WO2015107934A1 - Antiseptic agent composition - Google Patents
Antiseptic agent composition Download PDFInfo
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- WO2015107934A1 WO2015107934A1 PCT/JP2015/050117 JP2015050117W WO2015107934A1 WO 2015107934 A1 WO2015107934 A1 WO 2015107934A1 JP 2015050117 W JP2015050117 W JP 2015050117W WO 2015107934 A1 WO2015107934 A1 WO 2015107934A1
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- isothiazolin
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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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- 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
Definitions
- emulsions, latexes, water-based paints, water-based inks, paper coating agents, starch pastes, pigment slurries, concrete admixtures, cooling water, water treatment, water-based general household products, cosmetics, agricultural chemicals, etc. are altered by microbial contamination.
- a preservative composition characterized by containing as an active ingredient a compound represented by ON and / or the following general formula (1).
- the active ingredients are emulsions, latexes, water-based paints, water-based inks, paper coating agents, starch pastes, pigment slurries, concrete admixtures, cooling water, water treatment, water-based general household products, cosmetics, agricultural chemicals, and other water-based systems. It is an antiseptic that is added to industrial products and prevents deterioration and decay of products caused by microorganisms such as bacteria and fungi.
- bactericides and preservative compositions have been used in many fields of general industrial water-based products, and are used to control harmful microorganisms such as bacteria, molds, yeasts or algae.
- isothiazoline compounds have long been known as highly effective disinfectants and preservatives.
- 2-methyl-4,5-trimethylene-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, and the compound represented by the general formula (1) are all known as bactericides and preservatives.
- it has drawbacks such as insufficient bactericidal and antiseptic effects against certain types of microorganisms and lack of sustainability of effects.
- Japanese Patent No. 2029853 describes industrial sterilization comprising 5-chloro-2-methylisothiazolin-3-one / 2-methyl-4-isothiazolin-3-one mixture and 1,2-benzisothiazolin-3-one.
- An antiseptic composition is disclosed.
- a synergistic industrial disinfectant / preservative composition comprising a combination of 2-methyl-4-isothiazolin-3-one and 1,2-benzisothiazolin-3-one is known as Thorhemegzelshaftmit Beschlenkterhof. It is disclosed in Tung (Thor Chemical GmbH), International Patent PCT / EP98 / 05310.
- the object of the present invention is to synergize the active ingredient used, so that it can be used at a lower concentration compared to the concentration required when the active ingredient is used alone, Preservatives that have features such as reducing the degree of pollution caused by exposure to the environment, reducing costs, maintaining sterilization and antiseptic effects over a long period of time, and preventing shock when added to water-based industrial products. It is to provide a composition.
- the antiseptic composition of the present invention having an antibacterial active isothiazoline-based compound, one of which is 2-methyl-4,5-trimethylene-4-isothiazolin-3-one.
- the present invention is represented by (A) 2-methyl-4,5-trimethylene-4-isothiazolin-3-one and (B) 2-methyl-4-isothiazolin-3-one and / or the general formula (1).
- a preservative composition characterized by comprising a compound as an active ingredient.
- R represents an alkyl group or an allyl group having 8 to 22 carbon atoms
- n + m represents a number of 2 to 12, preferably 3 to 10.
- the preservative composition containing as an active ingredient has the advantage of not causing a shock when added to an aqueous industrial product because an organic solvent can be kept as low as possible in its production method. Compared with the synergistic action of the antibacterial effect by the combination of the compounds, there is an effect that the antibacterial spectrum is broadened and more antibacterial effect can be expected.
- the preservative composition of the present invention includes emulsion paints, latex emulsions, water-based paints, metalworking oils, starch pastes, paper coating solutions, fiber oils, concrete admixtures, cooling water, water treatment, water-based general household products, cosmetics.
- it exhibits a synergistic antiseptic effect for controlling and controlling alteration and contamination by microorganisms such as agricultural chemicals, and is effective in preventing slime damage caused by microorganisms in the papermaking process and factory cooling water system.
- it is a useful preservative composition that is low in toxicity, has no concern about pollution, and does not adversely affect the target composition.
- 2-Methyl-4,5-trimethylene-4-isothiazolin-3-one which is one of the active ingredients of the present composition, is, for example, skin compared to 5-chloro-2-methyl-4-isothiazolin-3-one. Irritant is notably low. In addition, it is an environmentally friendly antibacterial active substance. By using this compound as one of the active ingredients of this composition, there are no disadvantages that cause allergies to the user, and industrial wastewater. It has the advantage that it is very easy to handle in terms of legal regulations.
