, iodide and periodate Compounds selected from the group; (e) metal bromate, sodium bromate, potassium bromate or mixtures thereof; And (f) solvent Isothiazolone composition comprising: [Formula 1]

In Chemical Formula 1, R ₁ and R ₂ may each be a hydrogen atom or a halogen atom, or R ₁ and R ₂ may be combined to form a benzene ring. R ₃ is a hydrogen atom or an alkyl group of C ₁ to C ₁₈ . The method of claim 1, The isothiazolone composition is (a) 0.1 to 20% by weight of 3-isothiazolone compound; (b) 0.1 to 25% by weight of alkali metal nitrate; (c) 0.001 to 20% by weight of alkali metal chloride salt; (d) 0.0001 to 0.01 weight percent of a compound selected from the group consisting of iodic acid, periodic acid, iodide and periodicate; (e) 0.001 to 1.0 weight percent of metal bromate; And (f) solvent balance Isothiazolone composition comprising a. The method of claim 2, (C) the isothiazolone composition having an amount of the alkali metal chloride salt in an amount of 0.01 to 15% by weight based on the isothiazolone composition. The method of claim 2, (C) the isothiazolone composition having an alkali metal chloride salt content of 0.1 to 10% by weight based on the isothiazolone composition. The method of claim 2, (D) Isothiazolone composition, wherein the content of the compound selected from the group consisting of iodic acid, periodic acid, iodide and periodic acid salt is 0.001 to 0.005% by weight relative to the isothiazolone composition. The method of claim 2, The isothiazolone composition of (e) the metal bromate is 0.001 to 0.2% by weight based on the isothiazoron composition. The method of claim 2, The isothiazolone composition of (e) the metal bromate is 0.001 to 0.05% by weight based on the isothiazoron composition. The method of claim 1, The 3-isothiazolone compound of formula (1) of (a) 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 , Isothiazolone composition which is benzisothiazolone or mixtures thereof. The method of claim 1, The alkali metal nitrate of (b) is isothiazolone composition selected from the group consisting of lithium nitrate, sodium nitrate and potassium nitrate. The method of claim 1, The alkali metal salt chloride salt of (c) is isothiazolone composition selected from the group consisting of sodium chloride and potassium chloride salt. The method of claim 8, The 3-isothiazolone compound of formula 1 of (a) is a mixture of 5-chloro-2-methyl-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one, The mixing weight ratio is 1:20 to 20: 1, isothiazolone composition. delete The method of claim 1, The solvent (f) 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. (Iii) 0.1 to 20% by weight of 3-isothiazolone compound represented by the following Chemical Formula 1; (b) 0.1 to 25% by weight of alkali metal nitrate; (C) adding 0.001 to 20% by weight of an alkali metal carbonate salt to (f) the remainder of the solvent to prepare a mixed solution; And (Ii) (d) lithium iodate, sodium iodate, sodium iodate, potassium iodate, ammonium iodate, lithium periodate, and periodic acid Sodium periodate, potassium periodate, ammonium periodate, iodic acid, periodic acid dihydrate, or mixtures thereof iodide, periodic acid, iodide and periodic 0.0001 to 0.01 weight percent of a compound selected from the group consisting of acid salts; And (e) adding 0.001 to 1.0% by weight of a metal bromate, which is sodium bromate, potassium bromate, or a mixture thereof, to the mixed solution of step (iii) to prepare an isothiazolone composition. Method for stabilizing isothiazolone comprising: [Formula 1]

In Chemical Formula 1, R ₁ and R ₂ may each be a hydrogen atom or a halogen atom, or R ₁ and R ₂ may be combined to form a benzene ring. R ₃ is a hydrogen atom or an alkyl group of C ₁ to C ₁₈ .

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