CN100400521C - Isothiazolone composition and method for stabilizing isothiazolone - Google Patents
Isothiazolone composition and method for stabilizing isothiazolone Download PDFInfo
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- CN100400521C CN100400521C CNB038181568A CN03818156A CN100400521C CN 100400521 C CN100400521 C CN 100400521C CN B038181568 A CNB038181568 A CN B038181568A CN 03818156 A CN03818156 A CN 03818156A CN 100400521 C CN100400521 C CN 100400521C
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- isothiazoline
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- 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
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- 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
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Abstract
The present invention relates to an isothiazolone composition and a method for stabilizing the same, and particularly to an isothiazolone composition that does not comprise alkali earth metal salt of a divalent metal such as magnesium chloride, which causes salt shock, and thus that can be stably used as a sterilizer in a dispersion or emulsion such as paint acrylate or latex, therefore effectively preventing growth of microorganisms, and that has superior storage stability due to its low precipitation formation rate because it comprises a precipitation-preventing agent, and a method for stabilizing the same.
Description
Background of invention
(a) invention field
The present invention relates to the method for isothiazoline one compositions and stable isothiazolinone.Specifically, the present invention relates to a kind of isothiazoline one compositions, wherein do not contain the divalent alkaline-earth metal salt such as the magnesium chloride that can cause salt bunch, therefore in dispersion liquid or emulsion such as acrylate paint or latex etc., can stably be used as sterilant, thereby can effectively prevent microbial growth, because it is low that said composition forms sedimentary speed, therefore has excellent stability in storage.
(b) explanation of correlation technique
Isothiazolinone has the broad-spectrum sterilization activity to many harmful organisms of being derived from animal and plant such as bacterium, mould, algae etc., and it is added in makeup, the coating etc. as inhibitor, can suppress the harmful microbe growth.
But, decompose because isothiazolinone is understood as alcohol or in water at polar organic solvent, so As time goes on its biological activity can reduce.Therefore, the stability that improves isothiazolinone in polar organic solvent or water has been carried out big quantity research.
In order to improve the stability of isothiazolinone in polar organic solvent or water, United States Patent (USP) 3870785 has proposed to add the method as stablizer such as metal nitrate, nitrite in composition.United States Patent (USP) 4165318 has proposed to add the method for the material of formaldehyde or release formaldehyde as stablizer in the isothiazoline one compositions.In addition, United States Patent (USP) 4824957 has proposed to add the method for organic hydroxylic solvent as stablizer in the isothiazoline one compositions.
But, because a variety of causes, the preferred amount that reduces the stablizer that is used for the stable sterilant that comprises iso thiazoline ketone compound.
For example, dispersion liquid or emulsion such as acrylate paint or latex etc. need prevent variation and the decomposition that microorganism is caused, and this dispersion liquid or emulsion and salt anaphylaxis particularly can not mix well with the sterilant that contains the divalent ion salt that can cause coagulation.In addition, fungicide active ingredient can participate in coagulation, therefore, if product that will be to be stored filters, then may reduce fungicide active ingredient or it is removed.
At present, add metal nitrate as stablizer, particularly add magnesium chloride or magnesium nitrate as stablizer to 3-isothiazoline one compositions.Isothiazoline one compositions commonly used comprises the isothiazolinone of 1-20wt% and the nitrate of 15-25wt%.
The isothiazoline one compositions also comprises the divalent metal as the pH neutralizing agent, particularly magnesium oxide.But, contain a large amount of divalent metal salts such as magnesian isothiazoline one compositions preferably is not used in sterilant, because it is because " salt bunch " of divalent metal salt and will going wrong.
Summary of the invention
The present invention relates to the method for isothiazoline one compositions and stable isothiazolinone.More particularly, the present invention relates to a kind of isothiazoline one compositions, wherein do not contain the divalent alkaline-earth metal salt such as the magnesium chloride that can cause salt bunch (salt shock), therefore in dispersion liquid or emulsion such as acrylate paint or latex etc., can stably be used as sterilant, thereby can effectively prevent microbial growth, because it is low that said composition forms sedimentary speed, therefore has excellent stability in storage.
The accompanying drawing summary
Fig. 1 illustrates the photo of the isothiazoline one compositions of embodiment 1, comparative example 1 and contrast according to the salt bunch result of test 1.
Fig. 2 illustrates 10 times of diluents of isothiazoline one compositions of embodiment 1 and comparative example 1 according to test 1 salt bunch result's photo.
Fig. 3 illustrates the photo of embodiment 1 and comparative example's 1 isothiazoline one compositions according to the salt bunch result of test 2 (acrylate paint emulsions).
Fig. 4 illustrates the photo of embodiment 1 and comparative example's 1 isothiazoline one compositions according to the salt bunch result of test 3 (latex).
Detailed description of preferred embodiments
The present invention finishes in order to address the above problem, an object of the present invention is to provide a kind of isothiazoline one compositions, wherein do not contain the divalent alkaline-earth metal salt such as the magnesium chloride that can cause salt bunch, therefore in dispersion liquid or emulsion such as acrylate paint or latex etc., can stably be used as microbial inhibitor, thereby can effectively prevent the harmful microbe growth, because said composition contains the stablizer that increases isothiazolinone stability of solution synergy that has of three kinds of proper ratio, so even the concentration of the disclosed composition of its concentration ratio prior art is much lower, it is also very low that it forms sedimentary speed, therefore has excellent stability in storage.
Another object of the present invention provides a kind of method that is used for stablizing isothiazolinone.
In order to realize these purposes, the invention provides a kind of isothiazoline one compositions, it comprises the 3-iso thiazoline ketone compound that the Chemical formula 1 below (a) is represented; (b) base metal nitrate; (c) an alkali metal salt hydrochlorate; (d) solvent:
[Chemical formula 1]
In the superincumbent Chemical formula 1,
R
1And R
2Be hydrogen atom, halogen atom or C independently
1-C
4Alkyl or aryl; With
R
3Be hydrogen atom, C
1-C
18Alkyl, C
2-C
18Thiazolinyl, C
2-C
18Alkynyl, have the C of trilateral to the octagon ring
3-C
12Cycloalkyl, C
10-C
24Aralkyl or C
10-C
24Aryl.
