CN102365022A - Microbicide - Google Patents
Microbicide Download PDFInfo
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- CN102365022A CN102365022A CN2010800147699A CN201080014769A CN102365022A CN 102365022 A CN102365022 A CN 102365022A CN 2010800147699 A CN2010800147699 A CN 2010800147699A CN 201080014769 A CN201080014769 A CN 201080014769A CN 102365022 A CN102365022 A CN 102365022A
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- Prior art keywords
- microbicide
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- acetic acid
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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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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D65/00—Accessories or auxiliary operations, in general, for separation processes or apparatus using semi-permeable membranes
- B01D65/02—Membrane cleaning or sterilisation ; Membrane regeneration
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/50—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2321/00—Details relating to membrane cleaning, regeneration, sterilization or to the prevention of fouling
- B01D2321/16—Use of chemical agents
- B01D2321/168—Use of other chemical agents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/02—Non-contaminated water, e.g. for industrial water supply
- C02F2103/023—Water in cooling circuits
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/04—Disinfection
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/20—Prevention of biofouling
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- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Zoology (AREA)
- General Health & Medical Sciences (AREA)
- Environmental Sciences (AREA)
- Wood Science & Technology (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Dentistry (AREA)
- Environmental & Geological Engineering (AREA)
- Hydrology & Water Resources (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Water Supply & Treatment (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Thiazole And Isothizaole Compounds (AREA)
Abstract
Provided is a microbicide having 5-chloro-2-methyl-4-isothiazolin-3-one as the active component and a reduced amount of residual materials and hydrolysates from the organic solvents used in the industrial manufacturing method thereof. The microbicide, which includes 5-chloro-2-methyl-4-isothiazolin-3-one as the active component and has a total amount of the organic solvent and the hydrolysate thereof of no more than 200ppm when the concentration of the active component is 10 wt%, is obtained by a manufacturing method involving a process for the cyclization of sulfide amides and a process for neutralizing hydrogen halide salts of a compound comprising a 3-isothiazolone ring, wherein acetic acid ester containing no more than 0.1 wt% of water is used as the reacting solvent for the cyclization process, a hydrocarbon compound having a water content of no more than 0.1 wt% is added to the hydrogen halide salt obtained by filtering the acetic ester fluid dispersions of the hydrogen halide salt and the resulting mixture is filtered, solvents are exchanged, and the processes are carried out in an atmosphere with a water content of no more than 0.1%.
Description
Technical field
The present invention relates to the microbicide of 5-chloro-2-methyl-4-isothiazoline-3-ketone as active ingredient; In more detail, relate to the microbicide that the content of in the manufacturing process of this active ingredient employed organic solvent residue thing and hydrolysate thereof is minimized.
Background technology
5-chloro-2-methyl-4-isothiazoline-3-ketone has the biologically active that suppresses microbial growth, therefore is used as the preservative or the bactericide of various industrial goods.In addition, the active ingredient that also can be used as the slimicide (slime control agent) of the Acarasiales that organic matter of being used for preventing by microorganisms such as the bacterium that produces derived from water treatment facilities or cooling water system or algae etc. constitutes is used.
Particularly in water treatment facilities or cooling water system,,, except suppressing Acarasiales, also require different performances for the water treatment operation according to the purpose of water treatment or the device form of cooling water system (closed system or open system etc.) etc.For example; Water treatment in the high purification that is used for discharge water or various row's water reuses; Because the influence of the pollutant that is contained in the processed water; The mesh of diffusion barrier stops up the very big problem that is regarded as, and therefore requires to reduce polyvalent metal ion as its reason (for example, with reference to patent documentation 1.), or as the essential factor that the flow of diffusion barrier descends, the existence of the protein in the processed water etc. is regarded as problem, therefore requires its cohesion is removed (for example, with reference to patent documentation 2).In addition; For utilizing again of plant drainage biological treatment of water is being carried out in the water treatment of film separating treatment, due to the chlorine due to film deterioration or the chlorine bacteria inactivation rate cause total organic carbon (TOC) to increase, this is regarded as problem; Requirement is handled (for example, with reference to patent documentation 3 it.)。In addition, in semiconductor device is made in the manufacturing of employed cleaning with ultra-pure water, need in each of the film device more than 2, add slimicide, be difficult to control, to this problem, requirement is carried out (for example, with reference to patent documentation 4 easily.)。Further, in reverse osmosis membrane (RO film) processing method,, require water is reclaimed (for example, with reference to patent documentation 5) to heavens for condensed water is discharged to the problem outside the system as draining.And further proposed, in the Water Purifiers that has used the RO membrane separation device,, ion interchange unit (for example, with reference to patent documentation 6) is set in order further to reduce the concentration of RO film permeate water.Hence one can see that, and desired performance or the problem that is regarded as problem are various in comprising the water treatment operation of Acarasiales control.
