CN1541529A - Sustained releasing agent for preventing and treating alga and legionella bacteria series and its compositions - Google Patents
Sustained releasing agent for preventing and treating alga and legionella bacteria series and its compositions Download PDFInfo
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- CN1541529A CN1541529A CNA2004100332018A CN200410033201A CN1541529A CN 1541529 A CN1541529 A CN 1541529A CN A2004100332018 A CNA2004100332018 A CN A2004100332018A CN 200410033201 A CN200410033201 A CN 200410033201A CN 1541529 A CN1541529 A CN 1541529A
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- legionella bacteria
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B26—HAND CUTTING TOOLS; CUTTING; SEVERING
- B26B—HAND-HELD CUTTING TOOLS NOT OTHERWISE PROVIDED FOR
- B26B13/00—Hand shears; Scissors
- B26B13/12—Hand shears; Scissors characterised by the shape of the handles
- B26B13/14—Hand shears; Scissors characterised by the shape of the handles without gripping bows in the handle
- B26B13/16—Hand shears; Scissors characterised by the shape of the handles without gripping bows in the handle spring loaded, e.g. with provision for locking the blades or the handles
Abstract
A sustained-release agent for controlling algae and Legionella bacteria containing dithiol compounds exhibiting sustained release properties by microencapsulation and cyclodextrin inclusion as an effective ingredient is provided. It is improved in skin irritation and useful in controlling algae and Legionella bacteria present in recycled water of a cooling tower, circulating cooling water of a freezing apparatus, cold and warm water systems, heat accumulation systems such as warm water pools, bathrooms or the like. The sustained-release agent for controlling algae and Legionella bacteria contains: a dithiol compound of the formula 1 and additionally one or more of corrosion inhibitors, scale inhibitors, defoamers and surfactants. In formula, R1 and R2 exhibit H or halogen and are each the same or different. The sustained release is microencapsulation and cyclodextrin inclusion. For an example, 95% by weight of microencapsulated formulations are mixed with 30% by weight of diethanolamine as corrosion inhibitors and 2% by weight of dimethyl silicone oil as defoamers.
Description
Technical field
The present invention relates to the agent for preventing and eliminating of water system algae, legionella bacteria.More specifically, the algae, the legionella bacteria that the present invention relates to be used for preventing and kill off the existence such as cold warm water system, accumulation of heat water system at the recirculated cooling water of cycle water, refrigerating plant of cooling tower and heated pool and outdoor bathing place etc. remove, make slowly-releasing alga that skin irritation is improved and legionella bacteria agent for preventing and eliminating, with and composition.
Background technology
What in recent years, the legionaires' disease problem that causes of the legionella bacteria of surviving in the open loop system cooling water by air-conditioning equipment etc. occurred is many.These cooling towers in the aerosol inlet chamber of cooling water, become the occurrence cause of legionaires' disease during near the window in room or the outer gas inlet port of air-conditioning etc.Particularly when needed air-conditioning summer, the water temperature of cooling tower uprised (about 15 ℃～35 ℃), and organic substance concentrates in tower, so algae or microorganism etc. enter from the outside, became the place of suitable algae reproduction or microorganism or pathogen propagation.In addition, biomembrane that is produced by microorganism or algae or foundry loam etc. are attached on the pipe, cause obstacles such as the low or filter obstruction of the heat exchanger effectiveness of heat exchanger, in addition, if propagation such as pathogenetic bacteria, particularly legionella bacteria are also dispersed, to become special pneumonia, for example legionaires' disease or Pang are put forward the cause of disease of Acker heat (Port Application テ イ ア Star Network Hot) etc.As countermeasure for such problem that causes by algae, microorganism, the method that anti-algae, antibacterial agent suppress the propagation of algae or microorganism, cell class is injected in use in circulating water etc., and will install and innerly carry out the physics cleaning and clean or use remover to carry out the clean method of chemistry etc.
As injecting the method that antibacterial agent suppresses the propagation of bacterium class, mainly use the organic compounds such as surfactant, hydrazine class and maleimide, isothiazoline compounds, phosphonium compounds, nitroalcohol compounds of halogen antibacterial agent such as chlorine or bromine, chlorine dioxide or quaternary ammonium salt etc.But there is the problem that is easy to etching apparatus and pipe in above-mentioned halogen compound, in above-mentioned organic compound, has the toxicity problem of skin irritation or sensitization, carcinogenicity etc. or renders a service inadequate problem.In addition, viewpoint or the problem of continuation, also necessary many medicaments, the problem that carrying capacity of environment is big used of existence from rendeing a service.As the method that addresses these problems, in order to suppress propagation, perhaps continue to add anti-algae, antibacterial agent, perhaps must must add at regular intervals.(for example, referring to patent documentation 1 and 2).
Dithiode class antibacterial agent by general formula (I) expression in the public clear 57-42603 communique of known spy is the material with high antibacterial activity, generally use (referring to patent documentation 3) mainly as paper grade (stock) foundry loam agent for preventing and eliminating, but the also the same toxicity problem with skin irritation etc. of this compound or under the alkali condition or the problem of easy decomposition under reducing substances or nucleopilic reagent (sulphide, amine etc.) with other organic compounds.In WO02/089578,, the method with this antibacterial agent microencapsulation has been proposed in order to address these problems.But, also unknown for removing the Legionella effective method.(for example, referring to patent documentation 4)
In addition, there is the skin irritation height in the dithiode class, when using with the powder form, because powder flies upward the problem that causes skin macula or bubble when touching skin, the problem that is difficult to launch during with the solid pharmaceutical preparation form.In addition, since water-soluble low, when using, must be dissolved in the hydrophilic kind solvent with the water treatment agent form, exist and be difficult to aqueous solution preparationization, be difficult to the problem of in open cycle system cools water, using.
Open in the flat 5-257011 communique the spy, introduced cyclodextrin and connect compound, reported alleviating of skin irritation, still with common bag as the known isothiazoline class of industrial bactericide, for the dithiode compound without any the record (for example, referring to patent documentation 5).