The present invention also provides a kind of method that is used for stablizing isothiazolinone, comprises the steps: the 3-iso thiazoline ketone compound that the top Chemical formula 1 of (a) 0.1-20wt% is represented; (b) base metal nitrate of 0.1-25wt%; (c) alkaline carbonate of 0.001-20wt% adds in the solvent of (d) equal amount, the preparation mixing solutions:
[Chemical formula 1]
In the superincumbent Chemical formula 1,
R
1And R
2Be hydrogen atom, halogen atom or C independently
1-C
4Alkyl or aryl; With
R
3Be hydrogen atom, C
1-C
18Alkyl, C
2-C
18Thiazolinyl, C
2-C
18Alkynyl, have the C of trilateral to the octagon ring
3-C
12Cycloalkyl, C
10-C
24Aralkyl or C
10-C
24Aryl.
The present invention is described in detail in detail below.
The invention is characterized in: it comprises the 3-iso thiazoline ketone compound that the Chemical formula 1 below (a) is represented; (b) base metal nitrate; (c) an alkali metal salt hydrochlorate; (d) solvent is as neccessary composition:
[Chemical formula 1]
In the superincumbent Chemical formula 1,
R
1And R
2Be hydrogen atom, halogen atom or C independently
1-C
4Alkyl or aryl; With
R
3Be hydrogen atom, C
1-C
18Alkyl, C
2-C
18Thiazolinyl, C
2-C
18Alkynyl, have the C of trilateral to the octagon ring
3-C
12Cycloalkyl, C
10-C
24Aralkyl or C
10-C
24Aryl.
(a) the 3-iso thiazoline ketone compound has the broad-spectrum sterilization activity to many harmful organisms of being derived from animal and plant such as bacterium, mould, algae etc., and it is added in makeup, the coating etc. as inhibitor, can suppress the harmful microbe growth.
In isothiazoline one compositions of the present invention, (a) content of the 3-iso thiazoline ketone compound represented of Shang Mian Chemical formula 1 0.1-20wt% preferably.If (a) content of 3-iso thiazoline ketone compound is lower than 0.1wt%, then because the low and feasible isothiazoline one compositions of making of sterilant content can not be in industrial application.If content is higher than 20wt%, then stability reduces.
About (a) 3-iso thiazoline ketone compound, can preferably use 5-chloro-2-methyl-4-isothiazoline-3-ketone, 2-methyl-4-isothiazoline-3-ketone, 4,5-two chloro-2-methyl-4-isothiazoline-3-ketone, 5-chloro-2-n-octyl-3-isothiazolinone, 4,5-two chloro-2-n-octyl-3-isothiazolinone, benzisothiazole ketone or its mixture.
When the mixture of the 3-iso thiazoline ketone compound that uses (a) Chemical formula 1 to represent, preferably use the mixture of 5-chloro-2-methyl-4-isothiazoline-3-ketone and 2-methyl-4-isothiazoline-3-ketone, its ratio of mixture preferably 1: 20-20: 1.
Isothiazoline one compositions of the present invention also comprises (b) base metal nitrate as stablizer, is used to prevent the isothiazoline ketone decomposition.
In order to prevent that the isothiazoline one compositions from forming precipitation, be extensive use of metal nitrate, use magnesium nitrate usually.But, if magnesium nitrate content is lower than the 0.1wt% of isothiazoline one compositions, then can not reach the sedimentary effect that prevents of expection, if be higher than 25wt%, the decreased solubility of magnesium nitrate then, thereby being the divalence magnesium ions, the precipitation that causes magnesium nitrate self, worse result will cause salt bunch, thus polymer dispersion liquid that can not be stable aqueous.
But, because the stablizer base metal nitrate that isothiazoline one compositions of the present invention comprises, rather than main divalent alkaline-earth metal salt such as magnesium nitrate with used as stabilizers in the isothiazoline one compositions of prior art, therefore can suppress salt bunch, thereby can stablize the isothiazoline one compositions.
(b) the base metal nitrate content 0.1-25wt% of isothiazoline one compositions preferably.If content is lower than 0.1wt%, then can not effectively prevent isothiazolinone precipitation, if be higher than 25wt%, decreased solubility then, product cost improves, and makes composition uneconomical.
About (b) base metal nitrate, can preferably use lithium nitrate, SODIUMNITRATE, saltpetre or its mixture, most preferably SODIUMNITRATE.
Isothiazoline one compositions of the present invention also comprises (c) an alkali metal salt hydrochlorate, and it is to be produced by basic metal that imports as the pH neutralizing agent and hydrochloric acid (chloric acid) reaction.
The magnesium oxide that always is widely used as the pH neutralizing agent of isothiazoline one compositions reacts the back with MgCl in composition
2The form of (magnesium chloride) exists.If MgCl
2Content be higher than the 9wt% of composition, the decreased solubility of magnesium chloride then, thus cause the precipitation of magnesium chloride self, more serious result is that divalent metal magnesium will cause salt bunch, thus polymer dispersion liquid that can not be stable aqueous.
But, because the pH neutralizing agent alkaline carbonate that isothiazoline one compositions of the present invention comprises, rather than main magnesium oxide in the isothiazoline one compositions, therefore can prevent salt bunch as the pH neutralizing agent.
(c) the preferably 0.001-20wt% of isothiazoline one compositions, more preferably 0.01-15wt%, most preferably 0.1-10wt% of an alkali metal salt phosphate content.If content is lower than 0.001wt%, then the pH of the isothiazoline one compositions that obtains can not be controlled in the industrial acceptable scope because the concentration of the alkaline carbonate that imports as the pH neutralizing agent is too low, if content is higher than 20wt%, the stability decreases of composition then, product cost improves, and makes composition uneconomical.
