EP1507771A4 - Isothiazolonzusammensetzung und verfahren zur stabilisierung von isothiazolon - Google Patents

Isothiazolonzusammensetzung und verfahren zur stabilisierung von isothiazolon

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Publication number
EP1507771A4
EP1507771A4 EP03755296A EP03755296A EP1507771A4 EP 1507771 A4 EP1507771 A4 EP 1507771A4 EP 03755296 A EP03755296 A EP 03755296A EP 03755296 A EP03755296 A EP 03755296A EP 1507771 A4 EP1507771 A4 EP 1507771A4
Authority
EP
European Patent Office
Prior art keywords
isothiazolone
group
stabilizing
isothiazolone composition
composition
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP03755296A
Other languages
English (en)
French (fr)
Other versions
EP1507771A1 (de
Inventor
Wan-Pyo Hong
Jin-Man Kim
Ki-Seung Choi
Jin-Ho Kim
Ki-Man Park
Hi-Weon Jung
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
SK Chemicals Co Ltd
Original Assignee
SK Chemicals Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from KR1020020062096A external-priority patent/KR20030093086A/ko
Application filed by SK Chemicals Co Ltd filed Critical SK Chemicals Co Ltd
Publication of EP1507771A1 publication Critical patent/EP1507771A1/de
Publication of EP1507771A4 publication Critical patent/EP1507771A4/de
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D275/00—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings
    • C07D275/02—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings not condensed with other rings
    • C07D275/03—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D275/00—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings
    • C07D275/04—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings condensed with carbocyclic rings or ring systems
    • C07D275/06—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings condensed with carbocyclic rings or ring systems with hetero atoms directly attached to the ring sulfur atom

Definitions

  • the present invention relates to an isothiazolone composition and a method for stabilizing the same, and more specifically to an isothiazolone composition that does not comprise a divalent alkali earth metal salt such as magnesium chloride, which causes salt shock, and thus can be stably used for a sterilizer in a dispersion or an emulsion such as paint acrylate or latex, etc., therefore effectively preventing the growth of microorganisms, and that has superior storage stability due to its low rate of precipitation formation.
  • Isothiazolone which has extensive sterilizing activity for many harmful organisms originating from animals and plants such as bacteria, mold, algae, etc., is added to cosmetics, paints, etc. as an inhibitor for the growth of harmful microorganisms.
  • US Patent No. 3,870,785 has suggested a method of adding a metal nitrate salt, a nitrite salt, etc. to the composition as a stabilizer.
  • US Patent No. 4,165,318 has suggested a method of adding formaldehyde or a formaldehyde-eluting material to an isothiazolone composition as a stabilizer.
  • US Patent No. 4,824,957 has suggested a method of adding an organic hydroxylic solvent to an isothiazolone composition as a stabilizer.
  • a dispersion or an emulsion such as paint acrylate or latex, etc.
  • a sterilizer comprising salts of divalent ions which cause coagulation.
  • sterilization active ingredients may be incorporated into the coagulation, thus the sterilization active ingredient may be reduced or removed if a product to be stored is filtered.
  • a metal nitrate salt particularly magnesium chloride or magnesium nitrate
  • a 3-isothiazolone composition as a stabilizer.
  • a commonly used isothiazolone composition comprises 1 to 20 wt% of isothiazolone and 15 to 25 wt% of a nitrate salt.
  • isothiazolone compositions comprise divalent metal, particularly magnesium oxide, as a pH-neutralizing agent.
  • divalent metal particularly magnesium oxide
  • an isothiazolone composition comprising a substantial amount of a divalent metal salt such as magnesium oxide cannot be preferably used for a sterilizer because it has a problem due to "salt shock" of bivalent metal salts.
  • the present invention relates to an isothiazolone composition and a method for stabilizing the same, and more specifically to an isothiazolone composition that does not comprise a divalent alkali earth metal salt such as magnesium chloride, which causes salt shock, and thus that can be stably used for a sterilizer in a dispersion or an emulsion such as paint acrylate or latex, etc., therefore effectively preventing the growth of microorganisms, and that has superior storage stability due to its low rate of precipitation formation.
