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

• 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.
• 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.
• R-i and R 2 are independently a hydrogen atom, a halogen atom, or a C C alkyl group or aryl group;
• 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 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.
• 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 (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 (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 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 (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 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.
• 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.
• 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.
• 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.
• 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.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Agricultural Chemicals And Associated Chemicals (AREA)
• Thiazole And Isothizaole Compounds (AREA)
• Compositions Of Macromolecular Compounds (AREA)

Applications Claiming Priority (15)

Publications (2)

Family

ID=29587971

Family Applications (1)

Country Status (5)

Families Citing this family (15)

Citations (1)

Family Cites Families (13)

• 2003
  • 2003-05-28 CN CNB038181568A patent/CN100400521C/zh not_active Expired - Fee Related
  • 2003-05-28 WO PCT/KR2003/001047 patent/WO2003099799A1/en active IP Right Grant
  • 2003-05-28 EP EP03755296A patent/EP1507771A4/de not_active Withdrawn
  • 2003-05-28 AU AU2003232654A patent/AU2003232654B2/en not_active Ceased
  • 2003-05-28 JP JP2004507456A patent/JP2005527626A/ja active Pending

Patent Citations (1)

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events