Patent documentation 1: special public clear 57-42603 communique
Patent documentation 2: the spy opens flat 7-256266 communique
Patent documentation 3: the spy opens the 2002-263659 communique
Patent documentation 4: the international brochure that discloses No. 02/089578
Patent documentation 5: the spy opens flat 5-257011 communique
Summary of the invention
The objective of the invention is to prevent and kill off the bacterium of the algae of existence in the cold warm water system, accumulation of heat water system etc. at the recirculated cooling water of cycle water at cooling tower, refrigerating plant and heated pool or outdoor bathing place etc. or legionella bacteria etc., make the stripping slowly-releasingization of dithiode class by microencapsulation or connecing of bag, improve continuation, reduce the toxicity of the skin irritation etc. of dithiode class when being attached on the skin simultaneously.In addition, the dithiode class of using among the present invention is effective under low concentration, so carrying capacity of environment is few.In addition, agent for preventing and eliminating of the present invention, agent for preventing and eliminating composition for mould also be effective.
The inventor has carried out repeating research in order to address the above problem, found that, use microencapsulation or wrap the dithiode compound of connecing, have good preventive effect, finished the present invention according to these discoveries for algae that in water system, survives and legionella bacteria by cyclodextrin.
That is, the present invention relates to the following:
(1) the slowly-releasing alga and the legionella bacteria agent for preventing and eliminating that are improved of a kind of skin irritation, this agent for preventing and eliminating be necessary composition with the dithiode compound of general formula (I) expression,
In the formula, R1 and R2 represent hydrogen atom or halogen atom, separately can be identical or different.
(2) slowly-releasing alga and the legionella bacteria agent for preventing and eliminating that is improved as the 1st described skin irritation is characterized in that slowly-releasing turns to microencapsulation.
(3) slowly-releasing alga and the legionella bacteria agent for preventing and eliminating that is improved as the 1st described skin irritation is characterized in that slowly-releasing turns to by cyclodextrin and wraps connecing.
(4) the slowly-releasing alga and the legionella bacteria agent for preventing and eliminating that are improved of a kind of skin irritation is characterized in that each described agent for preventing and eliminating of (1)～(3) is used for cooling-tower circulating water.
(5) the slowly-releasing alga and the legionella bacteria agent for preventing and eliminating composition that are improved of a kind of skin irritation, it is characterized in that, the dithiode compound with general formula (I) expression serve as must composition the slowly-releasing alga that is improved of skin irritation and the legionella bacteria agent for preventing and eliminating in cooperate at least a of preservative, scale preventative, defoamer and surfactant
In the formula, R1 and R2 represent hydrogen atom or halogen atom, separately can be identical or different.
(6) algae and the legionella bacteria agent for preventing and eliminating that are improved of a kind of skin irritation is characterized in that (5) described composition is used for cooling-tower circulating water.
Embodiment
The dithiode compound that the present invention uses is the known compound that has good effect as the foundry loam agent for preventing and eliminating, is used in paper industry in machine hand's preface.
As the dithiode compound of general formula (I) expression, can enumerate 4,5-two chloro-1,2-dithiode-3-ketone, 4-phenyl-5-chloro-1,2-dithiode-3-ketone, 1,2-dithiode-3-ketone also can use their mixture.Wherein, preferred 4,5-two chloro-1,2-dithiode-3-ketone.
The dithiode compound of general formula (I) expression in micro-capsule or the content in connecing of the bag thing have no particular limits, as addition, with respect to the water system of legionella bacteria existence, the dithiode compound concentrations preferably in the scope of 0.1～100000mg/L, more preferably 1～100mg/L.
Among the present invention, also can use other antibacterial agent.As and the antibacterial agent of usefulness, can enumerate surfactant series bactericidal agents such as quaternary ammonium salt, hydrazine class or maleimide, iso thiazolinium compound phosphonium compounds, the bromine nitro compound, pyrithione (ピ リ チ オ Application) compounds etc., specifically, N, N-dimethyl-N, N-two positive decyl ammonium chlorides, N, N-dimethyl-N, N-di-n-octyl ammonium chloride, N, N-dimethyl-N-octyl group-N-decyl ammonium chloride, N, the different nonyl of N-dimethyl-N--N-decyl ammonium chloride, N-cetyl-N, N, the N-trimethyl ammonium chloride, N-cetyl-N, N, the N-trimethylammonium bromide, N, N-dimethyl-N-octadecyl-N-(3-(trimethoxysilyl) propyl group) ammonium chloride, hydrazine, hydrazine hydrate, the sorbic acid hydrazine, maleimide, N-methyl maleimide, the N-ethyl maleimide, citraconimide, N-methyl citraconimide, N-ethyl citraconimide, 2,3-dimethyl maleimide, N-methyl-2,3-dimethyl maleimide, N-ethyl-2,3-dimethyl maleimide, N-(2-ethoxy) maleimide, N-cyclohexyl maleimide, N-4-hydroxy-cyclohexyl maleimide, N-phenylmaleimide, N-p-hydroxybenzene maleimide, N-is to the hydroxybenzyl maleimide, 5-chloro-2-methyl-4-isothiazoline-3-ketone, 2-methyl-4-isothiazoline-3-ketone, 5-chloro-2-n-octyl isothiazoline-3-ketone, 1, the 2-benzisothiazole-3-ketone, four (methylol) Phosphonium sulphate, four (methylol) Phosphonium phosphate, four (methylol) Phosphonium nitrate, four (methylol) phosphonium salt hydrochlorates, four (methylol) Phosphonium bromates, four (methylol) Phosphonium fluorate, 2-bromo-2-nitropropane-1, the 3-glycol, 2,2-two bromo-2-nitropropane-1-ethanol, 2,2-two bromo-3-nitro propionamides, two (2-pyridinethiol-1-oxide) mantoquita, two (2-pyridinethiol-1-oxide) zinc salt, two (2-pyridinethiol-1-oxide) molysite, 2-pyridine radicals sulfenyl-1-oxide sodium salt, pyrithione (ピ リ チ オ Application) disulphide, glutaraldehyde, hydrogen peroxide, 1-bromo-3-chloro-5, the 5-dimethyl hydantoin, the di-2-ethylhexylphosphine oxide thiocyanates, clorox, 1,5-pentanediol (ペ Application Application ジ ア one Le), 3-(3, the 4-dichlorophenyl)-1, the 1-di 2 ethylhexyl phosphonic acid, 2,3,3-triiodo allyl alcohol, wherein preferred 2,2-two bromo-3-nitro propionamides, 2-bromo-2-nitropropane-1, the 3-glycol, 5-chloro-2-methyl-4-isothiazoline-3-ketone, 2-methyl-4-isothiazoline-3-ketone.