In recent years, as new problem, require further reduction highly to handle the TOC in the water.No matter be in the treatment system of RO film; Still in the pure water that requires height water quality is made; According to purposes; The TOC of number ppb～tens of ppb degree is regarded as problem, particularly in the purposes that needs the extreme high purity pure water that is used for electronic material manufacturings such as semiconductor, is becoming deep problem in recent years.In addition, in sterilization processing of the Legionnella bacterium in cooling water system and the Acarasiales control, can exist low molecular organic compound in water system, to decompose the problem that is supplied on the contrary to the nutrient source of Acarasiales.Particularly for the Acarasiales in closed system control, because to compare drainage discharge few with the open loop cooling water system, thereby make the holdup time elongated, therefore be difficult to bring into play Acarasiales control effect sometimes.Because the low-molecular-weight organic compound of in this system, being sneaked into becomes branch to enter into microorganism soon, therefore need low-molecular-weight organic compound be blended in the system.
For it is handled, for example, can study the situation of the performance that improves membrane separation device, but, be difficult to fully reduce TOC from technological layer.In addition,, also can study, but so not only make processing operation numerous and diverse, and processing cost is risen the situation of appending postprocessing working procedures in order to reduce the TOC that handles water.Therefore, need the countermeasure that can be applicable to treatment process in the past easily.
In addition; For 5-chloro-2-methyl-4-isothiazoline-3-ketone; Be in the past halogenation cyclisation operation through comprising the sulfide amide intermediate and the compound that obtains by this operation with 3-isothiazolone ring the halogenation hydrogen salt in the manufacturing process of operation (for example, with reference to patent documentation 7,8.) make, commercially available.In this manufacturing approach, therefore acetic acid esters uses its halogenation cyclization solvent as the sulfide amide intermediate in industry because its reaction conversion ratio is high.In addition, in the cleaning abstraction process of compound, also with an organic solvent.These organic solvents are removed in the final operation of manufacturing process, but are difficult to fully remove, and might remain in the end article as impurity.But; This residue is micro-, for example, and in the water treatment purposes; For employed 5-chloro-2-methyl-4-isothiazoline-3-ketone concentration in the Acarasiales control; In processed water, be generally about several mg/L, so the concentration of the residue in the processed water is also low, is not regarded as problem in the past especially.
The prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2006-95425 communique
Patent documentation 2: TOHKEMY 2004-267830 communique
Patent documentation 3: japanese kokai publication hei 11-33371 communique
Patent documentation 4: japanese kokai publication hei 09-294989 communique
Patent documentation 5: japanese kokai publication hei 10-202066 communique
Patent documentation 6: TOHKEMY 2000-317457 communique
Patent documentation 7: japanese kokai publication sho 59-31772 communique
Patent documentation 8: the special public clear 45-38330 communique of Japan
Summary of the invention
The problem that invention will solve
But; No matter confirm through the inventor, be in the water treatment purposes, and still the residue at trace can become the purposes of problem, for example be used in the purposes of Water Purifiers; Low-molecular-weight organic compound in such residue becomes branch to see through membrane separation device, leaks to handle in the water.In the treatment system of RO film, also confirm to exist this leakage.But in the past seldom with the performance improvement of microbicide self as problem; Be used to prevent the air-polluting situation that causes by smears or cement thereby the known volatile ingredient content that compound with 3-isothiazolone ring arranged is few, but do not known by the public with the situation that is used for purpose as slimicide.
Therefore; The object of the present invention is to provide a kind of microbicide; It is with the microbicide of 5-chloro-2-methyl-4-isothiazoline-3-ketone as active ingredient; Compare with existing product, can reduce the organic solvent residue thing used in the industrial manufacturing process of this active ingredient and the content of hydrolysate thereof fully.
The means that are used to deal with problems
The present invention relates to microbicide; It is to contain the microbicide of 5-chloro-2-methyl-4-isothiazoline-3-ketone as active ingredient; This microbicide is characterised in that the total content of organic solvent and hydrolysate thereof and the concentration of above-mentioned active ingredient satisfy following formula (1).
The organic solvent of representing by ppm and the total content of hydrolysate thereof * (10/B)≤200ppm (1)
In the formula (1), the numerical value of the active ingredient concentration that B representes to be represented by weight %.
In addition, in this manual, ppm, ppb are the weight specific concentration.
In a mode of the present invention, organic solvent is acetic acid esters and/or hydrocarbon compound.
In another mode of the present invention, organic solvent is acetic acid esters or is acetic acid esters and hydrocarbon compound.
In addition, in a mode of the present invention, hydrocarbon compound is a toluene.
In a mode of the present invention, acetic acid esters is in particular and is selected from least a in the group of being made up of ethyl acetate and butyl acetate.
Further, in a mode of the present invention, the total content of acetic acid esters and hydrolysate thereof and the concentration of above-mentioned active ingredient satisfy following formula (1 ').
The acetic acid esters of representing by ppm and the total content of hydrolysate thereof * (10/B)≤60ppm (1 ')
In the formula (1 '), the numerical value of the active ingredient concentration that B representes to be represented by weight %.
Further, in another mode of the present invention, the content of acetate and the concentration of above-mentioned active ingredient satisfy following formula (1 ").