  • a divalent alkali earth metal salt such as magnesium chloride
  • Fig. 1 is a photograph showing salt shock results of isothiazolone compositions of Example 1 , Comparative Example 1 , and a Control according to Experiment 1.
  • Fig. 2 is a photograph showing salt shock results of 10-fold dilutions of the isothiazolone compositions of Example 1 and Comparative Example 1 according to Experiment 1.
  • Fig. 3 is a photograph showing salt shock results of isothiazolone compositions of Example 1 and Comparative Example 1 according to Experiment 2 (paint acrylate emulsion).
  • Fig. 4 is a photograph showing the salt shock results of the isothiazolone compositions of Example 1 and Comparative Example 1 according to Experiment 3 (latex emulsion).
  • the present invention is made to solve the above-mentioned problems, and it is an object of the present invention to provide an isothiazolone composition that does not comprise an alkali earth metal salt of a divalent metal such as magnesium chloride, which causes salt shock, and thus can be stably used for a microorganism inhibitor in a dispersion or an emulsion such as paint acrylate or latex, etc., therefore effectively preventing the growth of harmful microorganisms, and that has superior storage stability because it comprises appropriate ratios of three kinds of stabilizers having synergy for increasing stability of an isothiazolone solution, and thus has a low rate of precipitation formation even at a much lower concentration than those disclosed in the prior art.
  • an isothiazolone composition comprising (a) a 3-isothiazolone compound represented by the following Chemical Formula 1 ; (b) an alkali metal nitrate salt; (c) an alkali metal chloride salt; and (d) a solvent: [Chemical Formula 1]
  • R-i and R 2 are independently a hydrogen atom, a halogen atom, or a C C alkyl group or aryl group;
  • R 3 is a hydrogen atom, a C ⁇ -C-
  • the present invention also provides a method for stabilizing isothiazolone comprising the step of adding (a) 0.1 to 20 wt% of a 3- isothiazolone compound represented by the above Chemical Formula 1; (b) 0.1 to 25 wt% of an alkali metal nitrate salt; and (c) 0.001 to 20 wt% of an alkali metal carbonate salt to (d) a solvent making up the balance to prepare a mixed solution: [Chemical Formula 1]
  • Ri and R 2 are independently a hydrogen atom, a halogen atom, or a C ⁇ -C alkyl group or aryl group; and,
  • R 3 is a hydrogen atom, a CrC 18 alkyl group, a C 2 -C 18 alkenyl group, a C 2 -Ci 8 alkinyl group, a C 3 -C* ⁇ 2 cycloalkyl group having trigonal to octagonal rings, a C 10 -C 24 aralkyl group, or a C ⁇ o-C 24 aryl group.
  • the present invention will now be explained in detail.
  • the present invention is characterized by comprising (a) a 3- isothiazolone compound represented by the following Chemical Formula 1 ; (b) an alkali metal nitrate salt; (c) an alkali metal chloride salt; and (d) a solvent as essential ingredients: [Chemical Formula 1]
  • Ri and R 2 are independently a hydrogen atom, a halogen atom, a
  • R 3 is a hydrogen atom, a C ⁇ -C ⁇ 8 alkyl group, a C 2 -C* ⁇ 8 alkenyl group, a C 2 -C-i 8 alkinyl group, a C 3 -d 2 cycloalkyl group having trigonal to octagonal rings, a C ⁇ 0 -C 24 aralkyl group, or C* ⁇ 0 -C 24 aryl group.
  • the (a) 3-isothiazolone compound which has extensive sterilizing activity for many harmful microorganisms originating from animals and plants such as bacteria, mold, algae, etc., is added to cosmetics, paints, etc. to be used for an inhibitor for growth of harmful microorganisms.
  • the (a) 3-isothiazolone compound of the above Chemical Formula 1 is preferably contained in an amount of 0.1 to 20 wt% in the isothiazolone composition of the present invention. If the content of the (a) 3- isothiazolone compound is less than 0.1 wt%, the resulting isothiazolone composition cannot be commercially used because of a low content of sterilizer. And, if the content exceeds 20 wt%, stability becomes deteriorated.
  • the isothiazolone composition of the present invention comprises the (b) alkali metal nitrate salt as a stabilizer for preventing decomposition of isothiazolone.