- the preservative composition of the present invention comprises (A) 2-methyl-4,5-trimethylene-4-isothiazolin-3-one and (B) 2-methyl-4-isothiazolin-3-one and / or the above general formula.
- the mixing ratio with the compound represented by (1) is preferably 50: 1 to 1:50, more preferably 20 to 1: 1 to 20, and most preferably 5 to 1: 1. .
- the preservative composition of the present invention 2-methyl-4,5-trimethylene-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one and / or represented by the above general formula (1)
- the preservative containing the compound as an active ingredient is preferably 1.0 to 40% by weight, more preferably 2.0% by weight, based on the total amount of the preservative composition. Concentration of ⁇ 10% by weight.
- Bisaminopropyl dodecylamine is a representative compound represented by the general formula (1).
- the preservative composition having the composition of the present invention can be diluted with water and / or an organic solvent as necessary.
- organic solvents include glycols such as ethylene glycol, diethylene glycol, propylene glycol and dipropylene glycol, cellsolves such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether, and carbitols such as diethylene glycol monomethyl ether and diethylene glycol monoethyl ether. Is mentioned.
- surfactants such as nonionic surfactants such as polyoxyalkylene ether, polyoxyallyl ether, polyoxyalkylene amino ether, glycerin fatty acid ester, sorbitan fatty acid ester, fatty acid sodium, alkyl sulfate, polyoxysulfate
- Anionic surfactants such as ethylene salts, alkylbenzene sulfonates, ⁇ -olefin sulfonates, alkyl phosphates, amphoteric surfactants such as alkyldimethylamine oxide, alkylcarboxybetaines, alkylsulfobetaines, amide amino acid salts, etc.
- Additives such as organic acids such as succinic acid, citric acid and tartaric acid and salts thereof, known chelating agents, antifoaming agents and rust preventives can be used.
- it may contain one or more other antibacterial active substances selected depending on the field of application. Examples of antibacterial active substances are as follows.
- isothiazoline-based compounds such as 5-chloro-2-methyl-4-isothiazolin-3-one, 4,5-dichloro-2-methylisothiazolin-3-one, 2-n-octylisothiazolin-3-one, Cationic compounds such as 1,2-benzisothiazolin-3-one, N-methyl-1,2-benzisothiazolin-3-one, 2-n-butyl-1,2-benzisothiazolin-3-one, such as N-alkyl-N, N′-dimethylbenzylammonium chloride, di-n-decyldimethylammonium chloride, benzethonium chloride, cetylpyridinium chloride, didecyldiammonium propionate, didecyldimethylammonium carbonate, chlorohexidine (hydrochloride, glucone) Acid salt, acetate salt) Bromine compounds such as hexamethylene biguanide (hydrochlor
- the process for producing the industrial preservative composition of the present invention includes 2-methyl-4,5-trimethylene-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one and / or the above-mentioned general
- a general method is to add water to the preservative composition containing the compound represented by the formula (1) as an active ingredient and stir and mix as necessary.
- a method of adding the industrial preservative composition thus obtained to the target general industrial water-based product is general, but depending on the target general industrial water-based product, 2-methyl-4,5-trimethylene -4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, and the compound represented by the general formula (1) can be added separately.
- the preservative composition of the present invention is a general industrial water-based product such as emulsion, latex, water-based paint, water-based ink, paper coating agent, starch paste, pigment slurry, concrete admixture, cooling water, water treatment, water-based general household products, It is used in cosmetics, agricultural chemicals, etc., but the amount added is the active ingredient (2-methyl-4,5-trimethylene-4-isothiazolin-3-one, 2 -Methyl-4-isothiazolin-3-one, a compound represented by the general formula (1)) is preferably added so that the concentration is 0.001 wt% to 1.0 wt%, more preferably 0. Add to about 005 wt% to 0.5 wt%.
- a known method such as a dropping method, a coating method, a spraying method, or a dipping method can be used.
- 2-Methyl-4,5-trimethylene-4-isothiazolin-3-one can be produced by a known production method.
- 2-Methyl-4-isothiazolin-3-one is commercially available from Chemicrea under the trade name ZONEN-MT.