The content of the acetate of representing by ppm * (10/B)≤10ppm (1 ")
Formula (in 1 "), the numerical value of the active ingredient concentration that B representes to be represented by weight %.
In other modes of the present invention; The 5-chloro-2-methyl-4-isothiazoline-3-ketone of active ingredient for obtaining through following manufacturing process; Said manufacturing process be comprise the halogenation cyclisation operation of sulfide amide intermediate and the halogenation hydrogen salt of the compound that obtains by above-mentioned operation that carries out as required with 3-isothiazolone ring in the manufacturing process of the 5-chloro-2-methyl-4-isothiazoline-3-ketone of operation; In this manufacturing process: using moisture is that acetic acid esters below the 0.1 weight % is as the reaction dissolvent of above-mentioned halogenation cyclisation operation; After the cyclisation operation and carrying out above-mentioned in and under the situation of operation before it; With moisture is that hydrocarbon compound below the 0.1 weight % is added into through the acetic acid esters dispersion liquid to resulting above-mentioned halogenation hydrogen salt and filters in the moist press cake that obtains; Filter, become above-mentioned hydrocarbon compound thereby above-mentioned acetic acid esters is carried out solvent exchange; Be to implement the atmosphere below moisture is 0.1 weight % from above-mentioned halogenation cyclisation operation to above-mentioned at least solvent exchange operation simultaneously.
In other modes of the present invention, said microbicide contains the active ingredient of 1～30 weight %.
The invention provides a kind of slimicide that is applicable to Water Purifiers with reverse osmosis membrane.
In addition, a kind of Acarasiales control method with Water Purifiers of reverse osmosis membrane is provided among the present invention, this method has been used above-mentioned microbicide.
The invention effect
The present invention utilizes above-mentioned formation that the microbicide of a kind of active ingredient for 5-chloro-2-methyl-4-isothiazoline-3-ketone can be provided; Wherein, The halogenation cyclization solvent of material thioether amide intermediate, clean organic solvent that dissolving uses and the residual quantity of hydrolysate (in other words, employed organic solvent and hydrolysate thereof in the manufacturing process of above-mentioned active ingredient) has obtained sufficient reduction as the extraction of product.
The present invention utilizes above-mentioned formation that the microbicide of a kind of active ingredient for 5-chloro-2-methyl-4-isothiazoline-3-ketone can be provided; Wherein, Even adopt the halogenation cyclization solvent of the high acetic acid esters of its reaction conversion ratio as the material thioether amide intermediate, the residual quantity of acetic acid esters and hydrolysate thereof has also obtained sufficient reduction.The microbicide that particularly can provide a kind of acetate residual quantity to be minimized.
In addition, carry out Acarasiales control, compare with the situation of using existing product and can significantly reduce the TOC that handles in the water through in membrane separation devices such as RO membrane separation device, using microbicide of the present invention.
Embodiment
In microbicide of the present invention; The concentration of active ingredient 5-chloro-2-methyl-4-isothiazoline-3-ketone satisfies following formula (1) with the total content of employed organic solvent in manufacturing process and hydrolysate thereof; Therefore, in fact do not contain employed organic solvent and hydrolysate thereof in manufacturing process.
The organic solvent of representing by ppm and the total content of hydrolysate thereof * (10/B)≤200ppm (1)
In the formula (1), the numerical value of the active ingredient concentration that B representes to be represented by weight %.
The right of above-mentioned formula (1) is preferably 100ppm, and more preferably 60ppm allows if measure the sensitivity of machine, then further is preferably 40ppm.
Active ingredient 5-chloro-2-methyl-4-isothiazoline-3-ketone can mix with the form of free cpds, perhaps also can mix with the form of hydrogen halides (for example hydrogen chloride, hydrogen bromide etc.) salt.
As above-mentioned organic solvent, for example be organic solvent that in the manufacturing process of 5-chloro-2-methyl-4-isothiazoline-3-ketone, uses etc., for example can be acetic acid esters (for example is preferably ethyl acetate, butyl acetate; Ethyl acetate more preferably.), hydrocarbon compound (for example toluene, hexane, cyclohexane etc.) or their mixture or other organic solvent (for example acetate, alcohol etc.).
In addition, the concentration of the total content of ethyl acetate and hydrolysate thereof and above-mentioned active ingredient preferably satisfies following formula (1 ').
The ethyl acetate of representing by ppm and the total content of hydrolysate thereof * (10/B)≤60ppm (1 ')
In the formula (1 '), the numerical value of the active ingredient concentration that B representes to be represented by weight %.Allow if measure the sensitivity of machine, the right of formula (1 ') is 40ppm more preferably.
Further, the concentration of the content of acetate and above-mentioned active ingredient preferably satisfies following formula (1 ").
The content of the acetate of representing by ppm * (10/B)≤10ppm (1 ")
Formula (in 1 "), the numerical value of the active ingredient concentration that B representes to be represented by weight %.Allow if measure the sensitivity of machine, (the right of 1 ") further is preferably 5ppm to formula.Through reducing the content of acetate, for example can be easy to see through membrane separation devices such as RO membrane separation device, the amount of acetate is reduced.