  • a metal nitrate salt In order to prevent formation of a precipitation of the isothiazolone composition, a metal nitrate salt has been widely used, generally magnesium nitrate.
  • the content of the magnesium nitrate is less than 0.1 wt% of the isothiazolone composition, precipitation-preventing effects cannot be anticipated, and if it exceeds 25 wt%, solubility of magnesium nitrate decreases to cause precipitation of magnesium nitrate itself, and worse, divalent ion magnesium causes salt shock and thus aqueous polymer dispersion cannot be stabilized.
  • the isothiazolone composition of the present invention comprises an alkali metal nitrate salt as a stabilizer, instead of an alkali earth metal salt of a divalent metal such as magnesium nitrate that has been predominantly used as a stabilizer in an isothiazolone composition of the prior art, salt shock is inhibited which makes the isothiazolone composition stable.
  • the content of the (b) alkali metal nitrate salt is preferably 0.1 to 25 wt% of the isothiazolone composition. If the content is less than 0.1 wt%, precipitation of isothiazolone cannot be effectively prevented, and if it exceeds 25 wt%, solubility decreases and product cost increases, making the composition uneconomical.
  • lithium nitrate, sodium nitrate, potassium nitrate, or a mixture thereof can be preferably used, and sodium nitrate is most preferable.
  • the isothiazolone composition of the present invention comprises (c) an alkali metal chloride salt that is produced by the reaction of an alkali metal introduced as a pH neutralizing agent with chloric acid.
  • Magnesium oxide which has been widely used as a pH neutralizing agent of an isothiazolone composition, reacts in the composition to exist in the form of MgCI2 (magnesium chloride). If the content of the MgCI2 exceeds 9 wt% of the composition, solubility of magnesium chloride decreases to cause precipitation of magnesium chloride itself, and more seriously, divalent metal magnesium causes salt shock and thus the aqueous polymer dispersion cannot be stabilized.
  • the isothiazolone composition of the present invention comprises an alkali metal carbonate salt as a pH- neutralizing agent, instead of magnesium oxide that has been predominantly used as a pH-neutralizing agent of an isothiazolone composition, salt shock is prevented.
  • the (c) alkali metal chloride salt is preferably contained in an amount of 0.001 to 20 wt% of the isothiazolone composition, more preferably in an amount of 0.01 to 15 wt%, and most preferably 0.1 to 10 wt%. If the content is less than 0.001 wt%, the pH of the resulting isothiazolone composition cannot be controlled within a commercially acceptable range because the concentration of the alkali metal carbonate salt introduced as a pH-neutralizing agent is too low, and if the content exceeds 20 wt%, stability of the composition decreases and product cost increases, thus making the composition uneconomical.
  • the (c) alkali metal chloride salt is preferably sodium chloride, or potassium chloride with an alkali metal carbonate salt introduced thereto, or a mixture thereof.
  • the alkali metal carbonate salt introduced as a pH- neutralizing agent is preferably sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, or a mixture thereof.
  • the isothiazolone composition comprises a (d) solvent.
  • the solvent water, ethyleneglycol, propyleneglycol, dipropyleneglycol, polypropyleneglycol, diethyleneglycol, triethyleneglycol, 1 ,5-pentanediol, 2,4-pentanediol, benzyl alcohol or a mixture thereof can be preferably used.
  • the isothiazolone composition of the present invention may further comprise (e) iodic acid, periodic acid, iodate, periodate or a mixture thereof; (f) a metal bromic acid; and (g) chlorite salt, alone or in combination of appropriate ratios, as a stabilizer for preventing the decomposition of isothiazolone. More preferably, a combination of the three kinds of precipitation- preventing agents is added.
  • the present invention can effectively inhibit the precipitation by introducing a small amount of a mixture of three kinds of additives having superior effects for inhibiting formation of a precipitation to the isothiazolone composition.
  • the isothiazolone composition can be more effectively stabilized by using a mixture of compounds selected from a group consisting of (e) iodic acid, periodic acid, iodate salt, periodate salt, or a mixture thereof; (f) a metal bromic acid salt; and (g) chlorite salt, than by using the compound of (e), (f), and (g) alone.