- a compound represented by the above general formula (1), for example, bis (aminopropyl) dodecylamine, is commercially available from Lonza Corporation under the trade name Lonzabac 12.
- the preservative composition of the present invention comprises 2-methyl-4,5-trimethylene-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one and / or a combination of the above general formula (1) However, it is larger than the antibacterial activity exhibited when each of these compounds is used alone, and a synergistic effect can be expected.
- the following examples show the synergistic action of two antibacterial active substances in the preservative composition of the present invention. Moreover, the following comparative examples show the antibacterial activity of the preservative composition alone and the antibacterial activity of a combination of other isothiazoline compounds.
- Formulation 1-6 Preparation of Formulation 1-6 (Formulation Example 1) 5 grams of 2-methyl-4,5-trimethylene-4-isothiazolin-3-one (hereinafter abbreviated as MTI) was weighed, and 93 grams of purified water was added and stirred and dissolved. Further, 2 grams of 2-methyl-4-isothiazolin-3-one (Zonen MT manufactured by Chemicrea Co., Ltd., active ingredient concentration: 50%, hereinafter abbreviated as MIT) was added and stirred, and MTI was 5.0% and MIT was 1.0%. An antiseptic composition 1 was obtained.
- MTI 2-methyl-4,5-trimethylene-4-isothiazolin-3-one
- Test method Dispense the bacterial solution and spore suspension adjusted to 10 6 cells / ml to a 96-well cell culture plate, add each preparation described above for evaluation to a maximum addition concentration of 3000 ppm and 2000 ppm, and pipette. And mix. After mixing, the same operation is repeated for columns 1 to 11 to mix, and column 12 is blank.
- the minimum growth inhibitory concentration (hereinafter abbreviated as MIC) is measured by culturing 96-well cell culture plates in a 37 ° C incubator for 24 hours, yeast for 30 hours at 30 ° C, and mold for 28 hours at 28 ° C. did.
- the MIC is measured by comparing the turbidity of the control sample and each preparation-added sample. The case where no turbidity could be confirmed was evaluated as “ ⁇ ”, and the case where turbidity could be confirmed was evaluated as “+”.
- Example 1 The evaluation results of Formulation 1 are shown in Table 1.
- aqueous emulsion was used as a sample for evaluation.
- Formulations 1 to 6 described above were added to the evaluation samples so that the active ingredient concentrations were 25 ppm, 50 ppm, and 100 ppm.
- Each sample was inoculated with 4% inoculum and stored in a 30 ° C incubator. Seven days after the inoculation, the remaining state of microorganisms was confirmed by a smear painting method. This was repeated a total of 4 times.
- the remaining state of the microorganism was determined according to the criteria shown in Table 2 according to the amount of the microorganism remaining on the normal agar medium.
- Table 3 shows the evaluation results of the samples to which the preservative composition 1 was added to the sample for evaluation at an active ingredient concentration of 25 ppm, 50 ppm, and 100 ppm.
- Example 3 shows the evaluation results of the samples in which the preservative composition 2 was added to the evaluation samples at 25 ppm, 50 ppm, and 100 ppm as active ingredient concentrations.
- Example 4 Table 3 shows the evaluation results of the samples to which the preservative composition 3 was added to the evaluation samples at 25 ppm, 50 ppm, and 100 ppm as active ingredient concentrations.
- Table 3 shows the evaluation results of samples obtained by adding the industrial preservative composition 4 to the evaluation samples at 25 ppm, 50 ppm, and 100 ppm as active ingredient concentrations.
- Table 3 shows the evaluation results of the samples in which the industrial preservative composition 5 was added to the evaluation samples at 25 ppm, 50 ppm, and 100 ppm as active ingredient concentrations.
- Test method Dispense the bacterial solution and spore suspension adjusted to 10 6 cells / ml to a 96-well cell culture plate, and add each preparation described above for evaluation to a maximum additive concentration of 3000 ppm, 2000 ppm, 5000 ppm, or 4000 ppm. And mix by pipetting. After mixing, the same operation is repeated for columns 1 to 11 to mix, and column 12 is blank.
- the minimum growth inhibitory concentration (hereinafter abbreviated as MIC) is measured by culturing 96-well cell culture plates in a 37 ° C incubator for 24 hours, yeast for 30 hours at 30 ° C, and mold for 28 hours at 28 ° C. did.