(c) sodium-chlor or Repone K or its mixture preferably introduced with alkaline carbonate of an alkali metal salt hydrochlorate.The alkaline carbonate that imports as the pH neutralizing agent is yellow soda ash, salt of wormwood, sodium bicarbonate, saleratus or its mixture preferably.
The isothiazoline one compositions also comprises (d) solvent.As solvent, can preferably make water, ethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, glycol ether, triglycol, 1,5-pentanediol, 2,4-pentanediol, phenylcarbinol or its mixture.
About another preferred embodiment of the present invention, isothiazoline one compositions of the present invention can also comprise (e) acid iodide, Periodic acid, iodate, periodate or its mixture; (f) metal bromate hydrochlorate; (g) chlorite, they make up the back as stablizer separately or with suitable ratio, are used to prevent the isothiazoline ketone decomposition.More preferably be these three kinds and prevent the precipitation agent combination.
In addition, when storing the isothiazoline one compositions, because the decomposition of compound in the decomposition of byproduct and the storage process in the production process, the precipitation that is different from salt bunch on a small quantity will be formed.This to be deposited in industrial be disadvantageous, because this will destroy the outward appearance of product.
But the present invention can effectively suppress precipitation by add these the three kinds spieces with additive of excellent inhibition precipitation formation effect in the isothiazoline one compositions.Specifically, use is selected from (e) acid iodide, Periodic acid, iodate, periodate or its mixture; (f) metal bromate hydrochlorate; (g) mixture of chloritic compound is than using separately compound (e), (f) and (g) can more effectively stablizing the isothiazoline one compositions.
(e) the preferably 0.0001-0.01wt% of isothiazoline one compositions, more preferably 0.001-0.005wt% of the content of acid iodide, Periodic acid, iodate, periodate or its mixture.If content is lower than 0.0001wt%, then can not effectively prevent the iso thiazoline ketone compound precipitation, if be higher than 0.01wt%, then production cost improves, thereby makes said composition uneconomical.
(e) acid iodide, Periodic acid, iodate, periodate or its mixture are preferably selected from lithium iodate, sodium iodate, Potassium Iodate, ammonium iodate, Periodic acid lithium, sodium periodate, potassium periodate, ammonium periodate, acid iodide, Periodic acid dihydrate or its mixture, more preferably acid iodide, Periodic acid dihydrate, sodium iodate, Potassium Iodate or its mixture.
(f) the metal bromate hydrochlorate is another and prevents precipitation agent, and its content is the 0.001-1.0wt% of isothiazoline one compositions preferably, more preferably 0.01-0.2wt%.If content is lower than 0.001wt%, then can not effectively prevent the isothiazolinone precipitation, if be higher than 1.0wt%, then production cost improves, thereby makes said composition uneconomical.
(f) the metal bromate hydrochlorate is preferably selected from sodium bromate, potassium bromate and composition thereof.
(g) chlorite is that another kind prevents precipitation agent, and its content is 0.001-10wt% preferably, more preferably 0.01-1.0wt%, most preferably 0.05-0.2wt%.If content is lower than 0.001wt%, then can not effectively prevent the isothiazolinone precipitation, if be higher than 10wt%, then production cost improves, thereby makes said composition uneconomical.
(g) preferably Textone, potassium chlorite or its mixture of chlorite.
Isothiazoline one compositions of the present invention preferably includes: (a) the 3-iso thiazoline ketone compound of 0-20wt%; (b) base metal nitrate of 0.1-25wt%; (c) an alkali metal salt hydrochlorate of 0.001-20wt%; (d) solvent of equal amount, and alone or in combination three kinds prevent precipitation agent (e), (f) and (g).These three kinds prevent that precipitation agent from preferably including: (e) acid iodide of 00001-0.01wt%, Periodic acid, iodate, periodate or its mixture; (f) the metal bromate hydrochlorate of 0.01-1.0wt%; (g) chlorite of 0.001-10wt%.
The present invention also provides a kind of isothiazolinone method for compositions that is used for stablizing, and comprises the steps (i): the 3-iso thiazoline ketone compound that the following Chemical formula 1 of (a) 0.1-20wt% is represented; (b) base metal nitrate of 0.1-25wt%; (c) alkaline carbonate of 0.001-20wt% adds in the solvent of (d) equal amount, the mixing solutions of preparation isothiazolinone:
[Chemical formula 1]
In the superincumbent Chemical formula 1,
R
1And R
2Be hydrogen atom, halogen atom or C independently
1-C
4Alkyl or aryl; With
R
3Be hydrogen atom, C
1-C
18Alkyl, C
2-C
18Thiazolinyl, C
2-C
18Alkynyl, have the C of trilateral to the octagon ring
3-C
12Cycloalkyl, C
10-C
24Aralkyl or C
10-C
24Aryl.
(a) the preferred 5-chloro-2-methyl of 3-iso thiazoline ketone compound-4-isothiazoline-3-ketone, 2-methyl-4-isothiazoline-3-ketone, 4,5-two chloro-2-methyl-4-isothiazoline-3-ketone, 5-chloro-2-n-octyl-3-isothiazolinone, 4,5-two chloro-2-n-octyl-3-isothiazolinone, benzisothiazole ketone or its mixture.
According to the method that is used for stablizing isothiazolinone of the present invention, (c) alkaline carbonate adds as the pH neutralizing agent.Form with an alkali metal salt hydrochlorate behind alkaline carbonate that adds and the hydrochloric acid reaction in the isothiazoline one compositions exists.
(c) the preferably 0.01-15wt% of isothiazoline one compositions, more preferably 0.1-10wt% of the add-on of alkaline carbonate.
(c) preferably yellow soda ash, salt of wormwood, sodium bicarbonate, saleratus or its mixture of alkaline carbonate.
In addition, (d) solvent is preferably selected from water, ethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, glycol ether, triglycol, 1,5-pentanediol, 2,4-pentanediol, phenylcarbinol or its mixture.