In the present invention,, compare, be able to abundant reduction as the organic solvent of impurity and the total content of hydrolysate thereof with commercial articles for active ingredient 5-chloro-2-methyl-4-isothiazoline-3-ketone.As this 5-chloro-2-methyl-4-
Neutralization, dewater and method that the distillation of organic solvent is removed.
But,, can not satisfy above-mentioned condition usually as the organic solvent of impurity and the total content of hydrolysate thereof for containing 5-chloro-2-methyl-4-isothiazoline-3-ketone of obtaining by this manufacturing approach microbicide as active ingredient.That is, for example, be organic solvent even hydrocarbon compound such as toluene is removed in distillation, acetic acid esters also is difficult to distillation and removes, and remains in the end article with the mode of residual solvent.According to the inventor's analysis, be that its residual quantity probably adds up to 5000～15000ppm in the 5-chloro-2-methyl-4-isothiazoline-3-ketone about 10 weight % in concentration.The easy residual this point of acetic acid esters is normally well-known, so this value is the benchmark of the total amount of the residual organic solvent that contained in the 5-chloro-2-methyl-4-isothiazoline-3-ketone that in existing manufacturing process, uses acetic acid esters to make and hydrolysate thereof.
Therefore, in the present invention, can preferably use the 5-chloro-2-methyl-4-isothiazoline-3-ketone that obtains by following manufacturing approach as active ingredient.Promptly; Can use the 5-chloro-2-methyl-4-isothiazoline-3-ketone that obtains through following manufacturing process; This manufacturing process be comprise the halogenation cyclisation operation of sulfide amide intermediate and the halogenation hydrogen salt of the compound that obtains by above-mentioned operation that carries out as required with 3-isothiazolone ring in the known manufacturing process of the 5-chloro-2-methyl-4-isothiazoline-3-ketone of operation; Wherein, using moisture is that 0.1 weight % acetic acid esters following, that be preferably below the 0.01 weight % (for example is preferably ethyl acetate, butyl acetate; Ethyl acetate more preferably.) as the reaction dissolvent of above-mentioned halogenation cyclisation operation; After the cyclisation operation and under corresponding situation in above-mentioned and before the operation; With moisture be below the 0.1 weight %, the hydrocarbon compound (for example toluene, hexane, cyclohexane etc.) that is preferably below the 0.01 weight % is added into through the acetic acid esters dispersion liquid to resulting above-mentioned halogenation hydrogen salt and filters in the moist press cake that obtains; Filter, become above-mentioned hydrocarbon compound thereby above-mentioned dispersion liquid is carried out solvent exchange; Be simultaneously from above-mentioned halogenation cyclisation operation to above-mentioned at least solvent exchange operation below moisture is 0.1 weight %, be preferably the atmosphere below the 0.05 weight %, for example in dry inert gas (for example nitrogen, argon etc.) or in dry air, implement.In addition; So-called " be moisture be 0.1 weight % below from above-mentioned halogenation cyclisation operation to above-mentioned at least solvent exchange operation, be preferably the atmosphere below the 0.05 weight % and implement " means; Moisture is below the 0.01 weight %, is preferably gas below the 0.001 weight % and is blown in advance and carries out in the system after moisture removes, Yi Bian moisture is below the 0.01 weight %, is preferably gas below the 0.001 weight % and is blown on one side moisture to be managed in the system and implements operation.
In above-mentioned manufacturing process, halogenation cyclisation operation, in and operation, enrichment process etc. can adopt known method.Specifically; In above-mentioned solvent exchange operation; Filtering in the moist press cake that obtains through acetic acid esters dispersion liquid above-mentioned halogenation hydrogen salt; Add the hydrocarbon compound of its 1～5 times of amount, carry out 1～5 time, preferred 1～2 time and filter, can solvent be exchanged for hydrocarbon compound from acetic acid esters thus.Filtration is preferably filtration under diminished pressure or centrifugal filtration etc., centrifugal filtration more preferably.In addition, the operation from halogenation cyclisation operation to above-mentioned at least solvent exchange operation is preferably carried out dry inert gas atmosphere.According to above-mentioned manufacturing process; Possibly not contain employed organic solvent and hydrolysate thereof in manufacturing process in fact in resulting 5-chloro-2-methyl-4-isothiazoline-3-ketone, particularly can be contained acetic acid esters hardly or as the acetate of its hydrolysate or the 5-chloro-2-methyl-4-isothiazoline-3-ketone of alcohols.
Further, the enrichment process time needs the long period more than 20 hours usually, and in contrast to this, in above-mentioned manufacturing process, this time can be 10～15 hours, and required time is shortened 25～50%.In addition, the productive rate of 5-chloro-2-methyl-4-isothiazoline-3-ketone can improve 5～10% with comparing usually also.
For microbicide of the present invention, can above-mentioned active ingredient be dissolved in the water.