- the MIC is measured by comparing the turbidity of the control sample and each preparation-added sample. The case where no turbidity could be confirmed was evaluated as “ ⁇ ”, and the case where turbidity could be confirmed was evaluated as “+”.
- Tables 4 to 6 show the Psudomonas aeruginosa NBRC 12589, Candida albicans NBRC 1594, Aspergillus niger NBRC 6143 index and the NBRC 6342 index for the MTI, MIT, and Lonzabac-12 single agents and each agent combination system.
- the FIC index (Fractional Inhibition Concentration Index) was calculated by the following equation (1).
- FIC index Qa / QA + Qb / QB (1) (Where Qa is the MIC value of the A component when the A component and the B component are used in combination. QA is the MIC value of A component alone, Qb is the MIC value of the B component when the A component and the B component are used together. QB represents the MIC value of the B component alone)
- the FIC index represents the effect of the combined use of the A component and the B component. When the FIC index is 1, it indicates that there is an additive action by the combined use of the A component and the B component.
- the FIC index When the FIC index is greater than 1, it indicates that there is an antagonistic action by the combined use of the A component and the B component. When the FIC index is less than 1, it indicates that there is a synergistic effect by the combined use of the A component and the B component.
- Table 4 shows the MIC value and FIC index for MTI, MIT single agent and each mixing ratio.
- Example 12 Table 5 shows the MIC value and FIC index of MTI, Lonzabac 12 (adjusted to pH 6.4) alone and each mixing ratio.
- Table 6 shows the MIC value and FIC index when a mixed product of MTI and MIT (MTI / MIT ratio 1: 1) and Lonzabacl 12 (pH adjusted to 6.4) were combined at each mixing ratio. From Table 4, Table 5, and Table 6, 2-methyl-4,5-trimethylene-4-isothiazolin-3-one (MTI) and 2-methyl-4-isothiazolin-3-one (MIT) and / or the above general
- the preservative composition containing the compound represented by the formula (1) as an active ingredient can be expected to have a synergistic effect as compared with the preservative composition containing each single agent as an active ingredient.
- Preservative composition 11 was added to 80.0 grams and 20.0 grams of preservative composition 12 was added and stirred to obtain a preservative composition 14 having an MTI of 4.0% and an MIT of 1.0%.
- Preservative composition 11 was added to 50.0 grams and 50.0 grams of preservative composition 12 was added and stirred to obtain preservative composition 15 having an MTI of 2.5% and an MIT of 2.5%.
- Preservative composition 11, preservative composition 12, and preservative composition 13 were added in the same amount and stirred, and MTI, MIT and bis (aminopropyl) dodecylamine were 1: 1: 1, and the active ingredient concentration was 5.0%. Of antiseptic composition 17 was obtained.
- Preservative composition 19 50.0 grams of preservative composition 12 and 50.0 grams of preservative composition 13 were added and stirred to obtain preservative composition 19 having MIT 2.5% and bis (aminopropyl) dodecylamine 2.5%. It was.
- Example 14 Preservative compositions 14, 15, 16, and 17 described above were added to the aqueous acrylic emulsion so that the active ingredient concentrations were 25 ppm, 50 ppm, and 100 ppm. Each sample was inoculated with 4% inoculum and stored in a 30 ° C incubator. Seven days after the inoculation, the remaining state of the microorganism was confirmed on a normal agar medium by a streak smearing method. This was repeated a total of 4 times.
- the remaining state of the microorganism was determined according to the criteria shown in Table 7 according to the amount of the microorganism remaining on the normal agar medium.
- Table 8 shows the evaluation results of the aqueous acrylic emulsion.
- the bacterial solution was prepared in the same manner as in paragraph 0073.
- Example 15 Preservative compositions 15, 16, 17, and 18 described above were added to the nonionic surfactant (polyoxyethylene monolaurate 1% aqueous solution) so that the active ingredient concentrations were 25 ppm, 50 ppm, and 100 ppm. Each sample was inoculated with 1% inoculum and stored in a 30 ° C incubator. Seven days after the inoculation, the remaining state of the microorganism was confirmed on a normal agar medium by a streak smearing method. This was repeated a total of 3 times.
- the nonionic surfactant polyoxyethylene monolaurate 1% aqueous solution
- Table 9 shows the evaluation results with a nonionic surfactant (polyoxyethylene monolaurate 1% aqueous solution).