About another preferred embodiment of the present invention,, also to be selected from (e) acid iodide, Periodic acid, iodate, periodate or its mixture to the adding of isothiazoline one compositions in the method that is used for stablizing isothiazolinone; (f) metal bromate hydrochlorate; (g) chloritic compound and composition thereof is as preventing precipitation agent, further to stablize the isothiazoline one compositions.The preferred different mixture that prevents precipitation agent of two or more mechanisms of action that adds proper ratio.
(e) the preferably 0.0001-0.01wt% of isothiazoline one compositions, more preferably 0.001-0.005wt% of the add-on of acid iodide, Periodic acid, iodate, periodate or its mixture.If content is lower than 0.0001wt%, then can not effectively prevent the isothiazolinone precipitation, if be higher than 0.01wt%, then As time goes on, color can change, production cost improves, thereby makes this method uneconomical.(e) acid iodide, Periodic acid, iodate, periodate or its mixture are preferably selected from lithium iodate, sodium iodate, Potassium Iodate, ammonium iodate, Periodic acid lithium, sodium periodate, potassium periodate, ammonium periodate, acid iodide, Periodic acid dihydrate or its mixture, more preferably acid iodide, Periodic acid dihydrate, sodium iodate, Potassium Iodate or its mixture.
(f) the preferably 0.001-1.0wt% of isothiazoline one compositions, more preferably 0.001-0.2wt% of the add-on of metal bromate hydrochlorate.If content is lower than 0.001wt%, then can not effectively prevent the isothiazolinone precipitation, if be higher than 0.2wt%, then production cost improves, thereby makes this method uneconomical.(f) the metal bromate hydrochlorate is preferably selected from sodium bromate, potassium bromate and composition thereof.
(g) the preferably 0.001-10wt% of isothiazoline one compositions, more preferably 0.01-1.0wt%, most preferably 0.05-0.2wt% of chloritic add-on.If content is lower than 0.001wt%, then can not effectively prevent the isothiazolinone precipitation, if be higher than 10wt%, then production cost improves, thereby makes this method uneconomical.(g) chlorite is preferably selected from Textone, potassium chlorite and composition thereof.
As mentioned above, isothiazoline one compositions of the present invention because do not contain can cause the divalent alkaline-earth metal salt such as the magnesium chloride of salt bunch, so can effectively suppress the harmful microbe growth, therefore can stably be used in dispersion liquid or emulsion such as acrylate paint or the latex etc.
Therefore, isothiazoline one compositions of the present invention can be used as microbial inhibitor in the microorganism growth environment, the example of microorganism growth environment has cooling tower, air scrubber, boiler, ore plaster, the waste water treatment plant, waterwork, reverse osmosis filtration system, ultrafiltration system, water ballast, vaporizer-condenser, heat exchanger, the oil that is used for converting pulp, plastics, emulsion and dispersion agent, coating, latex, apply agent, metalworking fluid etc., isothiazoline one compositions of the present invention can effectively suppress harmful microorganism such as bacterium, mould, the growth of algae etc.
Explain the present invention with reference to following embodiment and comparative example.But these embodiment just illustrate the present invention, rather than restriction the present invention.
Embodiment
[embodiment 1-13 and comparative example 1]
Preparation 3-isothiazolinone strong solution, it is formed and content is shown in table 1.As the 3-iso thiazoline ketone compound, use ratio of mixture to be about 3: 1 the 5-chloro-2-methyl-4-isothiazoline-3-ketone (CMI) and the mixture of 2-methyl-4-isothiazoline-3-ketone (MI).
As shown in table 1, embodiment 1-13 and comparative example's 1 sample prepares with following method: 3-iso thiazoline ketone compound, SODIUMNITRATE, yellow soda ash, magnesium nitrate (comparative example), magnesium oxide (comparative example) and water are mixed, and adding is used to prevent sedimentary KIO
3, NaBrO
3And NaClO
2
Table 1 (wt%)
| Sample | Iso thiazoline ketone compound | Mg(NO 3) 2 | MgCl 2 | NaNO 3 | NaCl | KIO 3 | NaBrO 3 | NaClO 2 |
| Embodiment 1 | 13.84 | - | - | 17.0 | 5.7 | 0.00 2 | ||
| Embodiment 2 | 13.84 | - | - | 17.0 | 5.7 | 0.00 5 | ||
| Embodiment 3 | 13.84 | - | - | 17.0 | 5.7 | 0.01 | ||
| Embodiment 4 | 13.84 | - | - | 17.0 | 5.7 | 0.002 | ||
| Embodiment 5 | 13.84 | - | - | 17.0 | 5.7 | 0.05 | ||
| Embodiment 6 | 13.84 | - | - | 17.0 | 5.7 | 0.20 | ||
| Embodiment 7 | 13.84 | - | - | 17.0 | 5.7 | 0.01 | ||
| Embodiment 8 | 13.84 | - | - | 17.0 | 5.7 | 0.1 | ||
| Embodiment 9 | 13.84 | - | - | 17.0 | 5.7 | 0.20 | ||
| Embodiment 10 | 13.84 | - | - | 17.0 | 5.7 | 0.00 5 | 0.05 | |
| Embodiment 11 | 13.84 | - | - | 17.0 | 5.7 | 0.00 5 | 0.1 | |
| Embodiment 12 | 13.84 | - | - | 17.0 | 5.7 | 0.05 | 0.1 | |
| Embodiment 13 | 13.84 | - | - | 17.0 | 5.7 | 0.00 5 | 0.05 | 0.1 |
| The comparative example 1 | 13.84 | 18.2 | 4.9 | - | - | - | - |
In the foregoing description 1-13 and comparative example's 1 sample, alkaline carbonate (sodium-chlor, Repone K) and magnesium chloride are to be used for pH neutralization and yellow soda ash, salt of wormwood, magnesium nitrate and the magnesium oxide introduced produce at composition.
Specifically, the alkaline carbonate of introducing as the pH neutralizing agent (yellow soda ash, salt of wormwood, sodium bicarbonate, saleratus) is that form with an alkali metal salt hydrochlorate (NaCl, KCl) exists in composition of the present invention.
[test 1]
Salt bunch test
For the sample according to embodiment 1-13 and comparative example 1 preparation, whether test causes salt bunch the results are shown in following table 2.