In addition, also can use divalent slaine (the for example nitrate or the chloride of metals such as calcium, magnesium, manganese, nickel, copper, zinc) as stabilization agent according to the amount that does not harm the object of the invention as required.This method is known, for example is recorded in No. 3870795 grades of United States Patent (USP).
In microbicide of the present invention, be generally 1～30 weight % as above-mentioned active ingredient concentration, be preferably 5～20 weight %.Under the dense situation of above-mentioned active ingredient, for example above-mentioned active ingredient surpasses under the situation of 30 weight %, and when using stabilization agent, the nitrate of the metal that uses as stabilization agent or the possibility that chloride is separated out uprise.In addition, under the light situation of above-mentioned active ingredient, under the situation of for example above-mentioned active ingredient less than 1 weight %, the stability of above-mentioned active ingredient trends towards variation, and then a large amount of use of having in use, and commercial value and mixing efficiency are poor.Therefore, from the aspect of practical application, preferably use according to 5～20 weight %.
As the usage amount of aforementioned stable agent, for example with respect to the 5-chloro-2-methyl-4-isothiazoline-3-ketone aqueous solution of 100 weight portions, usage amount is 1～30 weight portion, is preferably 15～25 weight portions.
Microbicide of the present invention can be as coating or cement, water treatment purposes.As coating purposes or cement purposes, can enumerate for example purposes such as antibacterial agent, mould inhibitor, antibacterial mildew inhibitor, preservative.As the water treatment purposes, can enumerate for example purposes such as slimicide, antibacterial agent, mould inhibitor, antibacterial mildew inhibitor, preservative.
Microbicide of the present invention goes for water treatment facilities or cooling water system.As water treatment facilities, applicable to the water treatment facilities that has for example used membrane separation device; For example, be particularly suitable for having the Water Purifiers of RO film with the Water Purifiers that uses milipore filter (UF film) separator, micro-filtration membrane (MF (Micro Filtration) film) separator, RO membrane separation device or their combination (for example use the UF membrane separation device, use the RO membrane separation device) known Water Purifiers as representative at back segment at leading portion.In addition, also can be used as slimicide and in the cyclicity cooling water system of for example closed system, use, or the preservative that can be used as the medicament that in water treatment facilities etc., uses uses.
When microbicide of the present invention uses as water treatment purposes such as slimicide, antibacterial agent, mould inhibitor, antibacterial mildew inhibitor, preservatives; As its usage amount; In processed water; Above-mentioned active ingredient concentration is generally 0.1mg/L～20mg/L, is preferably 0.1mg/L～10mg/L, further is preferably 0.1mg/L～5mg/L.In addition, interpolation can in processed water, carry out 1 time or be divided into 2 times with on carry out.For adding, for example under the situation of water treatment facilities, can be added in the supply water that membrane separation device is supplied with; Preferably add so that it contains at least in the supply water of supplying with to the RO membrane separation device.As the usage amount in coating purposes or the cement purposes, in coating or cement, active ingredient concentration is generally 100mg/kg～5000mg/kg, is preferably 500mg/kg～2000mg/kg.
Embodiment
Through embodiment the present invention is further carried out below bright specifically, but following record only be used for the explanation, the present invention is not limited to these embodiment.
Embodiment 1
The manufacturing of 5-chloro-2-methyl-4-isothiazoline-3-ketone
Using the moisture of 800g is the ethyl acetate of 0.05 weight %; To N; N '-dimethyl-3; 3 '-dithio dipropyl acidamide (150g, 0.54 mole, moisture 0.1 weight %) dilutes, and the chlorine that is blown into moisture and is 0.001 weight % reacts, and obtains the ethyl acetate slip of 5-chloro-2-methyl-4-isothiazoline-3-keto hydrochloride.
Slip to obtaining filters, and the use moisture is that the toluene of 0.05 weight % cleans resulting moist press cake, and ethyl acetate solvent is exchanged for toluene.The resultant crystallization 5-of 200g chloro-2-methyl-4-isothiazoline-3-ketone chlorate is dissolved in the water, and interpolation magnesium nitrate hexahydrate, magnesia, hydrochloric acid are 1～4 with pH regulator, obtain the aqueous solution.Under 40～80 ℃, the resulting aqueous solution is carried out 3 hours concentrating under reduced pressure, be cooled to room temperature after, carry out natural filtration, obtain the target product of 1300g.In addition, be moisture is the atmosphere of 0.05 weight %, to implement from above-mentioned halogenation cyclisation operation to the solvent exchange operation.
Use resulting 5-chloro-2-methyl-4-isothiazoline-3-ketone to prepare the 10 weight % aqueous solution of 5-chloro-2-methyl-4-isothiazoline-3-ketone.The 10 weight % aqueous solution are to adopt high-speed liquid chromatography to carry out quantitatively preparing of 5-chloro-2-methyl-4-isothiazoline-3-ketone.For the residual organic solvent and the hydrolysate thereof of the resulting aqueous solution, adopt gas-chromatography that ethyl acetate, butyl acetate, ethanol, butanols, toluene are carried out quantitatively; Adopt Capillary Electrophoresis that acetate is carried out quantitatively.The result is shown in table 1.Condition determination is as follows.