These sterilizations, antibacterial agent can separately or mix back and dithiode compound and usefulness, and its use level preferably is no more than the use level of dithiode compound.
Can and the sterilization of usefulness, antibacterial agent also can with can microencapsulation or the dithiode compound of connecing of bag and using.In addition, in the scope of not damaging the antibacterial ability by microencapsulation or the dithiode compound that obtains with connecing of cyclodextrin bag, also can and with halogen antibacterial agents such as chlorine, bromine, chlorine dioxide.
The macromolecular compound that is used to form the micro-capsule wall that uses in microencapsulation can be macromolecular compound of polyamide, saturated and unsaturated polyester resin, epoxy resin, polyurethane resin, silicones, melamine resin, gelatin, urea resin, phenolic resins etc. or the macromolecule of being made up of the mixture of these compounds, and there is no particular limitation.Wherein, preferred melamine resin, polyurethane resin, polyamide, preferred especially melamine resin.
Microencapsulation method for example can adopt the method for the following stated.Promptly, in order to prepare with agent for preventing and eliminating of the present invention is the micro-capsule of core material, for example, comprise core material with water-soluble polymers such as gelatin, by the core capsule method of its concentrated phase being separated, sclerosis forms the wall film, monomer is implanted in the core material of dispersity, made itself and water-soluble monomer polymerization on its interface of the solution that forms continuous phase, form the interface polycondensation of the wall film that contains core material.In addition, polymerization catalyst is adsorbed on the core material, any can use the known microencapsulation method of the feasible situ aggregation method that forms the wall film from outside encirclement initial stage condensation polymer that reacts then etc. etc., has no particular limits.
Connecing of the bag agent for preventing and eliminating that utilizes cyclodextrin of the present invention is meant uses cyclodextrin, and promptly the cyclodextrin of alpha-cyclodextrin, beta-schardinger dextrin-, gamma-cyclodextrin, methyl-alpha-cyclodextrin, methyl-beta-schardinger dextrin-, methyl-gamma-cyclodextrin, hydroxypropyl-alpha-cyclodextrin, HP-, hydroxypropyl-gamma-cyclodextrin etc. connects the material that forms with the dithiode compound bag of general formula (I) expression.
Connecing of bag method can be undertaken by the method for the following stated, but there is no particular limitation.
＜saturated water solution method 〉
Add in the saturated aqueous solution of cyclodextrin after the dithiode compound is dissolved in a spot of appropriate solvent directly or with it, stir 0.5 hour to a few hours the time when violent mixing, connecing of bag thing of the present invention is separated out with solid, shaped.During with its filtration, drying, obtain pulverous connecing of bag thing of the present invention.
＜kneading method 〉
The water that adds 0.3～3 times of amount in cyclodextrin is mediated, and obtains slurry.The dithiode compound directly or after being dissolved in a spot of appropriate solvent is added in the slurry of gained, mediate 0.5 hour, obtain connecing of bag thing of the present invention to a few hours.
Connecing of bag thing of the present invention is not direct stripping as agent for preventing and eliminating active component dithiode compound, even so attached to its skin irritation on the skin also a little less than, can be used as Powdered agent for preventing and eliminating and use, use after also powder can being processed into solid shape such as graininess or tablet in addition.
Preservative in the composition of the present invention can be enumerated, MEA, diethanol amine, triethanolamine, l, 2,3 triazole, alkyl BTA etc.
As scale preventative, can enumerate, SSS, contain sulfonic polymer, 1,4-naphthoquinones, 1,2-naphthoquinones, benzoquinones, phosphonate, orthophosphates, Quadrafos etc.
As defoamer, can enumerate the silicone oil of dimethicone, alkyl aralkyl modification, fluorine containing silicone oil, fatty acid glyceride, lecithin etc.
As surfactant, can enumerate the anion surfactant of alkylbenzenesulfonate, alkyl ether sulfate etc., aliphatic quaternary ammonium salt, benzalkonium chloride (salt ベ Application ザ コ ニ ウ ム salt), the non-ionic surface active agent of amphoteric surfactant of cationic surfactant of pyridiniujm etc., carboxybetaine, aminocarboxylate, imidazole salts betain etc., polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene fatty acid glyceride, polyglyceryl fatty acid ester, sucrose fatty ester etc.
As agent for preventing and eliminating composition of the present invention for the application method in the target water system, can enumerate, for example, by the agent for preventing and eliminating composition is directly added, drops into or is mixed in the water system, perhaps in advance the agent for preventing and eliminating composition is coated with or is immersed in fixed bed, the first-class method of filter.
Agent for preventing and eliminating of the present invention can be controlled the bacterium class of the legionella bacteria of existence in the changes in temperature water system, accumulation of heat water system of the recirculated cooling water of refrigerating plant, the circulation of 24 hours bathing pools etc. etc. etc., prevents its generation, its propagation.
As long as the content of dithiode compound in the agent for preventing and eliminating of microencapsulation or connecing of bag of general formula (I) expression is for reaching the necessary content of the object of the invention, and there is no particular limitation.
In addition, as the interpolation concentration of dithiode compound, for the water system of legionella bacteria or existence, the dithiode compound concentrations is preferably 0.1～100, in the 000mg/L scope, and 1～100mg/L more preferably.
Embodiment
The present invention is described by the following examples in further detail, but the invention is not restricted to these embodiment.
Synthesis example 1
At 160 dissolving 40 grams 4 in two dibutyl phthalates of restraining oneself, 5-two chloro-1,2-dithiode-3-ketone has prepared A liquid.Add A liquid in aqueous gelatin solution 300 grams 2% and carry out emulsification, prepared the O/W emulsion.With 10% aqueous sodium carbonate the pH of gained O/W emulsion is transferred to 8～9, add 80 gram melamine formaldehyde (MF)s.With citric acid pH is transferred to 5.5 then, stirred 2 hours at 70 ℃, the average grain diameter that has obtained having the melamine film is 2 microns the microencapsulation preparation (YF-12) that includes dithiode.