In general, cause the many magnesium ions that contain in the isothiazoline one compositions of salt bunch as stablizer.What prove is: whether the sample according to embodiment 1-13 and comparative example's 1 preparation can be as the sterilant of dispersion liquid or emulsion such as acrylate paint or latex etc., coagulation whether with the divalent ion anaphylaxis, that is, whether they can the stabilization of polymer aqueous dispersions.
During test, the 5ml detection agent is added drop-wise in the 10ml isothiazolinone solution to be tested.The Starso aqueous solution (Na with 5%
2SiO
39H
2O) as salt bunch detection agent.
Table 2
| Sample | Because the salt bunch precipitation that causes forms situation |
| Embodiment 1 | Do not precipitate after adding 5ml |
| Embodiment 2 | Do not precipitate after adding 5ml |
| Embodiment 3 | Do not precipitate after adding 5ml |
| Embodiment 4 | Do not precipitate after adding 5ml |
| Embodiment 5 | Do not precipitate after adding 5ml |
| Embodiment 6 | Do not precipitate after adding 5ml |
| Embodiment 7 | Do not precipitate after adding 5ml |
| Embodiment 8 | Do not precipitate after adding 5ml |
| Embodiment 9 | Do not precipitate after adding 5ml |
| Embodiment 10 | Do not precipitate after adding 5ml |
| Embodiment 11 | Do not precipitate after adding 5ml |
| Embodiment 12 | Do not precipitate after adding 5ml |
| Embodiment 13 | Do not precipitate after adding 5ml |
| The comparative example 1 | Begin to form precipitation after adding 1ml |
As can be seen from Table 2: salt bunch composition forms precipitation, and non-salt bunch composition does not form precipitation.
When in 10ml comparative example 1 sample, adding the 5ml detection agent, form white or gray precipitate.But, in the sample of embodiment 1, add detection agent and can not form precipitation.
Therefore can conclude: comparative example 1 sample is a salt bunch type, and the sample of embodiment 1 is a non-salt bunch type.
In the superincumbent test 1, use by the stable salt-free isothiazolinone solution of diol solvent thing in contrast.
Fig. 1 is the salt bunch result of isothiazolinone composition sample in test 1 of expression embodiment 1, comparative example 1 and contrast a photo.
In addition, Fig. 2 is the salt bunch result of 10 times of diluents in test 1 the photo of expression embodiment 1 and comparative example's 1 isothiazolinone composition sample.
As shown in Figure 1, comparative example 1 sample has formed white or gray precipitate.The sample of embodiment 1 does not form precipitation.As shown in Figure 2, the test of carrying out with 10 times of diluents of embodiment 1 and comparative example's 1 sample demonstrates same result.
Therefore can prove: do not contain the isothiazoline one compositions of divalent alkaline-earth metal salt such as magnesium chloride, that is, and with the stable isothiazoline one compositions of base metal nitrate can stable high concentrations polymer aqueous dispersion liquid.
[test 2]
Bunch generation test of salt in the acrylate paint emulsion
With whether causing salt bunch with sample that test 1 identical method detects embodiment 1-13 and comparative example 1, just in order to carry out actual proof, (ratio is 5ml: 10ml) to add the acrylate paint emulsion at the sample with embodiment 1-13 and comparative example 1, detect and whether taken place because the salt bunch coagulation that causes (precipitation) the results are shown in following table 3.
Table 3
| Sample | Because the situation that the salt bunch coagulation that causes (precipitation) forms |
| Embodiment 1 | There is not coagulation (precipitation) after adding 5ml |
| Embodiment 2 | There is not coagulation (precipitation) after adding 5ml |
| Embodiment 3 | There is not coagulation (precipitation) after adding 5ml |
| Embodiment 4 | There is not coagulation (precipitation) after adding 5ml |
| Embodiment 5 | There is not coagulation (precipitation) after adding 5ml |
| Embodiment 6 | There is not coagulation (precipitation) after adding 5ml |
| Embodiment 7 | There is not coagulation (precipitation) after adding 5ml |
| Embodiment 8 | There is not coagulation (precipitation) after adding 5ml |
| Embodiment 9 | There is not coagulation (precipitation) after adding 5ml |
| Embodiment 10 | There is not coagulation (precipitation) after adding 5ml |
| Embodiment 11 | There is not coagulation (precipitation) after adding 5ml |
| Embodiment 12 | There is not coagulation (precipitation) after adding 5ml |
| Embodiment 13 | There is not coagulation (precipitation) after adding 5ml |
| The comparative example 1 | Begin to form coagulation (precipitation) after adding 1ml |
As can be seen from Table 3: salt bunch type composition coagulation (precipitation), non-salt bunch type composition is coagulation (precipitation) not.
When in polymer aqueous dispersion liquid acrylate paint emulsion, introducing comparative example 1 sample, owing to coagulation (precipitation) bunch takes place salt.
Therefore can prove: comparative example 1 sample is a salt bunch type, and the sample of embodiment 1-13 is a non-salt bunch type.
Fig. 3 is salt bunch result's the photo of expression embodiment 1 and comparative example's 1 isothiazolinone composition sample.
As shown in Figure 3, wherein add the serious coagulation of acrylate paint emulsion of comparative example 1 isothiazoline one compositions, wherein added the acrylate paint emulsion coagulation not of the isothiazoline one compositions of embodiment 1, kept solution state.
Therefore can conclude: the isothiazoline one compositions that does not contain divalent alkaline-earth metal salt such as magnesium chloride, promptly, with the stable isothiazoline one compositions of base metal nitrate can stable high concentrations polymer aqueous dispersion liquid, therefore, technology such as the paint technology that can be used for preparing in the coating process is arrested in this combination, can not use existing Industrial products in these technologies.
[test 3]
Bunch test of salt in the latex
With whether causing salt bunch with sample that test 1 identical method detects embodiment 1-13 and comparative example 1, just in order to carry out actual proof, (ratio is 5ml: 10ml) to add latex at the sample with embodiment 1-13 and comparative example 1, detect and whether taken place because the salt bunch coagulation that causes (precipitation) the results are shown in following table 4.