- a bacterial solution of paragraph 0073 was prepared and added to a lignin-based concrete admixture to cause it to decay to 10 6 CFU / ml or more.
- Example 16 The preservative composition 15, 16, 17 described above is added to the rotten lignin-based concrete admixture so that the active ingredient concentration is 50 ppm and 100 ppm, and the image smearing method is performed 1 day, 3 days, and 7 days after the addition of the preservative. Thus, the remaining state of the microorganism was confirmed on a normal agar medium.
- Table 10 shows the evaluation results with the lignin-based concrete admixture.
- the preservative of the present invention includes 2-methyl-4,5-trimethylene-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one and / or a compound represented by the above general formula (1).
- As an active ingredient rot due to microbial contamination can be significantly avoided at low concentrations.
Abstract
This antiseptic agent composition, which is characterized by containing as effective ingredients 2-methyl-4,5-trimethylene-4-isothiazolin-3-one, and 2-methyl-4-isothiazolin-3-one and/or a compound represented by general formula (1), provides an antiseptic agent having exceptional antiseptic effect and being useable at low concentration.
Description
本発明は、例えばエマルション、ラテックス、水性塗料、水性インキ、紙用コーティング剤、澱粉糊、顔料スラリー、コンクリート混和剤、クーリングウォーター、水処理、水系一般家庭用品、化粧品、農薬等が微生物汚染により変質、腐敗するのを防止するために使用されるものであり、特に（Ａ）２－メチル－４，５－トリメチレン－４－イソチアゾリン－３－オンと（Ｂ）２－メチル－４－イソチアゾリン－３－オンおよび／または下記一般式（１）で表される化合物を有効成分として含有することを特徴とする防腐剤組成物に関するものである。
In the present invention, for example, emulsions, latexes, water-based paints, water-based inks, paper coating agents, starch pastes, pigment slurries, concrete admixtures, cooling water, water treatment, water-based general household products, cosmetics, agricultural chemicals, etc. are altered by microbial contamination. Used to prevent spoilage, in particular (A) 2-methyl-4,5-trimethylene-4-isothiazolin-3-one and (B) 2-methyl-4-isothiazoline-3 The present invention relates to a preservative composition characterized by containing as an active ingredient a compound represented by ON and / or the following general formula (1).
本発明に係る、２－メチル－４，５－トリメチレン－４－イソチアゾリン－３－オンと２－メチル－４－イソチアゾリン－３－オンおよび／または下記一般式（１）で表される化合物とを有効成分とする組成物は、エマルション、ラテックス、水性塗料、水性インキ、紙用コーティング剤、澱粉糊、顔料スラリー、コンクリート混和剤、クーリングウォーター、水処理、水系一般家庭用品、化粧品、農薬等の水系工業品に添加され、細菌、真菌などの微生物に起因する製品の変質、腐敗を防止する防腐剤である。
2-methyl-4,5-trimethylene-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one and / or a compound represented by the following general formula (1) according to the present invention: The active ingredients are emulsions, latexes, water-based paints, water-based inks, paper coating agents, starch pastes, pigment slurries, concrete admixtures, cooling water, water treatment, water-based general household products, cosmetics, agricultural chemicals, and other water-based systems. It is an antiseptic that is added to industrial products and prevents deterioration and decay of products caused by microorganisms such as bacteria and fungi.
従来から殺菌剤・防腐剤組成物は一般工業水系製品の多くの分野で用いられており、細菌類、カビ類、酵母類または藻類などの有害微生物を抑制するために使用される。その中でもイソチアゾリン系化合物は非常に効果的な殺菌剤・防腐剤として以前から知られている。
Conventionally, bactericides and preservative compositions have been used in many fields of general industrial water-based products, and are used to control harmful microorganisms such as bacteria, molds, yeasts or algae. Among them, isothiazoline compounds have long been known as highly effective disinfectants and preservatives.
２－メチル－４，５－トリメチレン－４－イソチアゾリン－３－オン、２－メチル－４－イソチアゾリン－３－オン、一般式（１）で表される化合物はいずれも殺菌・防腐剤として知られているが、ある種類の微生物に対して殺菌・防腐効果が不十分であるとか、効果の持続性に欠けるなどの欠点を有している。
2-methyl-4,5-trimethylene-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, and the compound represented by the general formula (1) are all known as bactericides and preservatives. However, it has drawbacks such as insufficient bactericidal and antiseptic effects against certain types of microorganisms and lack of sustainability of effects.