Embodiment 1
(1) preparation of sample
In 6 300mL conical flasks, add the 200mL pure water, carry out high pressure steam sterilization.Get 10.31 the gram YF-12, with pure water be metered into 100mL (4,5-two chloro-1, the concentration of 2-dithiode-3-ketone is 10,000mg/L).With the solution that obtains as specimen preparation solution.Add the specimen preparation solution of 20 μ L, 100 μ L, 200 μ L, 400 μ L, 600 μ L in the conical flask after sterilization, the NaOH or the HCl aqueous solution of preparation sterilization make pH in 6.5～7.5 scopes.Comprise blank solution, the concentration of substances is set at 0,1,5,10,20,30mg/L.
(2) preparation of bacterium suspension
At the legionella bacteria of BCYE inoculation of medium appropriate amount, cultivated to become the fresh cultured bacterium in advance on the same day of test.Scrape from medium with platinum loop and to get bacterium, it is suspended in the aqua sterilisa.After approximately being suspended to 107/mL, all add 2mL in each conical flask.The moment of adding bacterium is the moment of on-test.
(3) mensuration of bacterium number
After 0,6,12,24,48 hours on-tests, get experimental liquid, make a series of dilutions of 1,10,100,1,000,10,000 times, get dilution 0.1mL, spread upon on the WYO medium.Then, install in the vinyl bag, cultivate a week with its inversion and at 37 ℃ for avoiding dry.After cultivate finishing, measure bacterium colony, measured the legion that changes with change in concentration one belong to viable count, in time through and the legion that changes belongs to viable count.These results are as shown in table 1.
Embodiment 2
(1) preparation of sample
In 6 300mL conical flasks, add the 200mL pure water, carry out high pressure steam sterilization.Get 10.31 the gram YF-12, with pure water be metered into 100mL (4,5-two chloro-1, the concentration of 2-dithiode-3-ketone is 10,000mg/L).With the solution that obtains as specimen preparation solution.Add the specimen preparation solution of 20 μ L, 50 μ L, 100 μ L in the conical flask after sterilization, the NaOH or the HCl aqueous solution of preparation sterilization make pH in 6.5～7.5 scopes.Comprise blank solution, the concentration of substances is set at 0,0.1,0.25,0.5mg/L.
(2) preparation of bacterium suspension
At the legionella bacteria of BCYE inoculation of medium appropriate amount, cultivated to become the fresh cultured bacterium in advance on the same day of test.Scrape from medium with platinum loop and to get bacterium, it is suspended in the aqua sterilisa.Approximately be suspended to 10
7Behind individual/mL, all add 2mL in each conical flask.The moment of adding bacterium is the moment of on-test.After 24 hours on-tests, on the meaning of the continuation of the effect of confirming medicament, similarly added bacterium once more.
(3) mensuration of bacterium number
After 0,6,12,24,30,36,48 hours on-tests, get experimental liquid, make a series of dilutions of 1,10,100,1,000,10,000 times, get dilution 0.1mL, spread upon on the WYO medium.Then, install in the vinyl bag, cultivate a week with its inversion and at 37 ℃ for avoiding dry.After cultivate finishing, measure bacterium colony, measured the legion that changes with change in concentration one belong to viable count, in time through and the legion that changes belongs to viable count.These results are as shown in table 2.
Comparative example 1
Remove and use the aqueous solution (the ロ one system ア Application De Ha one ス She System that contains 5-chloro-2-methyl-4-isothiazoline-3-ketone 10 weight % and 2-methyl-4-isothiazoline-3-ketone 4 weight %, trade name: KATHON WT) replace YF-12, the concentration of 5-chloro-2-methyl-4-isothiazoline-3-ketone and 2-methyl-4-isothiazoline-3-ketone adds up to and is set at 0,1,5,10,20, beyond the 30mg/L, operates according to mode similarly to Example 1.These results are as shown in table 1.
Comparative example 2
Remove and use 2-bromo-2-nitropropane-1,3-glycol (Nagase chemical Co., Ltd's system, trade name: Block ロ ノ Port one Le) replace operating according to mode similarly to Example 1 beyond the YF-12.These results are as shown in table 1.
Comparative example 3
Remove and use the aqueous solution (the ロ one system ア Application De Ha one ス She System that contains 5-chloro-2-methyl-4-isothiazoline-3-ketone 10 weight % and 2-methyl-4-isothiazoline-3-ketone 4 weight %, trade name: KATHON WT) replace YF-12, the concentration of 5-chloro-2-methyl-4-isothiazoline-3-ketone and 2-methyl-4-isothiazoline-3-ketone adds up to and is set at 0,0.1,0.25, beyond the 0.5mg/L, operates according to mode similarly to Example 2.These results are as shown in table 2.