  • the (e) iodic acid, periodic acid, iodate, periodate, or a mixture thereof is preferably contained in an amount of 0.0001 to 0.01 wt% of the isothiazolone composition, more preferably 0.001 to 0.005 wt%. If the content is less than 0.0001 wt%, precipitation of the isothiazolone compound cannot be effectively prevented, and if it exceeds 0.01 wt%, production cost increases, thus making the composition uneconomical.
  • the (e) iodic acid, periodic acid, iodate, periodate, or a mixture thereof is preferably selected from a group consisting of lithium iodate, sodium iodate, potassium iodate, ammonium iodate, lithium periodate, sodium periodate, potassium periodate, ammonium periodate, iodic acid, periodic acid dihydrate, or a mixture thereof, and more preferably iodic acid, periodic acid dihydrate, sodium iodic acid, potassium iodic acid or a mixture thereof.
  • the (f) metal bromic acid, the other precipitation-preventing agent is preferably contained in an amount of 0.001 to 1.0 wt% of the isothiazolone composition, more preferably 0.01 to 0.2 wt%. If the content is less than 0.001 wt%, precipitation of isothiazolone cannot be effectively prevented, and if it exceeds 1.0 wt%, production cost increases, thus making the composition uneconomical.
  • the (f) metal bromic acid salt is preferably selected from a group consisting of sodium bromate, potassium bromate and a mixture thereof.
  • the (g) chlorite salt, the other precipitation-preventing agent is preferably contained in an amount of 0.001 to 10 wt%, more preferably 0.01 to 1.0 wt%, and most preferably 0.05 to 0.2 wt%. If the content is less than 0.001 wt%, precipitation of the isothiazolone cannot be effectively prevented, and if it exceeds 10 wt%, the production cost increases, thus making the composition uneconomical.
  • the (g) chlorite salt is preferably sodium chlorite, potassium chlorite or a mixture thereof.
  • the isothiazolone composition of the present invention preferably comprises (a) 0. to 20 wt% of a 3-isothiazolone compound; (b) 0.1 to 25 wt% of an alkali metal nitrate salt; (c) 0.001 to 20 wt% of an alkali metal chloride salt; and (d) a solvent making up the balance, and the three kinds of precipitation-preventing agents of (e), (f), and (g) alone or in combination.
  • the three kinds of precipitation- preventing agents preferably comprise (e) 0.0001 to 0.01 wt% of iodic acid, periodic acid, iodate, periodate, or a mixture thereof; (f) 0.01 to 1.0 wt% of a metal bromic acid salt; and (g) 0.001 to 10 wt% of chlorite salt.
  • the present invention also provides a method for stabilizing the isothiazolone composition
  • a method for stabilizing the isothiazolone composition comprising the step of (i) adding (a) 0.1 to 20 wt% of a 3-isothiazolone compound represented by the following Chemical Formula 1 ; (b) 0.1 to 25 wt% of an alkali metal nitrate salt; and (c) 0.001 to 20 wt% of an alkali metal carbonate salt to (d) a solvent making up the balance, to prepare a mixed solution of the isothiazolone composition: [Chemical Formula 1]
  • Ri and R 2 are independently a hydrogen atom, a halogen atom, or a C* ⁇ -C 4 alkyl group or aryl group; and, R 3 is a hydrogen atom, a C* ⁇ -C ⁇ 8 alkyl group, a C 2 -C- ⁇ s alkenyl group, a C 2 -Ci 8 alkinyl group, a C 3 -C ⁇ 2 cycloalkyl group having trigonal to ocgonal rings, a C ⁇ 0 -C 24 aralkyl group, or a C* ⁇ 0 -C 24 aryl group.
  • the (a) 3-isothiazolone compound is preferably selected from a group consisting of 5-chloro-2-methyl-4-isothiazolin-3-on, 2-methyl-4- isothiazolin-3-on, 4,5-dichloro-2-methyl-4-isothiazolin-3-on, 5-chloro-2-n- octyl-3-isothiazolone, 4,5-dichloro-2-n-octyl-3-isothiazolone, benzisothiazolone, or a mixture thereof.
  • the (c) alkali metal carbonate salt is added as a pH-neutralizing agent.
  • the introduced alkali metal carbonate salt reacts with chloric acid in the isothiazolone composition to exist in the form of an alkali metal chloride salt.