イソチアゾリン系化合物を組み合わせて使用することは既に知られている。たとえば、２－メチル－４－イソチアゾリン－３－オンと２－ｎ－オクチルイソチアゾリン－３－オンを含有する相乗効果を有する組成物が欧州特許出願第０６７６１４０Ａ１号に開示されている。
It is already known to use isothiazoline compounds in combination. For example, a synergistic composition containing 2-methyl-4-isothiazolin-3-one and 2-n-octylisothiazolin-3-one is disclosed in European Patent Application No. 0676140A1.
日本特許第２０２９８５３号には、５－クロロ－２－メチルイソチアゾリン－３－オン／２－メチル－４－イソチアゾリン－３－オン混合物および１，２－ベンズイソチアゾリン－３－オンからなる工業用殺菌・防腐剤組成物が開示されている。
Japanese Patent No. 2029853 describes industrial sterilization comprising 5-chloro-2-methylisothiazolin-3-one / 2-methyl-4-isothiazolin-3-one mixture and 1,2-benzisothiazolin-3-one. An antiseptic composition is disclosed.
また、２－メチル－４－イソチアゾリン－３－オンと１，２－ベンゾイソチアゾリン－３－オンの組み合わせからなる、相乗作用を有する工業用殺菌・防腐剤組成物が、トールへミーゲゼルシャフトミットベシュレンクテルハフツング（Ｔｈｏｒ Ｃｈｅｍｉｃ ＧｍｂＨ）社、国際特許ＰＣＴ／ＥＰ９８／０５３１０に開示されている。
In addition, a synergistic industrial disinfectant / preservative composition comprising a combination of 2-methyl-4-isothiazolin-3-one and 1,2-benzisothiazolin-3-one is known as Thorhemegzelshaftmit Beschlenkterhof. It is disclosed in Tung (Thor Chemical GmbH), International Patent PCT / EP98 / 05310.
本発明の目的は、使用される有効成分を相乗的に作用させ、その結果、有効成分を単独で使用した場合に必要な濃度に比べ、より低い濃度で使用することができる、そのため、人、環境が被曝して汚染される程度が減少する、コスト削減が可能である、長期にわたり殺菌・防腐効果が維持できる、水系工業製品に添加した際、ショック等を起こしにくい等の特徴を有する防腐剤組成物を提供することである。
The object of the present invention is to synergize the active ingredient used, so that it can be used at a lower concentration compared to the concentration required when the active ingredient is used alone, Preservatives that have features such as reducing the degree of pollution caused by exposure to the environment, reducing costs, maintaining sterilization and antiseptic effects over a long period of time, and preventing shock when added to water-based industrial products. It is to provide a composition.
この目的は、抗菌活性なイソチアゾリン系化合物を有し、そのうちの１つが２－メチル－４，５－トリメチレン－４－イソチアゾリン－３－オンである本発明の防腐剤組成物により達成される。本発明は、（Ａ）２－メチル－４，５－トリメチレン－４－イソチアゾリン－３－オンと（Ｂ）２－メチル－４－イソチアゾリン－３－オンおよび／または一般式（１）で表される化合物を有効成分とすることを特徴とする防腐剤組成物である。
This object is achieved by the antiseptic composition of the present invention having an antibacterial active isothiazoline-based compound, one of which is 2-methyl-4,5-trimethylene-4-isothiazolin-3-one. The present invention is represented by (A) 2-methyl-4,5-trimethylene-4-isothiazolin-3-one and (B) 2-methyl-4-isothiazolin-3-one and / or the general formula (1). A preservative composition characterized by comprising a compound as an active ingredient.
（式中、Ｒは炭素数８から２２のアルキル基またはアリル基を表し、ｎ＋ｍは２～１２、好ましくは３～１０の数を表す）
(In the formula, R represents an alkyl group or an allyl group having 8 to 22 carbon atoms, and n + m represents a number of 2 to 12, preferably 3 to 10.)