The high-speed liquid chromatography analysis condition
Device: Tianjin, island HPLC system
Post: ODS bitt
Detector: UV
Analytical conditions for gas chromatography
Device: Tianjin, island GC system
Post: polar column
Detector: FID
The capillary electrophoresis analysis condition
Device: HP capillary electrophoresis system
Post: capillary column having coated layer
Detector: UV
Embodiment 2
The manufacturing of 5-chloro-2-methyl-4-isothiazoline-3-ketone
Use moisture be the butyl acetate of 0.05 weight % replace moisture be the ethyl acetate of 0.05 weight % as the solvent in the chlorination reaction, in addition likewise obtain the target product with embodiment 1.
Use resulting 5-chloro-2-methyl-4-isothiazoline-3-ketone; Adopt the 10 weight % aqueous solution that prepare 5-chloro-2-methyl-4-isothiazoline-3-ketone with embodiment 1 same method, likewise its residual organic matter and hydrolysate thereof are carried out quantitatively with embodiment 1.The result is shown in table 1.
Relatively more synthetic example 1
The manufacturing of 5-chloro-2-methyl-4-isothiazoline-3-ketone
Chlorination reaction
Using the moisture of 800g is the ethyl acetate of 0.5 weight %; To N; N '-dimethyl-3; 3 '-dithio dipropyl acidamide (150g, 0.54 mole, moisture 0.8 weight %) dilutes, and is blown into chlorine and reacts, and obtains the ethyl acetate slip of 5-chloro-2-methyl-4-isothiazoline-3-keto hydrochloride.
Filter, neutralize and concentrate
To filter resulting crystallization 5-chloro-2-methyl-4-isothiazoline-3-keto hydrochloride 180g to the slip that obtains and be dissolved in the water, interpolation magnesium nitrate hexahydrate, magnesia, hydrochloric acid are 1～4 with pH regulator, obtain the aqueous solution.Under 40～80 ℃, the resulting aqueous solution is carried out 6 hours concentrating under reduced pressure, be cooled to room temperature after, carry out natural filtration, obtain 1150g target product.In addition, be moisture is the atmosphere of 0.05 weight %, to implement from above-mentioned halogenation cyclisation operation to solvent exchange operation.
Use resulting 5-chloro-2-methyl-4-isothiazoline-3-ketone, likewise prepare the 10 weight % aqueous solution of 5-chloro-2-methyl-4-isothiazoline-3-ketone, likewise its residual organic matter and hydrolysate thereof are carried out quantitatively with embodiment 1 with embodiment 1.The result is shown in table 1.
Relatively more synthetic example 2
The manufacturing of 5-chloro-2-methyl-4-isothiazoline-3-ketone
Use moisture be the butyl acetate of 0.5 weight % replace moisture be the ethyl acetate of 0.5 weight % as the solvent in the chlorination reaction, in addition likewise obtain the target product with relatively more synthetic example 1.
Use resulting 5-chloro-2-methyl-4-isothiazoline-3-ketone, likewise prepare the 10 weight % aqueous solution of 5-chloro-2-methyl-4-isothiazoline-3-ketone, likewise its residual organic matter and hydrolysate thereof are carried out quantitatively with embodiment 1 with embodiment 1.The result is shown in table 1.
Table 1
| Organic solvent and hydrolysate thereof | Embodiment 1 | Embodiment 2 | Relatively more synthetic example 1 | Relatively more synthetic example 2 |
| Ethyl acetate | ?＜10ppm | ?＜10ppm | ?2200ppm | ＜10ppm |
| Butyl acetate | ?＜10ppm | ?＜10ppm | ?＜10ppm | 5000ppm |
| Acetate | ?＜10ppm | ?＜10ppm | ?3200ppm | 3500ppm |
| Ethanol | ?＜10ppm | ?＜10ppm | ?2200ppm | 20ppm |
| Butanols | ?＜10ppm | ?＜10ppm | ?＜10ppm | 1000ppm |
| Toluene | ?＜10ppm | ?＜10ppm | ?＜10ppm | ＜10ppm |
Embodiment 3, comparative example 1,2
The TOC of the permeate water in the RO membrane module reduces effect
The 10 weight % aqueous solution of 5-chloro-2-methyl-4-isothiazoline-3-ketone that use is made by embodiment 1 and relatively synthetic example 1～2 are as slimicide.The RO film uses 4 inches assemblies of DOW system BW-10, will operate to press to be adjusted into 1.5Mpa.Supply water in the RO membrane module uses the dechlorination water that penetrates active carbon.For the residual free chloro concentration of dechlorination water, confirm as 0 through the DPD method.For slimicide, be that the mode of 0.15mg/L is added according to the concentration that makes 5-chloro-2-methyl-4-isothiazoline-3-ketone in supplying with water.TOC to the processing water that penetrates the RO membrane module measures.Result (ppb) is shown in table 2.