  • the (c) alkali metal carbonate is preferably introduced in an amount of 0.01 to 15 wt% of the isothiazolone composition, more preferably 0.1 to 10 wt%.
  • the (c) alkali metal carbonate is preferably sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate or a mixture thereof.
  • the (d) solvent is preferably selected from a group consisting of water, ethyleneglycol, propyleneglycol, dipropyleneglycol, polypropyleneglycol, diethyleneglycol, triethyleneglycol, 1 ,5-pentanediol, 2,4-pentanediol, benzyl alcohol or a mixture thereof.
  • the method for stabilizing isothiazolone further adds a compound selected from a group consisting of (e) iodic acid, periodic acid, iodate, periodate or a mixture thereof; (f) a metal bromate; (g) chlorite salt, and a mixture thereof to the isothiazolone composition as a precipitation-preventing agent to further stabilize the isothiazolone composition.
  • a compound selected from a group consisting of (e) iodic acid, periodic acid, iodate, periodate or a mixture thereof; (f) a metal bromate; (g) chlorite salt, and a mixture thereof to the isothiazolone composition as a precipitation-preventing agent to further stabilize the isothiazolone composition.
  • the mixture of two or more kinds of precipitation-preventing agents, which have different operation mechanisms, are preferably added in appropriate ratios.
  • the (e) iodic acid, periodic acid, iodate, periodate, or a mixture thereof is preferably added in an amount of 0.0001 to 0.01 wt% of the isothiazolone composition, more preferably 0.001 to 0.005 wt%. If the content is less than 0.0001 wt%, precipitation of isothiazolone cannot be effectively prevented, and if it exceeds 0.01 wt%, the color changes with the passage of time, and production cost increases thus making the method uneconomical.
  • the (e) iodic acid, periodic acid, iodate, periodate or a mixture thereof is preferably selected from a group consisting of lithium iodate, sodium iodate, potassium iodate, ammonium iodate, lithium periodate, sodium periodate, potassium periodate, ammonium periodate, iodic acid, periodic acid dihydrate or a mixture thereof, and iodic acid, periodic acid dihydrate, sodium iodic acid, potassium iodic acid or a mixture thereof are more preferable.
  • the (f) metal bromate is preferably added in an amount of 0.001 to 1.0 wt% of the isothiazolone composition, more preferably 0.001 to 0.2 wt%. If the content is less than 0.001 wt%, precipitation of isothiazolone cannot be effectively prevented, and if it exceeds 0.2 wt%, production cost increases, thus making the method uneconomical.
  • the (f) metal bromate is preferably selected from a group consisting of sodium bromate, potassium bromate and a mixture thereof.
  • the (g) chlorite salt is preferably added in an amount of 0.001 to 10 wt% of the isothiazolone composition, more preferably 0.01 to 1.0 wt%, and most preferably 0.05 to 0.2 wt%. If the content is less than 0.001 wt%, precipitation of isothiazolone cannot be effectively prevented, and if it exceeds 10 wt%, production cost increases, thus making the method uneconomical.
  • the (g) chlorite salt is preferably selected from sodium chlorite, potassium chlorite and a mixture thereof.
  • the isothiazolone composition of the present invention can be stably used in a dispersion or emulsion such as paint acrylate or latex, etc. because it does not comprise a divalent metal alkali earth metal salt such as magnesium chloride, which causes salt shock, therefore effectively inhibiting the growth of harmful microorganisms.
  • the isothiazolone composition of the present invention can be used for a microorganism inhibitor in microorganism habitats such as a cooling water tower, an air washer, a boiler, a mineral slurry, a wastewater disposal plant, a decorative fountain, a reversed osmotic filtration system, an ultrafiltration system, ballast water, an evaporation condenser, a heat exchanger, and for pulp and paper processing oils, plastics, emulsions and dispersants, paint, latex, coating agents metal processing oils, etc., to effectively inhibit the growth of harmful microorganisms such as bacteria, mold, algae, etc.
  • a microorganism inhibitor in microorganism habitats such as a cooling water tower, an air washer, a boiler, a mineral slurry, a wastewater disposal plant, a decorative fountain, a reversed osmotic filtration system, an ultrafiltration system, ballast water, an evaporation condenser, a heat exchanger, and for pulp and paper processing oils
  • 3-isothiazolone solutions were prepared with the compositions and contents given in the following Table 1.