Table 1
| Add concentration (mg/L) | After 0 hour | After 6 hours | After 12 hours | After 24 hours | After 48 hours | |
| Embodiment 1 | ??0 | ?10 5 | ????10 5 | ????10 5 | ????10 5 | ????10 5 |
| ??1 | ?10 5 | ????4.5×10 3 | ????＜10 | ????＜10 | ????＜10 | |
| ??5 | ?10 5 | ????＜10 | ????＜10 | ????＜10 | ????＜10 | |
| ??10 | ?10 5 | ????＜10 | ????＜10 | ????＜10 | ????＜10 | |
| ??20 | ?10 5 | ????＜10 | ????＜10 | ????＜10 | ????＜10 | |
| ??30 | ?10 5 | ????＜10 | ????＜10 | ????＜10 | ????＜10 | |
| Comparative example 1 | ??0 | ?10 5 | ????10 5 | ????10 5 | ????10 5 | ????10 5 |
| ??1 | ?10 5 | ????10 5 | ????5.5×10 4 | ????3.5×10 4 | ????2.1×10 5 | |
| ??5 | ?10 5 | ????4.1×10 4 | ????5.5×10 3 | ????1.1×10 3 | ????＜10 | |
| ??10 | ?10 5 | ????4.9×10 3 | ????7.8×10 2 | ????＜10 | ????＜10 | |
| ??20 | ?10 5 | ????8.9×10 2 | ????＜10 | ????＜10 | ????＜10 | |
| ??30 | ?10 5 | ????＜10 | ????＜10 | ????＜10 | ????＜10 | |
| Comparative example 2 | ??0 | ?10 5 | ????10 5 | ????10 5 | ????10 5 | ????10 5 |
| ??1 | ?10 5 | ????10 5 | ????10 5 | ????10 5 | ????10 5 | |
| ??5 | ?10 5 | ????10 5 | ????5.6×10 4 | ????2.1×10 5 | ????6.5×10 5 | |
| ??10 | ?10 5 | ????8.9×10 4 | ????2.1×10 4 | ????3.6×10 3 | ????＜10 | |
| ??20 | ?10 5 | ????2.7×10 4 | ????5.6×10 3 | ????＜10 | ????＜10 | |
| ??30 | ?10 5 | ????5.1×10 3 | ????＜10 | ????＜10 | ????＜10 |
Table 2
| Add concentration (mg/L) | After 0 hour | After 6 hours | After 12 hours | After 24 hours | Inoculate bacterium after 24 hours | After 30 hours | After 36 hours | After 48 hours | |
| Embodiment 2 | ??0 | ??10 6 | ??8×10 5 | ??7×10 5 | ??6×10 5 | ??5×10 6 | ??4×10 6 | ??4×10 6 | ??3×10 6 |
| ??0.1 | ??10 6 | ??3×10 5 | ??5×10 4 | ??1×10 4 | ??3×10 5 | ??2×10 5 | ??3×10 4 | ||
| ??0.25 | ??10 6 | ??2×10 5 | ??2×10 4 | ??3×10 2 | ??2×10 5 | ??2×10 5 | ??1×10 3 | ||
| ??0.5 | ??10 6 | ??4×10 3 | ??1×10 3 | ??1×10 2 | ??2×10 5 | ??5×10 4 | ??＜10 | ||
| Comparative example 3 | ??0 | ??10 6 | ??8×10 5 | ??7×10 5 | ??6×10 5 | ??5×10 6 | ??4×10 6 | ??4×10 6 | ??3×10 6 |
| ??0.1 | ??10 6 | ??3×10 5 | ??2×10 5 | ??7×10 4 | ??4×10 5 | ??3×10 5 | ??2×10 5 | ||
| ??0.25 | ??10 6 | ??2×10 5 | ??6×10 4 | ??2×10 4 | ??2×10 5 | ??2×10 5 | ??1×10 4 | ||
| ??0.5 | ??10 6 | ??1×10 5 | ??4×10 4 | ??2×10 3 | ??2×10 5 | ??2×10 5 | ??8×10 3 |
(individual/as mL) to compare, use the embodiment 1 of YF-12 was 4.5 * 10 after 6 hours to viable count during from the result of table 1 as can be seen, with the interpolation concentration 1mg/L of each medicament shown in embodiment 1, the comparative example 1,2
3About individual/mL, after 12 hours＜10/mL about, after 24 hours＜10/mL about, after 48 hours＜10/mL about, in contrast, the comparative example 1,2 that uses known bactericide is 10
4～10
5About individual/mL.In addition, in the table 2, during lower interpolation concentration 0.5, inoculate 48 hours of YF-12 once more after＜10/mL about, in contrast, use in the comparative example 3 of known bactericide, be 8 * 10 after 48 hours
3About individual/mL, thus contain the dithiode compound be the antibacterial agent of microencapsulation of principal component under low concentration for the power of preventing and kill off of legionella bacteria also than known bactericide excellence.
In addition, as can be seen, even inoculated bacterium once more for the continuation of confirming bactericide after 24 hours, YF-12 also has degerming power in the table 2, even after the sterilization, the effect of medicament also continues.
Synthesis example 2
The preparation " bag connects compound 1 " of connecing of cyclodextrin bag thing:, in mortar, mediate up to becoming muddy at 30 gram beta-schardinger dextrin-s (, selling) Zhong Jiashui with trade name セ Le デ Star Network ス B-100 from Japan Food Chemical Co., Ltd.Add 5 grams 4 therein, 5-two chloro-1,2-dithiode-3-ketone (エ of Co., Ltd. one ピ one ア イ コ one Port レ one シ ヨ Application System of society, マ イ Network ロ バ Application 86 former medicines) continues to mediate.Viscosity increases gradually after about 20 minutes, but stops to mediate when being stabilized in certain certain viscosity number, carries out drying, pulverizing, obtains required connecing of bag thing powder.
Measure the infrared absorption spectroscopy of this powder, confirmed that the distinctive absorption band of non-existent dithiode compound moves to high wave number direction in beta-schardinger dextrin-, for bag connects compound.
The dithiode compound of dithiode compound → connecing of bag: 1516～1521cm
-1→ 1526～1531cm
-1, 1626～1631cm
-1→ 1680～1685cm
-1
Synthesis example 3
The preparation " bag connects compound 1 " of connecing of cyclodextrin bag thing:, in mortar, mediate up to becoming muddy at 30 gram 2-HP-(derive from Japan Food Chemical Co., Ltd, sell) Zhong Jiashui with trade name セ Le デ Star Network ス HP-β-CD.Add 4 grams 4 therein, 5-two chloro-1,2-dithiode-3-ketone (エ of Co., Ltd. one ピ one ア イ コ one Port レ one シ ヨ Application System of society, マ イ Network ロ バ Application 86 former medicines) continues to mediate.Viscosity increases gradually after about 20 minutes, but stops to mediate when being stabilized in certain certain viscosity number, carries out drying, pulverizing, obtains required connecing of bag thing powder.
The same with synthesis example 2, this powder has been confirmed also the specific absorption band of dithiode compound in its infrared absorption spectroscopy moves to high wave number direction, become bag and connect compound.
Embodiment 3
After 6 300mL containers that added the 200mL pure water are carried out high pressure steam sterilization, with ultimate density be 0,1,5,10,20, the such mode of 30mg/L adds " bag connects compound 1 ".Get the legionella bacteria of fresh cultured, in pure water, adjust to about 10
7Individual/mL, in each container, add 10mL, make finally to reach 10
5Individual/mL.Mix constantly, after 0,6,12,24,48 hour, get liquid, 10 times of dilution series in a plurality of stages have been made, and be seeded in the WYO α medium, 37 ℃ cultivated for 1 week after, measure the bacterium colony that occurs, checked the legion that changes with change in concentration one belong to viable count and in time through and legion's genus viable count of changing.The result is as shown in table 3.