本発明の組成を有する２－メチル－４，５－トリメチレン－４－イソチアゾリン－３－オンと２－メチル－４－イソチアゾリン－３－オンおよび／または上記一般式（１）で表される化合物とを有効成分とする防腐剤組成物は、その製造方法に有機溶媒を極力低く抑えることが可能であるため、水系工業製品に添加した際、ショックを起こさないという利点を有し、従来のイソチアゾリン系化合物の組み合わせによる抗菌効果の相乗的作用に比べ、抗菌スペクトルが広がり、より抗菌効果が期待できる、という効果がある。
2-methyl-4,5-trimethylene-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one having the composition of the present invention and / or a compound represented by the above general formula (1) The preservative composition containing as an active ingredient has the advantage of not causing a shock when added to an aqueous industrial product because an organic solvent can be kept as low as possible in its production method. Compared with the synergistic action of the antibacterial effect by the combination of the compounds, there is an effect that the antibacterial spectrum is broadened and more antibacterial effect can be expected.
本発明の防腐剤組成物は、エマルションペイント、ラテックスエマルション、水性塗料、金属加工油、澱粉のり、紙用塗工液、繊維油剤、コンクリート混和剤、クーリングウォーター、水処理、水系一般家庭用品、化粧品、農薬などの微生物による変質・汚染を抑制防除するのに相乗的防腐効果を発揮し、また製紙工程や工場冷却水系において微生物に起因して生ずるスライム障害の防止にも有効である。しかも低毒性で公害の心配がなく、対象組成物に対する悪影響を及ぼすこともない有用な防腐剤組成物である。
The preservative composition of the present invention includes emulsion paints, latex emulsions, water-based paints, metalworking oils, starch pastes, paper coating solutions, fiber oils, concrete admixtures, cooling water, water treatment, water-based general household products, cosmetics. In addition, it exhibits a synergistic antiseptic effect for controlling and controlling alteration and contamination by microorganisms such as agricultural chemicals, and is effective in preventing slime damage caused by microorganisms in the papermaking process and factory cooling water system. Moreover, it is a useful preservative composition that is low in toxicity, has no concern about pollution, and does not adversely affect the target composition.
本組成物の有効成分の１つである２－メチル－４，５－トリメチレン－４－イソチアゾリン－３－オンは、たとえば、５－クロロ－２－メチル－４－イソチアゾリン－３－オンに比べ皮膚刺激性が顕著に低い。また環境に配慮された抗菌活性物質であり、この化合物を本組成物の有効成分の一つとして使用することにより、使用者にとって、アレルギーを引き起こしたりするような欠点を抱えず、また、産業排水中の法的な規制の面からも非常に扱いやすい利点を有している。
2-Methyl-4,5-trimethylene-4-isothiazolin-3-one, which is one of the active ingredients of the present composition, is, for example, skin compared to 5-chloro-2-methyl-4-isothiazolin-3-one. Irritant is notably low. In addition, it is an environmentally friendly antibacterial active substance. By using this compound as one of the active ingredients of this composition, there are no disadvantages that cause allergies to the user, and industrial wastewater. It has the advantage that it is very easy to handle in terms of legal regulations.
本発明の防腐剤組成物は、（Ａ）２－メチル－４，５－トリメチレン－４－イソチアゾリン－３－オンと（Ｂ）２－メチル－４－イソチアゾリン－３－オンおよび／または上記一般式（１）で表される化合物との混合割合が好ましくは重量比５０：１～１：５０であり、より好ましくは重量比２０～１：１～２０、最も好ましくは５～１：１である。
The preservative composition of the present invention comprises (A) 2-methyl-4,5-trimethylene-4-isothiazolin-3-one and (B) 2-methyl-4-isothiazolin-3-one and / or the above general formula. The mixing ratio with the compound represented by (1) is preferably 50: 1 to 1:50, more preferably 20 to 1: 1 to 20, and most preferably 5 to 1: 1. .
本発明の防腐剤組成物において、２－メチル－４，５－トリメチレン－４－イソチアゾリン－３－オンと２－メチル－４－イソチアゾリン－３－オンおよび／または上記一般式（１）で表される化合物とを有効成分とする防腐剤は、いずれの場合も防腐剤組成物の全量に対して１．０重量％～４０重量％の濃度とするのが好ましく、より好ましくは２．０重量％～１０重量％の濃度である。
In the preservative composition of the present invention, 2-methyl-4,5-trimethylene-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one and / or represented by the above general formula (1) In any case, the preservative containing the compound as an active ingredient is preferably 1.0 to 40% by weight, more preferably 2.0% by weight, based on the total amount of the preservative composition. Concentration of ˜10% by weight.