  • 3- isothiazolone compound a mixture of 5-chloro-2-methyl-4-isothiazolin-3-on (CMI) and 2-methyl-4-isothiazolin-3-on (Ml) with the mixing ratio of approximately 3:1 was used.
  • Example 1 As described in Table 1 , the samples of Examples 1 to 13 and Comparative Example 1 were prepared by mixing the 3-isothiazolone compound, sodium nitrate, sodium carbonate, magnesium nitrate (Comparative Example), magnesium oxide (Comparative Example), and water and adding KI0 3 , NaBr0 3 , and NaCI0 2 for preventing precipitation. [Table 1] (wt%)
  • the alkali metal carbonate (sodium chloride, potassium chloride) and magnesium chloride are those produced in the composition by sodium carbonate, potassium carbonate, magnesium nitrate and magnesium oxide introduced for pH neutralization.
  • the alkali metal carbonate (sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate) introduced as a pH-neutralizing agent exists in the form of an alkali metal chloride salt (NaCI, KCI) in the composition of the present invention.
  • NaCI, KCI alkali metal chloride salt
  • an isothiazolone composition causing salt shock comprises many magnesium ions as a stabilizer. It was confirmed whether or not samples prepared according to Examples 1 to 13 and Comparative Example 1 can be used as a sterilizer for a dispersion or emulsion such as paint acrylate or latex, etc. that sensitively reacts with divalent ions and coagulates, that is, whether or not they can stabilize a polymer aqueous dispersion.
  • the salt shock composition forms precipitation, and the non salt shock types did not form precipitation.
  • Example 1 is of a salt shock type, and that of Example 1 is of a non salt shock type.
  • Fig. 1 is a photo showing the salt shock results of isothiazolone composition samples of Example 1 , Comparative Example 1 , and a control, in Experiment 1.
  • Fig. 2 is a photo showing the salt shock results of 10- fold dilutions of isothiazolone composition samples of Example 1, and Comparative Example 1 in Experiment 1.
  • the isothiazolone composition that does not comprise an alkali earth metal salt of a divalent metal such as magnesium chloride that is, an isothiazolone composition stabilized by an alkali metal nitrate salt, can stabilize a polymer aqueous dispersion of a high concentration.
  • Fig. 3 is a photo showing the salt shock results of isothiazolone composition samples of Example 1 and Comparative Example 1.
  • an isothiazolone composition that does not comprise an alkali earth metal salt of a divalent metal such as magnesium chloride, that is, an isothiazolone composition stabilized by an alkali metal nitrate salt can stabilize a polymer aqueous dispersion of a high concentration, and thus it can be used for a process such as let down during preparation of paint, to which the existing commercial products cannot be applied.
  • the salt shock type composition formed coagulation (precipitation), but the non salt shock type compositions did not form coagulation (no precipitation).
  • Comparative Example 1 formed coagulation (precipitation) by salt shock, when introduced in a polymer aqueous dispersion of latex emulsion.
  • those of Examples 1 to 13 did not form coagulation (no precipitation).
  • Comparative Example 1 is of a salt shock type, but those of Examples 1 to 13 are of non salt shock types.
  • Fig. 4 is a photo showing the salt shock results of isothiazolone composition samples of Example 1 and Comparative Example 1 in Experiment 3.
  • the sample of Comparative Example 1 showed a large change in concentration of main ingredients after being stored at 65 ° C for 28 days, thus the ratio of CMI/MI decreased and precipitate formed. Since, of the two main ingredients of the isothiazolone solution, i.e. CMIT and MIT, the stability of CMIT is lower than that of MIT, the result that the initial ratio of 3:1 decreased means that CMI precipitated by the amount of decrease.
  • Examples 1 to 13 which were prepared by adding KI0 3 , NaBr0 3 , and NaCI0 2 as stabilizers, showed minor changes in concentrations of main ingredients after being stored for 28 days, and particularly when the mixture of KI0 3 , NaBr0 3 and NaCI0 2 of appropriate ratios were added, there was little change of concentrations of main ingredients, and the ratio of CMI/MI was large, hence a stabilized isothiazolone composition in which precipitation does not occur could be obtained.