Comparative example 4
Remove and use the aqueous solution (the ロ one system ア Application De Ha one ス She System that contains 5-chloro-2-methyl-4-isothiazoline-3-ketone 10 weight % and 2-methyl-4-isothiazoline-3-ketone 4 weight %, trade name: KATHON WT) replace " bag connects compound 1 ", the concentration of 5-chloro-2-methyl-4-isothiazoline-3-ketone and 2-methyl-4-isothiazoline-3-ketone adds up to and is set at 0,1,5,10,20, beyond the 30mg/L, operates according to mode similarly to Example 3.These results are as shown in table 3.
Comparative example 5
Remove and use 2-bromo-2-nitropropane-1,3-glycol (common name: Block ロ ノ Port one Le) replace operating according to mode similarly to Example 3 outside " bag connects compound 1 ".The result is as shown in table 3.
Table 3
| Add concentration (mg/L) | Viable count (individual/mL) | |||||
| After 0 hour | After 6 hours | After 12 hours | After 24 hours | After 48 hours | ||
| Embodiment 3 | ??0 | ?10 5 | ????10 5 | ????10 5 | ????10 5 | ????10 5 |
| ??1 | ?10 5 | ????4.5×10 3 | ????＜10 2 | ????＜10 2 | ????＜10 2 | |
| ??5 | ?10 5 | ????＜10 2 | ????＜10 2 | ????＜10 2 | ????＜10 2 | |
| ??10 | ?10 5 | ????＜10 2 | ????＜10 2 | ????＜10 2 | ????＜10 2 | |
| ??20 | ?10 5 | ????＜10 2 | ????＜10 2 | ????＜10 2 | ????＜10 2 | |
| ??30 | ?10 5 | ????＜10 2 | ????＜10 2 | ????＜10 2 | ????＜10 2 | |
| Comparative example 4 | ??0 | ?10 5 | ????10 5 | ????10 5 | ????10 5 | ????10 5 |
| ??1 | ?10 5 | ????10 5 | ????5.5×10 4 | ????3.5×10 4 | ????2.1×10 5 | |
| ??5 | ?10 5 | ????4.1×10 4 | ????5.5×10 3 | ????1.1×10 3 | ????＜10 2 | |
| ??10 | ?10 5 | ????4.9×10 3 | ????7.8×10 2 | ????＜10 2 | ????＜10 2 | |
| ??20 | ?10 5 | ????8.9×10 2 | ????＜10 2 | ????＜10 2 | ????＜10 2 | |
| ??30 | ?10 5 | ????＜10 2 | ????＜10 2 | ????＜10 2 | ????＜10 2 | |
| Comparative example 5 | ??0 | ?10 5 | ????10 5 | ????10 5 | ????10 5 | |
| ??1 | ?10 5 | ????10 5 | ????10 5 | ????10 5 | ????10 5 | |
| ??5 | ?10 5 | ????10 5 | ????5.6×10 4 | ????2.1×10 5 | ????6.5×10 5 | |
| ??10 | ?10 5 | ????8.9×10 4 | ????2.1×10 4 | ????3.6×10 3 | ????＜10 2 | |
| ??20 | ?10 5 | ????2.7×10 4 | ????5.6×10 3 | ????＜10 2 | ????＜10 2 | |
| ??30 | ?10 5 | ????5.1×10 3 | ????＜10 2 | ????＜10 2 | ????＜10 2 | |
As can be seen from Table 3, relatively the viable count during the interpolation concentration 1mg/L of each medicament as can be seen, using the embodiment 3 of " bag connects compound 1 " was 4.5 * 10 after 6 hours
3About individual/mL, after 12 hours is＜10
2About individual/mL, after 24 hours is＜10
2About individual/mL, after 48 hours is＜10
2About individual/mL, in the comparative example 1,2 that uses known bactericide, be 10
5About individual/mL, be that the micro-capsule of principal component is prevented and kill off the known bactericide excellence of force rate for legionella bacteria so contain the dithiode compound.
Embodiment 4
(1) preparation of sample
In 6 300mL conical flasks, add the 200mL pure water, carry out high pressure steam sterilization.Get 379 milligrams of compounds 2, be metered into 100mL with pure water.With the solution that obtains as specimen preparation solution.Add the specimen preparation solution of 20 μ L, 100 μ L, 200 μ L, 400 μ L, 600 μ L in the conical flask after sterilization, the NaOH or the HCl aqueous solution of preparation sterilization make pH in 7.0 scope.Comprise blank solution, the concentration of substances is set at 0,1,5,10,20,30mg/L.
(2) preparation of bacterium suspension
At the legionella bacteria of BCYE inoculation of medium appropriate amount, cultivated to become the fresh cultured bacterium in advance on the same day of test.Scrape from medium with platinum loop and to get bacterium, it is suspended in the aqua sterilisa.Approximately be suspended to 10
7Behind individual/mL, all add 2mL in each conical flask.The moment of adding bacterium is the moment of on-test.
(3) mensuration of bacterium number
After 0,6,12,24,48 hours on-tests, get experimental liquid, make a series of dilutions of 1,10,100,1,000,10,000 times, get dilution 0.1mL, spread upon on the WYO medium.Then, install in the vinyl bag, cultivate a week with its inversion and at 37 ℃ for avoiding dry.After cultivate finishing, measure bacterium colony, measured the legion that changes with change in concentration one belong to viable count, in time through and the legion that changes belongs to viable count.These results are as shown in table 4.
Embodiment 5
Except that pH is become 8, operate according to mode similarly to Example 4.These results are as shown in table 4.
Comparative example 6
Remove and use the aqueous solution (ロ one system ア Application De Ha one ス She System, the trade name: KATHON WT) replace bag to connect compound 2 that contains 5-chloro-2-methyl-4-isothiazoline-3-ketone 10 weight % and 2-methyl-4-isothiazoline-3-ketone 4 weight %.The concentration of 5-chloro-2-methyl-4-isothiazoline-3-ketone and 2-methyl-4-isothiazoline-3-ketone adds up to and is set at 0,1,5,10,20, beyond the 30mg/L, operates according to mode similarly to Example 4.These results are as shown in table 4.