Table 4
| Sample | Because the situation that the salt bunch coagulation that causes (precipitation) forms |
| Embodiment 1 | There is not coagulation (precipitation) after adding 5ml |
| Embodiment 2 | There is not coagulation (precipitation) after adding 5ml |
| Embodiment 3 | There is not coagulation (precipitation) after adding 5ml |
| Embodiment 4 | There is not coagulation (precipitation) after adding 5ml |
| Embodiment 5 | There is not coagulation (precipitation) after adding 5ml |
| Embodiment 6 | There is not coagulation (precipitation) after adding 5ml |
| Embodiment 7 | There is not coagulation (precipitation) after adding 5ml |
| Embodiment 8 | There is not coagulation (precipitation) after adding 5ml |
| Embodiment 9 | There is not coagulation (precipitation) after adding 5ml |
| Embodiment 10 | There is not coagulation (precipitation) after adding 5ml |
| Embodiment 11 | There is not coagulation (precipitation) after adding 5ml |
| Embodiment 12 | There is not coagulation (precipitation) after adding 5ml |
| Embodiment 13 | There is not coagulation (precipitation) after adding 5ml |
| The comparative example 1 | Begin to form coagulation (precipitation) after adding 1ml |
As can be seen from Table 4: a salt bunch type composition has formed coagulation (precipitation), and a non-salt bunch type composition does not form coagulation (precipitation).
When introducing comparative example 1 sample in the polymer aqueous dispersion liquid at latex, owing to coagulation (precipitation) bunch takes place salt.But the sample of embodiment 1-13 does not form coagulation (precipitation).
Therefore can conclude: comparative example 1 sample is a salt bunch type, and the sample of embodiment 1-13 is a non-salt bunch type.
Fig. 4 is expression embodiment 1 and comparative example's 1 the salt bunch result of isothiazolinone composition sample in test 3 a photo.
As shown in Figure 4, wherein add the serious coagulation of latex of comparative example 1 isothiazoline one compositions, wherein added the latex coagulation not of the sample of embodiment 1, kept solution state.
[test 4]
Precipitation forms test
Sample for according to embodiment 1-13 and comparative example's 1 preparation carries out storage stability test, the results are shown in following table 5.
In order to prove stability in storage, isothiazoline one compositions (embodiment 1-13 and comparative example's 1 sample) was placed 28 days in 65 ℃ baking oven, analyze the concentration that still is retained in the main component (MIT, CMIT) in the composition with HLPC.The results are shown in following table 5.
Table 5
As can be seen from Table 5: storage is after 28 days down at 65 ℃ for comparative example 1 sample, and the change in concentration of main component is very big, and therefore, the ratio of CMI/MI descends, and forms precipitation.Because two kinds of main components are arranged in the isothiazolinone solution, i.e. CMIT and MIT, the stability of CMIT is again than the poor stability of MIT, this statement of facts so initial ratio descends at 3: 1 since its content decline CMI precipitate.
And by adding the KIO as stablizer
3, NaBrO
3And NaClO
2After the sample of the embodiment 1-13 of preparation stored 28 days, the change in concentration of main component was very little, particularly as the KIO that adds suitable proportion
3, NaBrO
3And NaClO
2Mixture the time, the concentration of main component does not almost change, because the ratio of CMI/MI is very big, so can access the stable isothiazoline one compositions that precipitation not takes place.
Therefore, can prove by top test: add a small amount of iodate, metal bromate hydrochlorate and chlorite with the suitable proportion combination more stable 3-isothiazoline one compositions can access than each compound of independent use the time.
Isothiazoline one compositions of the present invention because do not contain can cause the divalent alkaline-earth metal salt such as the magnesium chloride of salt bunch, so can effectively suppress the harmful microbe growth, therefore can in dispersion liquid or emulsion such as acrylate paint or latex etc., stably use used as stabilizers, and owing to it forms the low stability in storage with excellence of sedimentary speed.
Claims (26)
1. isothiazoline one compositions comprises:
(a) the 3-iso thiazoline ketone compound represented of the Chemical formula 1 below the usefulness of 0.1-20wt%;
(b) base metal nitrate of 0.1-25wt%;
(c) an alkali metal salt hydrochlorate of 0.001-20wt%; With
(d) solvent of equal amount:
[Chemical formula 1]
Wherein,
R
1And R
2Be hydrogen atom, halogen atom or C independently
1-C
4Alkyl or aryl;
R
3Be hydrogen atom, C
1-C
18Alkyl, C
2-C
18Thiazolinyl, C
2-C
18Alkynyl, have the C of trilateral to the octagon ring
3-C
12Cycloalkyl, C
10-C
24Aralkyl or C
1-C
24Aryl,
Wherein said isothiazoline one compositions comprises the chlorite of 0.001-10wt%.
2. according to the isothiazoline one compositions of claim 1, wherein the 3-iso thiazoline ketone compound represented of (a) Chemical formula 1 is selected from 5-chloro-2-methyl-4-isothiazoline-3-ketone, 2-methyl-4-isothiazoline-3-ketone, 4,5-two chloro-2-methyl-4-isothiazoline-3-ketone, 5-chloro-2-n-octyl-3-isothiazolinone, 4,5-two chloro-2-n-octyl-3-isothiazolinone and benzisothiazole ketone, wherein said isothiazoline one compositions also comprises acid iodide, Periodic acid, iodate, periodate or its mixture of 0.0001-0.01wt%.
3. according to the isothiazoline one compositions of claim 1, wherein (b) base metal nitrate is selected from lithium nitrate, SODIUMNITRATE and saltpetre, and wherein said isothiazoline one compositions also comprises the metal bromate hydrochlorate of 0.001-1.0wt%.
4. according to the isothiazoline one compositions of claim 1, wherein (c) an alkali metal salt hydrochlorate is selected from sodium-chlor and Repone K.