  • the isothiazolone compostion of the present invention can be stably used as a sterilizer in a dispersion or emulsion such as paint acrylate or latex, etc. because it does not include an alkali earth metal salt of a divalent metal such as magnesium chloride, which causes salt shock, and thus it can effectively inhibit growth of harmful microorganisms, and it has superior storage stability due to its low precipitation forming rate.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Thiazole And Isothizaole Compounds (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
EP03755296A 2002-05-29 2003-05-28 Isothiazolonzusammensetzung und verfahren zur stabilisierung von isothiazolon Withdrawn EP1507771A4 (de)

Applications Claiming Priority (15)

Application Number Priority Date Filing Date Title
KR20020030023 2002-05-29
KR2002030023 2002-05-29
KR1020020062096A KR20030093086A (ko) 2002-05-29 2002-10-11 이소티아졸론 조성물 및 이소티아졸론의 안정화 방법
KR2002062096 2002-10-11
KR2002076857 2002-12-05
KR1020020076857A KR20030093087A (ko) 2002-05-29 2002-12-05 이소티아졸론 조성물 및 이소티아졸론의 안정화 방법
KR2003018625 2003-03-25
KR1020030018624A KR100975372B1 (ko) 2002-05-29 2003-03-25 이소티아졸론 조성물 및 이소티아졸론의 안정화 방법
KR2003018624 2003-03-25
KR1020030018625A KR100975373B1 (ko) 2002-05-29 2003-03-25 이소티아졸론 조성물 및 이소티아졸론의 안정화 방법
KR2003028973 2003-05-07
KR1020030028973A KR100975374B1 (ko) 2002-05-29 2003-05-07 이소티아졸론 조성물 및 이소티아졸론의 안정화 방법
KR1020030028974A KR100975375B1 (ko) 2002-05-29 2003-05-07 이소티아졸론 조성물 및 이소티아졸론의 안정화 방법
KR2003028974 2003-05-07
PCT/KR2003/001047 WO2003099799A1 (en) 2002-05-29 2003-05-28 Isothiazolone composition and method for stabilizing isothiazolone

Publications (2)

Publication Number Publication Date
EP1507771A1 EP1507771A1 (de) 2005-02-23
EP1507771A4 true EP1507771A4 (de) 2006-08-30

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EP (1) EP1507771A4 (de)
JP (1) JP2005527626A (de)
CN (1) CN100400521C (de)
AU (1) AU2003232654B2 (de)
WO (1) WO2003099799A1 (de)

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JP5194205B2 (ja) * 2004-02-19 2013-05-08 住化エンビロサイエンス株式会社 工業用抗菌組成物
JP5101826B2 (ja) * 2006-02-28 2012-12-19 日本曹達株式会社 イソチアゾロン系化合物を含有する水溶性製剤およびイソチアゾロン系化合物の安定化方法
AU2007202261B2 (en) * 2006-06-02 2012-06-28 Rohm And Haas Company Microbicidal composition
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CN103030733B (zh) * 2012-12-06 2014-12-10 青岛大学 一种侧链含苯异噻唑啉酮的聚丙烯酸酯防污共聚树脂及其制备方法
CN103319433A (zh) * 2013-07-08 2013-09-25 王建国 一种cmi工业杀菌剂的生产工艺
CN106472520A (zh) * 2016-09-23 2017-03-08 江苏辉丰农化股份有限公司 一种农药组合物
ES2885008T3 (es) * 2017-04-04 2021-12-13 Thor Gmbh Composición biocida estabilizada
KR102541313B1 (ko) 2018-01-12 2023-06-13 후지필름 가부시키가이샤 약액, 기판의 처리 방법
JP7043366B2 (ja) * 2018-08-08 2022-03-29 エステー株式会社 固形揮散製剤
CN109964947A (zh) * 2019-04-12 2019-07-05 嘉兴沃特泰科环保科技有限公司 非氧化杀菌剂
CN110037041A (zh) * 2019-04-30 2019-07-23 三河市霍夫曼化学品制造有限公司 一种异噻唑啉酮类复配微乳型杀菌防霉剂、其制备方法及应用
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EP1507771A1 (de) 2005-02-23
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