Comparative example 7
Remove and use 2-bromo-2-nitropropane-1,3-glycol (Nagase chemical Co., Ltd's system, trade name: Block ロ ノ Port one Le) replace bag to connect beyond the compound 2, operate according to mode similarly to Example 4.These results are as shown in table 4.
Reference example 1
Use 4,5-two chloro-1,2-dithiode-3-ketone (not connecing of bag) replaces bag to connect compound 2, when estimating with operation similarly to Example 4, produces precipitation, can not measure the legionella bacteria viable count through changing in time.
Table 4
| Add concentration (mg/L) | After 0 hour | After 3 hours | After 6 hours | After 12 hours | After 24 hours | After 48 hours | |
| Embodiment 4 | ??0 | ??1×10 7 | ????8×10 6 | ????6×10 6 | ??4×10 6 | ??2×10 6 | ??2×10 6 |
| ??1 | ??1×10 7 | ????＜10 | ????＜10 | ??＜10 | ??＜10 | ??＜10 | |
| ??5 | ??1×10 7 | ????＜10 | ????＜10 | ??＜10 | ??＜10 | ??＜10 | |
| ??10 | ??1×10 7 | ????＜10 | ????＜10 | ??＜10 | ??＜10 | ??＜10 | |
| ??20 | ??1×10 7 | ????＜10 | ????＜10 | ??＜10 | ??＜10 | ??＜10 | |
| ??30 | ??1×10 7 | ????＜10 | ????＜10 | ??＜10 | ??＜10 | ??＜10 | |
| Embodiment 5 | ??0 | ??3×10 7 | ????2×10 7 | ????1×10 7 | ??1×10 7 | ??8×10 6 | ??8×10 6 |
| ??1 | ??3×10 7 | ????2×10 1 | ????＜10 | ??＜10 | ??＜10 | ??＜10 | |
| ??5 | ??3×10 7 | ????＜10 | ????＜10 | ??＜10 | ??＜10 | ??＜10 | |
| ??10 | ??3×10 7 | ????＜10 | ????＜10 | ??＜10 | ??＜10 | ??＜10 | |
| ??20 | ??3×10 7 | ????＜10 | ????＜10 | ??＜10 | ??＜10 | ??＜10 | |
| ??30 | ??3×10 7 | ????＜10 | ????＜10 | ??＜10 | ??＜10 | ??＜10 | |
| Comparative example 6 | ??0 | ??6×10 6 | ????- | ????5×10 6 | ??4×10 6 | ??3×10 6 | ??3×10 6 |
| ??1 | ??6×10 6 | ????- | ????4×10 5 | ??2×10 5 | ??2×10 3 | ??1×10 3 | |
| ??5 | ??6×10 6 | ????- | ????3×10 5 | ??1×10 5 | ??2×10 3 | ??8×10 1 | |
| ??10 | ??6×10 6 | ????- | ????3×10 5 | ??1×10 5 | ??9×10 2 | ??3×10 1 | |
| ??20 | ??6×10 6 | ????- | ????3×10 5 | ??1×10 5 | ??4×10 2 | ??3×10 1 | |
| ??30 | ??6×10 6 | ????- | ????2×10 5 | ??5×10 4 | ??2×10 2 | ??2×10 1 | |
| Comparative example 7 | ??0 | ??6×10 6 | ????- | ????5×10 6 | ??4×10 6 | ??3×10 6 | ??3×10 6 |
| ??1 | ??6×10 6 | ????- | ????5×10 6 | ??3×10 6 | ??1×10 6 | ??8×10 5 | |
| ??5 | ??6×10 6 | ????- | ????5×10 5 | ??3×10 5 | ??2×10 3 | ??8×10 2 | |
| ??10 | ??6×10 6 | ????- | ????3×10 5 | ??8×10 4 | ??2×10 3 | ??8×10 1 | |
| ??20 | ??6×10 6 | ????- | ????2×10 5 | ??1×10 5 | ??2×10 3 | ??5×10 1 | |
| ??30 | ??6×10 6 | ????- | ????2×10 5 | ??1×10 5 | ??4×10 2 | ??3×10 1 |
From the result of table 4 as can be seen, viable count when the interpolation concentration 1mg/L of each medicament shown in the comparative example relatively (individual/mL) time, use bag to meet among the embodiment 4 of compound 2 deficiency＜10/mL after 3 hours, in contrast, using in the comparative example 6,7 of known bactericide is 10
3～10
6About individual/mL, so, have the degerming power of continuation excellence under low concentration even the agent for preventing and eliminating of connecing of dithiode compound bag compared with known bactericide legionella bacteria have quick-acting.In addition, from the result of embodiment 5 as can be seen,, also confirmed quick-acting under the low concentration, had the control of continuation excellence even under the alkali condition of pH8.
Embodiment 6
Containing fresh water algae (blue algae; Oscillatoria laeterirens) 10
5In the Detmer medium of individual/mL, dissolve a certain amount of compound 2, regulate 4 in the medium, 5-two chloro-1, the concentration of 2-dithiode-3-ketone is the sample of 1ppm, 10ppm, 20ppm, 30ppm, 20 ℃ of following continuous lightings 24 hours, jolting was cultivated.Judge by visual after 1 week.The result is as shown in table 5.
Embodiment 7
Containing fresh water algae (green algae; Graesiella emersonii was Chlorellapyrenoidosa originally) 10
5In the MIN medium of individual/mL, dissolve a certain amount of bag and connect compound 2, regulate 4 in the medium, 5-two chloro-1, the concentration of 2-dithiode-3-ketone is the sample of 1ppm, 10ppm, 20ppm, 30ppm, 23 ℃ of following continuous lightings 24 hours, jolting was cultivated.Judge by visual after 1 week.The result is as shown in table 5.
Embodiment 8
Containing fresh water algae (diatoms; Nitzschia closterium) 10
5In the MIN medium of individual/mL, dissolve a certain amount of bag and connect compound 2, regulate 4 in the medium, 5-two chloro-1, the concentration of 2-dithiode-3-ketone is the sample of 1ppm, 10ppm, 20ppm, 30ppm, 22 ℃ of following continuous lightings 24 hours, jolting was cultivated.Judge by visual after 1 week.The result is as shown in table 5.