Table 2
| Embodiment 3 | Comparative example 1 | Comparative example 2 | |
| Manufacturing approach | Embodiment 1 | Relatively more synthetic example 1 | Relatively more synthetic example 2 |
| TOC(ppb) | ?5～11 | ?20～46 | 32～44 |
Can know by table 1, compare that in the slimicide of the present invention, the amount of residual organic solvent and hydrolysate thereof significantly reduces with existing product.And, can know that by table 2 use under the situation of such slimicide, the TOC of the permeate water of RO membrane separation device is the so extremely low value of 5～11ppb.
Embodiment 4, comparative example 3
The TOC of the permeate water in the RO system reduces effect
To be about 0.1ppm as slimicide by concentration by 5-chloro-2-methyl-4-isothiazoline-3-ketone that embodiment 1 and relatively more synthetic example 1 are made is added in the supply water.For supplying with water, use heat exchanger that water for industrial use is adjusted into 25 ℃, uses sodium hydroxide and sulfuric acid that its pH is adjusted into 7, make its security personnel's filter that penetrates 10 μ m, with the supply water of the water that obtains thus as the RO film.For the RO unit, the mode of feedwater that the ultralow pressure membrane module of 8 inches of day east electrician's systems is become the membrane module of back segment according to the membrane module condensed water that makes leading portion is carried out 3 row and is connected (3 rows (bank) constitute), uses resulting unit, is 178m supplying with water
3/ h, permeate water are 135m
3/ h (the rate of recovery: turn round under the condition 75.8%).At first, in above-mentioned RO unit, will be added into to supply with in the water by 0.1ppm by the 5-chloro-2-methyl-4-isothiazoline-3-ketone that relatively synthesizes example 1 manufacturing and turn round 45 days continuously.Then, under the identical state of the setting of pump, then add 5-chloro-2-methyl-4-isothiazoline-3-ketone of making by embodiment 1 and turned round 45 days continuously.Measure the passing of the TOC of the permeate water (permeate water of 3 row membrane modules being compiled the permeate water that obtains for one) between each on-stream period.The analysis result of the TOC of permeate water is shown in following table 3.
Table 3
| Embodiment 4 | Comparative example 3 | |
| Manufacturing approach | Embodiment 1 | Relatively more synthetic example 1 |
| TOC(ppb) | ?8～19 | 50～75 |
In comparative example 3, handle the TOC miss the mark value (less than 30ppb) of water, but through changing to embodiment 4, even be that the TOC that handles water also declines to a great extent, and has reached the desired value of handling water under 75% the condition in the rate of recovery.
Claims (11)
1. microbicide; It is to contain the microbicide of 5-chloro-2-methyl-4-isothiazoline-3-ketone as active ingredient; This microbicide is characterised in that the total content of organic solvent and hydrolysate thereof and the concentration of above-mentioned active ingredient satisfy following formula (1):
The organic solvent of representing by ppm and the total content of hydrolysate thereof * (10/B)≤200ppm (1)
In the formula (1), the numerical value of the active ingredient concentration that B representes to be represented by weight %.
2. the described microbicide of claim 1, wherein, organic solvent is acetic acid esters and/or hydrocarbon compound.
3. the described microbicide of claim 2, wherein, organic solvent is acetic acid esters or is acetic acid esters and hydrocarbon compound.
4. claim 2 or 3 described microbicides, wherein, hydrocarbon compound is a toluene.
5. claim 2 or 3 described microbicides, wherein, acetic acid esters is to be selected from least a in the group of being made up of ethyl acetate and butyl acetate.
6. each described microbicide of claim 2～5, wherein, the total content of acetic acid esters and hydrolysate thereof and the concentration of said active ingredient satisfy following formula (1 '):
The acetic acid esters of representing by ppm and the total content of hydrolysate thereof * (10/B)≤60ppm (1 ')
In the formula (1 '), the numerical value of the active ingredient concentration that B representes to be represented by weight %.
7. each described microbicide of claim 2～5, wherein, the content of acetate and the concentration of said active ingredient satisfy following formula (1 "):
The content of the acetate of representing by ppm * (10/B)≤10ppm (1 ")
Formula (in 1 "), the numerical value of the active ingredient concentration that B representes to be represented by weight %.
8. each described microbicide of claim 1～7; Wherein, The 5-chloro-2-methyl-4-isothiazoline-3-ketone of active ingredient for obtaining through following manufacturing process; Said manufacturing process be comprise the halogenation cyclisation operation of sulfide amide intermediate and the halogenation hydrogen salt of the compound that obtains by above-mentioned operation that carries out as required with 3-isothiazolone ring in the manufacturing process of the 5-chloro-2-methyl-4-isothiazoline-3-ketone of operation, in this manufacturing process:
Using moisture is the reaction dissolvent of the following acetic acid esters of 0.1 weight % as above-mentioned halogenation cyclisation operation; After the cyclisation operation and carrying out above-mentioned in and under the situation of operation before it; With moisture is that hydrocarbon compound below the 0.1 weight % is added into through the acetic acid esters dispersion liquid to resulting above-mentioned halogenation hydrogen salt and filters in the moist press cake that obtains; Filter, thereby be above-mentioned hydrocarbon compound above-mentioned acetic acid esters solvent exchange; Be to implement the atmosphere below moisture is 0.1 weight % from above-mentioned halogenation cyclisation operation to above-mentioned at least solvent exchange operation simultaneously.