5. according to the isothiazoline one compositions of claim 1, wherein (d) solvent is selected from water, ethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, glycol ether, triglycol, 1,5-pentanediol, 2,4-pentanediol and phenylcarbinol.
6. according to the isothiazoline one compositions of claim 1, wherein the content of (c) an alkali metal salt hydrochlorate is the 0.1-15wt% of isothiazolinone composition weight.
7. according to the isothiazoline one compositions of claim 1, wherein the content of (c) an alkali metal salt hydrochlorate is the 0.1-10wt% of isothiazolinone composition weight.
8. according to the isothiazoline one compositions of claim 2, wherein the content of acid iodide, Periodic acid, iodate, periodate or its mixture is the 0.001-0.005wt% of isothiazolinone composition weight.
9. according to the isothiazoline one compositions of claim 3, wherein the content of metal bromate hydrochlorate is the 0.001-1.0wt% of isothiazolinone composition weight.
10. according to the isothiazoline one compositions of claim 3, wherein the content of metal bromate hydrochlorate is the 0.001-0.2wt% of isothiazolinone composition weight.
11. according to the isothiazoline one compositions of claim 1, wherein chloritic content is the 0.001-10wt% of isothiazolinone composition weight.
12. according to the isothiazoline one compositions of claim 1, wherein chloritic content is the 0.01-1wt% of isothiazolinone composition weight.
13. according to the isothiazoline one compositions of claim 1, wherein chloritic content is the 0.05-0.2wt% of isothiazolinone composition weight.
14. according to the isothiazoline one compositions of claim 2, wherein acid iodide, Periodic acid, iodate, periodate or its mixture are selected from lithium iodate, sodium iodate, Potassium Iodate, ammonium iodate, Periodic acid lithium, sodium periodate, potassium periodate, ammonium periodate, acid iodide, Periodic acid dihydrate and composition thereof.
15. according to the isothiazoline one compositions of claim 3, wherein the metal bromate hydrochlorate is sodium bromate or potassium bromate.
16. according to the isothiazoline one compositions of claim 1, wherein chlorite is Textone or potassium chlorite.
17. a method that is used for stablizing isothiazolinone comprises the steps: the 3-iso thiazoline ketone compound that the following Chemical formula 1 of (a) 0.1-20wt% is represented; (b) base metal nitrate of 0.1-25wt%; (c) alkaline carbonate of 0.001-20wt% adds in the solvent of (d) equal amount, the preparation mixing solutions:
[Chemical formula 1]
Wherein,
R
1And R
2Be hydrogen atom, halogen atom or C independently
1-C
4Alkyl or aryl; With
R
3Be hydrogen atom, C
1-C
18Alkyl, C
2-C
18Thiazolinyl, C
2-C
18Alkynyl, have the C of trilateral to the octagon ring
3-C
12Cycloalkyl, C
10-C
24Aralkyl or C
10-C
24Aryl,
Wherein this method comprises and will prevent that precipitation agent from adding in the mixing solutions, and described isothiazoline one compositions comprises the chlorite of 0.001-10wt%.
18. the method that is used for stablizing isothiazolinone according to claim 17, wherein the 3-iso thiazoline ketone compound represented of (a) Chemical formula 1 is selected from 5-chloro-2-methyl-4-isothiazoline-3-ketone, 2-methyl-4-isothiazoline-3-ketone, 4,5-two chloro-2-methyl-4-isothiazoline-3-ketone, 5-chloro-2-n-octyl-3-isothiazolinone, 4,5-two chloro-2-n-octyl-3-isothiazolinone and benzisothiazole ketone, wherein said isothiazoline one compositions also comprises acid iodide, Periodic acid, iodate, periodate or its mixture of 0.0001-0.01wt%.
19. according to the method that is used for stablizing isothiazolinone of claim 17, wherein (b) base metal nitrate is selected from lithium nitrate, SODIUMNITRATE and saltpetre, wherein said isothiazoline one compositions also comprises the metal bromate hydrochlorate of 0.001-1.0wt%.
20. according to the method that is used for stablizing isothiazolinone of claim 17, wherein (c) alkaline carbonate is selected from yellow soda ash, salt of wormwood, sodium bicarbonate and saleratus.
21. according to the method that is used for stablizing isothiazolinone of claim 17, wherein (d) solvent is selected from water, ethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, glycol ether, triglycol, 1,5-pentanediol, 2,4-pentanediol and phenylcarbinol.
22. according to the method that is used for stablizing isothiazolinone of claim 17, wherein the content of (c) alkaline carbonate is the 0.01-15wt% of isothiazolinone composition weight.
23. according to the method that is used for stablizing isothiazolinone of claim 17, wherein the content of (c) alkaline carbonate is the 0.1-10wt% of isothiazolinone composition weight.
24. according to the method that is used for stablizing isothiazolinone of claim 18, wherein acid iodide, Periodic acid, iodate, periodate or its mixture are selected from lithium iodate, sodium iodate, Potassium Iodate, ammonium iodate, Periodic acid lithium, sodium periodate, potassium periodate, ammonium periodate, acid iodide, Periodic acid dihydrate and composition thereof.
25. according to the method that is used for stablizing isothiazolinone of claim 19, wherein the metal bromate hydrochlorate is sodium bromate or potassium bromate.
26. according to the method that is used for stablizing isothiazolinone of claim 17, wherein chlorite is Textone or potassium chlorite.