Table 5
| Add concentration (ppm) | After 1 day | After 2 days | After 3 days | After 5 days | After 7 days | |
| Embodiment 6 | ?0 | ?1 | ?2 | ?3 | ?4 | ?4 |
| ?1 | ?1 | ?2 | ?3 | ?4 | ?4 | |
| ?10 | ?0 | ?1 | ?2 | ?3 | ?4 | |
| ?20 | ?0 | ?0 | ?0 | ?0 | ?1 | |
| ?30 | ?0 | ?0 | ?0 | ?0 | ?0 | |
| Embodiment 7 | ?0 | ?1 | ?2 | ?3 | ?4 | ?4 |
| ?1 | ?1 | ?2 | ?3 | ?4 | ?4 | |
| ?10 | ?0 | ?1 | ?1 | ?2 | ?3 | |
| ?20 | ?0 | ?0 | ?0 | ?0 | ?0 | |
| ?30 | ?0 | ?0 | ?0 | ?0 | ?0 | |
| Embodiment 8 | ?0 | ?1 | ?2 | ?3 | ?4 | ?4 |
| ?1 | ?1 | ?2 | ?3 | ?4 | ?4 | |
| ?10 | ?0 | ?1 | ?1 | ?1 | ?2 | |
| ?20 | ?0 | ?0 | ?0 | ?0 | ?0 | |
| ?30 | ?0 | ?0 | ?0 | ?0 | ?0 |
Numeral tone in the table, 4 for the denseest, and 1 expression is the band look slightly, and 0 expression does not change fully.
Embodiment 9
Soluble test
Bag connects compound 1, bag connects compound 2 and 4,5-two chloro-1,2-dithiode-3-ketone (RYH-86) is respectively do for oneself about 8g/L, about 19g/L, about 0.05g/L of the solvability in water at room temperature, so the agent for preventing and eliminating that the cyclodextrin bag connects contains the former medicine of RYH-86 of 10 number %, so can be dissolved in the water more than 10 times, also can be processed into water soluble preparation.
Embodiment 10
The example of microencapsulation algae and legionella bacteria agent for preventing and eliminating composition
Microencapsulation preparation (YF-12) 95 weight %
Diethanol amine (preservative) 3 weight %
Dimethicone (defoamer) 2 weight %
When in cooling-tower circulating water, only adding the microencapsulation preparation, bubble in use, but cooperated this composition of dimethicone not see foaming.
Embodiment 11
Bag connects the example of alga and legionella bacteria agent for preventing and eliminating composition
Bag meets compound 1 96 weight %
BTA (preservative) 2 weight %
Sodium alkyl benzene sulfonate 2 weight %
Compare in the situation of water with only bag being connect compound dissolution, obtained uniform dissolved matter.
The invention effect
Water according to the present invention is the control method of algae, legionella bacteria, contain little capsule or the cyclodextrin bag that dithiode class antiseptic is principal component by interpolation and connect compound, can control the legionella bacteria of existence in the changes in temperature water system, accumulation of heat water system etc. of the recirculated cooling water of freezing device, the circulation warm water of 24 hours bathing pools etc., prevent its propagation. In addition, the industrial agent for preventing and eliminating to corrupt bacterium etc. used etc. with, treating of wood with, fibre finishing of, coating industrial with, papermaking as metal processing also is useful.
Claims (6)
1. a slowly-releasing alga and legionella bacteria agent for preventing and eliminating that skin irritation is improved, this agent for preventing and eliminating be necessary composition with the dithiode compound of general formula (I) expression,
In the formula, R1 and R2 represent hydrogen atom or halogen atom, separately can be identical or different.
2. slowly-releasing alga that skin irritation as claimed in claim 1 is improved and legionella bacteria agent for preventing and eliminating is characterized in that slowly-releasing turns to microencapsulation.
3. slowly-releasing alga that skin irritation as claimed in claim 1 is improved and legionella bacteria agent for preventing and eliminating is characterized in that slowly-releasing turns to by cyclodextrin and wraps connecing.
4. a slowly-releasing alga and the legionella bacteria agent for preventing and eliminating that skin irritation is improved is characterized in that, each described agent for preventing and eliminating of claim 1～3 is used for cooling-tower circulating water.
5. a slowly-releasing alga and legionella bacteria agent for preventing and eliminating composition that skin irritation is improved, it is characterized in that, the dithiode compound with general formula (I) expression serve as must composition the slowly-releasing alga that is improved of skin irritation and the legionella bacteria agent for preventing and eliminating in cooperate at least a of preservative, scale preventative, defoamer and surfactant
In the formula, R1 and R2 represent hydrogen atom or halogen atom, separately can be identical or different.
6. an algae and the legionella bacteria agent for preventing and eliminating that skin irritation is improved is characterized in that the described composition of claim 5 is used for cooling-tower circulating water.
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|---|---|---|---|
| JP2003158684 | 2003-04-28 | ||
| JP158684/2003 | 2003-04-28 |
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| KR (1) | KR20040093387A (en) |
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| CN107703305A (en) * | 2017-09-12 | 2018-02-16 | 武汉生之源生物科技股份有限公司 | A kind of anti-corrosion method of homocysteine detection kit |
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| CN107098425A (en) * | 2017-05-05 | 2017-08-29 | 中科众沃生态科技（武汉）有限公司 | A kind of microcapsules water purification agent and preparation method thereof |
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| WO2002089578A1 (en) * | 2001-05-09 | 2002-11-14 | Toppan Forms Co., Ltd. | Microencapsulated antibacterial |
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2004
- 2004-03-18 KR KR1020040018263A patent/KR20040093387A/en not_active Application Discontinuation
- 2004-03-25 CN CNB2004100332018A patent/CN100452972C/en not_active Expired - Fee Related
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| CN107703305A (en) * | 2017-09-12 | 2018-02-16 | 武汉生之源生物科技股份有限公司 | A kind of anti-corrosion method of homocysteine detection kit |
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| CN100452972C (en) | 2009-01-21 |
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