9. each described microbicide of claim 1～8, wherein, said microbicide contains the active ingredient of 1～30 weight %.
10. each described microbicide of claim 1～9, wherein, said microbicide contains 5-chloro-2-methyl-4-isothiazoline-3-ketone as active ingredient, and it is as slimicide.
11. the Acarasiales control method with Water Purifiers of reverse osmosis membrane has been used the described microbicide of claim 1～10 in this method.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
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| JP2009-084528 | 2009-03-31 | ||
| JP2009084528 | 2009-03-31 | ||
| PCT/JP2010/055542 WO2010113857A1 (en) | 2009-03-31 | 2010-03-29 | Microbicide |
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| CN201410146810.8A Division CN103918666A (en) | 2009-03-31 | 2010-03-29 | Microbicide |
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| CN201410146810.8A Pending CN103918666A (en) | 2009-03-31 | 2010-03-29 | Microbicide |
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| JP (1) | JP5581312B2 (en) |
| KR (1) | KR101569556B1 (en) |
| CN (2) | CN102365022B (en) |
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| WO (1) | WO2010113857A1 (en) |
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| JP6789270B2 (en) * | 2018-09-06 | 2020-11-25 | 株式会社神鋼環境ソリューション | Water treatment method and water treatment equipment |
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| US4939266A (en) * | 1982-06-01 | 1990-07-03 | Rohm And Haas Company | Nitrosamine-free 3-isothiazolone |
| US5068344A (en) * | 1990-01-12 | 1991-11-26 | Rohm And Haas Company | Process for the preparation of salt free, water free 3-isothiazolone compounds |
| CN1062727A (en) * | 1990-12-11 | 1992-07-15 | 罗姆和哈斯公司 | The method for preparing the 3-isothiazolone compounds |
| EP0498347A1 (en) * | 1991-02-06 | 1992-08-12 | Bromine Compounds Ltd. | Process for the preparation of isothiazolone compounds |
| CN1071921A (en) * | 1991-10-30 | 1993-05-12 | 罗姆和哈斯公司 | Be used for suppressing to be formed the bromate and the method for nitrosamine by nitrate stabilized isothiazolones |
| CN101218216B (en) * | 2006-04-03 | 2010-08-25 | 北京天擎化工有限公司 | Preparation of N-substituted isothiazolinone derivatives |
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| CA1189514A (en) * | 1982-06-01 | 1985-06-25 | Horst O. Bayer | Nitrosamine-free 3-isothiazolones and process |
| JPH0466541A (en) * | 1990-07-03 | 1992-03-02 | Kurita Water Ind Ltd | Method for separating organic compound and separating agent |
| KR100212963B1 (en) * | 1995-12-21 | 1999-08-02 | 조민호 | A stabilized isothiazolone composition and process for preparing isothiazolones |
| US6376680B1 (en) * | 1995-12-21 | 2002-04-23 | Sk Chemicals Co., Ltd. | Process for the preparation of 3-isothiazolone mixture and composition comprising the mixture |
| JPH11171712A (en) * | 1997-09-19 | 1999-06-29 | Ichikawa Gosei Kagaku Kk | Isothiazolone preparation and its production |
| BRPI0702299B1 (en) * | 2006-06-02 | 2017-04-11 | Rohm & Haas | microbicidal composition |
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2010
- 2010-03-29 WO PCT/JP2010/055542 patent/WO2010113857A1/en active Application Filing
- 2010-03-29 CN CN201080014769.9A patent/CN102365022B/en active Active
- 2010-03-29 JP JP2011507178A patent/JP5581312B2/en not_active Expired - Fee Related
- 2010-03-29 KR KR1020117025535A patent/KR101569556B1/en not_active IP Right Cessation
- 2010-03-29 CN CN201410146810.8A patent/CN103918666A/en active Pending
- 2010-03-30 TW TW099109554A patent/TWI511669B/en active
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| US4939266A (en) * | 1982-06-01 | 1990-07-03 | Rohm And Haas Company | Nitrosamine-free 3-isothiazolone |
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| EP0498347A1 (en) * | 1991-02-06 | 1992-08-12 | Bromine Compounds Ltd. | Process for the preparation of isothiazolone compounds |
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| Publication number | Publication date |
|---|---|
| CN103918666A (en) | 2014-07-16 |
| JPWO2010113857A1 (en) | 2012-10-11 |
| WO2010113857A1 (en) | 2010-10-07 |
| KR101569556B1 (en) | 2015-11-16 |
| JP5581312B2 (en) | 2014-08-27 |
| CN102365022B (en) | 2014-05-14 |
| KR20120028862A (en) | 2012-03-23 |
| TW201100015A (en) | 2011-01-01 |
| TWI511669B (en) | 2015-12-11 |
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