Applications Claiming Priority (14)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR20020030023 | 2002-05-29 | ||
| KR1020020030023 | 2002-05-29 | ||
| KR1020020062096 | 2002-10-11 | ||
| KR1020020062096A KR20030093086A (en) | 2002-05-29 | 2002-10-11 | Isothiazolone composition and method for stabilizing isothiazolone |
| KR1020020076857A KR20030093087A (en) | 2002-05-29 | 2002-12-05 | Isothiazolone composition and method for stabilizing isothiazolone |
| KR1020020076857 | 2002-12-05 | ||
| KR1020030018624 | 2003-03-25 | ||
| KR1020030018625A KR100975373B1 (en) | 2002-05-29 | 2003-03-25 | Isothiazolone composition and method for stabilizing isothiazolone |
| KR1020030018625 | 2003-03-25 | ||
| KR1020030018624A KR100975372B1 (en) | 2002-05-29 | 2003-03-25 | Isothiazolone composition and method for stabilizing isothiazolone |
| KR1020030028973 | 2003-05-07 | ||
| KR1020030028974A KR100975375B1 (en) | 2002-05-29 | 2003-05-07 | Isothiazolone composition and method for stabilizing isothiazolone |
| KR1020030028974 | 2003-05-07 | ||
| KR1020030028973A KR100975374B1 (en) | 2002-05-29 | 2003-05-07 | Isothiazolone composition and method for stabilizing isothiazolone |
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| CN100400521C true CN100400521C (en) | 2008-07-09 |
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| Country | Link |
|---|---|
| EP (1) | EP1507771A4 (en) |
| JP (1) | JP2005527626A (en) |
| CN (1) | CN100400521C (en) |
| AU (1) | AU2003232654B2 (en) |
| WO (1) | WO2003099799A1 (en) |
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| JP5194205B2 (en) * | 2004-02-19 | 2013-05-08 | 住化エンビロサイエンス株式会社 | Industrial antibacterial composition |
| JP5101826B2 (en) * | 2006-02-28 | 2012-12-19 | 日本曹達株式会社 | Water-soluble preparation containing isothiazolone compound and method for stabilizing isothiazolone compound |
| BRPI0702299B1 (en) * | 2006-06-02 | 2017-04-11 | Rohm & Haas | microbicidal composition |
| EP2165604A4 (en) * | 2007-05-31 | 2012-06-13 | Chemicrea Inc | Stable microbiocidal composition |
| CN103570642B (en) * | 2012-08-01 | 2015-03-18 | 中国中化股份有限公司 | Isothiazolinone compound and application thereof as bactericide |
| CN103030733B (en) * | 2012-12-06 | 2014-12-10 | 青岛大学 | Polyacrylate antifouling copolymerization resin with side chain comprising benzisothiazolinone and preparation method thereof |
| CN103319433A (en) * | 2013-07-08 | 2013-09-25 | 王建国 | Production technology of CMI (cell-mediated immunity) industrial antibacterial agent |
| CN106472520A (en) * | 2016-09-23 | 2017-03-08 | 江苏辉丰农化股份有限公司 | A kind of composition pesticide |
| ES2885008T3 (en) * | 2017-04-04 | 2021-12-13 | Thor Gmbh | Stabilized biocidal composition |
| JP6916306B2 (en) | 2018-01-12 | 2021-08-11 | 富士フイルム株式会社 | Chemical solution, substrate processing method |
| JP7043366B2 (en) * | 2018-08-08 | 2022-03-29 | エステー株式会社 | Solid volatilization preparation |
| CN109964947A (en) * | 2019-04-12 | 2019-07-05 | 嘉兴沃特泰科环保科技有限公司 | Non-oxidative antimicrobial |
| CN110037041A (en) * | 2019-04-30 | 2019-07-23 | 三河市霍夫曼化学品制造有限公司 | A kind of isothiazolinone built-up microemulsion type biocide mildewcide, preparation method and application |
| CN111087653A (en) * | 2019-11-13 | 2020-05-01 | 嘉兴学院 | Preservative for waterborne polyurethane emulsion and preparation method thereof |
| CN113549358A (en) * | 2021-07-28 | 2021-10-26 | 陕西省石油化工研究设计院 | Composite preservative for paint and preparation method and application thereof |
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| CN1215555A (en) * | 1997-10-28 | 1999-05-05 | 罗姆和哈斯公司 | Stable microbicide formulation |
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| US3870795A (en) * | 1973-02-28 | 1975-03-11 | Rohm & Haas | Stabilization of solutions of 3-isothiazolones employing certain metal nitrates and nitrites |
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| US5145501A (en) * | 1991-11-12 | 1992-09-08 | Rohm And Haas Company | Bromate stabilizers for 3-isothiazolones |
| JP3176676B2 (en) * | 1991-12-24 | 2001-06-18 | ローム アンド ハース カンパニー | Sterilizing composition |
| KR100315355B1 (en) * | 1999-08-26 | 2001-11-30 | 류정열 | A mold for trunk floor having heat pipes for cooling itself |
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| US6403533B2 (en) * | 2000-01-27 | 2002-06-11 | Rohm And Haas Company | Stabilized microbicide formulation |
| KR100740054B1 (en) * | 2000-10-13 | 2007-07-16 | 에스케이케미칼주식회사 | Isothiazolone composition |
| KR100703997B1 (en) * | 2001-05-08 | 2007-04-04 | 에스케이케미칼주식회사 | Isothiazolone composition and stabilizing method, and method for suppressing micro-organism using the same |
| KR100703996B1 (en) * | 2001-05-08 | 2007-04-04 | 에스케이케미칼주식회사 | Isothiazolone composition and stabilizing method, and method for suppressing micro-organism using the same |
-
2003
- 2003-05-28 CN CNB038181568A patent/CN100400521C/en 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/en not_active Withdrawn
- 2003-05-28 AU AU2003232654A patent/AU2003232654B2/en not_active Ceased
- 2003-05-28 JP JP2004507456A patent/JP2005527626A/en active Pending
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| US4067878A (en) * | 1976-03-05 | 1978-01-10 | Rohm And Haas Company | Stabilization of solutions of 3-isothiazolones |
| CN1215555A (en) * | 1997-10-28 | 1999-05-05 | 罗姆和哈斯公司 | Stable microbicide formulation |
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| Publication number | Publication date |
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| WO2003099799A1 (en) | 2003-12-04 |
| AU2003232654A1 (en) | 2003-12-12 |
| EP1507771A4 (en) | 2006-08-30 |
| AU2003232654B2 (en) | 2007-05-17 |
| EP1507771A1 (en) | 2005-02-23 |
| CN1671674A (en) | 2005-09-21 |
| JP2005527626A (en) | 2005-09-15 |
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