上記一般式（１）で表される化合物の代表的なものに、ビスアミノプロピルドデシルアミンがある。
Bisaminopropyl dodecylamine is a representative compound represented by the general formula (1).
本発明の組成を有する防腐剤組成物は必要に応じて、例えば水および／または有機溶媒を使用して希釈することができる。好ましい有機溶媒としては、エチレングリコール、ジエチレングリコール、プロピレングリコール、ジプロピレングリコール等のグリコール類、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル等のセルソルブ類、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル等のカルビトール類が挙げられる。
The preservative composition having the composition of the present invention can be diluted with water and / or an organic solvent as necessary. Preferred organic solvents include glycols such as ethylene glycol, diethylene glycol, propylene glycol and dipropylene glycol, cellsolves such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether, and carbitols such as diethylene glycol monomethyl ether and diethylene glycol monoethyl ether. Is mentioned.
更にこの他に界面活性剤、例えばポリオキシアルキレンエーテル、ポリオキシアリルエーテル、ポリオキシアルキレンアミノエーテル、グリセリン脂肪酸エステル、ソルビタン脂肪酸エステル等のノニオン系界面活性剤や脂肪酸ナトリウム、硫酸アルキル塩、硫酸ポリオキシエチレン塩、アルキルベンゼンスルホン酸塩、α－オレフィンスルホン酸塩、アルキルリン酸塩等のアニオン系界面活性剤、アルキルジメチルアミンオキシド、アルキルカルボキシベタイン、アルキルスルホベタイン、アミドアミノ酸塩等の両性界面活性剤やコハク酸やクエン酸、酒石酸等の有機酸やその塩、公知のキレート剤、消泡剤、防錆剤等の添加剤を使用することができる。
In addition, surfactants such as nonionic surfactants such as polyoxyalkylene ether, polyoxyallyl ether, polyoxyalkylene amino ether, glycerin fatty acid ester, sorbitan fatty acid ester, fatty acid sodium, alkyl sulfate, polyoxysulfate Anionic surfactants such as ethylene salts, alkylbenzene sulfonates, α-olefin sulfonates, alkyl phosphates, amphoteric surfactants such as alkyldimethylamine oxide, alkylcarboxybetaines, alkylsulfobetaines, amide amino acid salts, etc. Additives such as organic acids such as succinic acid, citric acid and tartaric acid and salts thereof, known chelating agents, antifoaming agents and rust preventives can be used.
本発明の防腐剤組成物においては、２－メチル－４，５－トリメチレン－４－イソチアゾリン－３－オン、２－メチル－４－イソチアゾリン－３－オン、上記一般式（１）で表される化合物以外にも、適用分野に応じて選択される１または２以上の他の抗菌活性物質を含むことができる。抗菌活性物質の例を挙げると以下のとおりである。すなわち、イソチアゾリン系化合物、例えば、５－クロロ－２－メチル－４－イソチアゾリン－３－オン、４，５－ジクロロ－２－メチルイソチアゾリン－３－オン、２－ｎ－オクチルイソチアゾリン－３－オン、１，２－ベンゾイソチアゾリン－３－オン、Ｎ－メチル－１，２－ベンゾイソチアゾリン－３－オン、２－ｎ－ブチル－１，２－ベンゾイソチアゾリン－３－オン等、カチオン系化合物、例えば、Ｎ－アルキル－Ｎ，Ｎ’－ジメチルベンジルアンモニウムクロライド、ジ－ｎ－デシルジメチルアンモニウムクロライド、ベンゼトニウムクロライド、セチルピリジニウムクロライド、ジデシルジアンモニウムプロピオネート、ジデシルジメチルアンモニウムカーボネート、クロロヘキシジン（塩酸塩、グルコン酸塩、酢酸塩）、ポリヘキサメチレンビグアナイド（塩酸塩、リン酸塩、ステアリン酸塩）、ポリヘキサメチレングアニジン（塩酸塩、リン酸塩）等、臭素系化合物、例えば、２，２－ジブロモ－３－ニトリロプロピオンアミド、２－ブロモ－２－ニトロプロパン－１，３－ジオール、２，２－ジブロモ－２－ニトロメタノール、１，４－ビス（ブロモアセトキシ）－２－ブテン、１，２－ビス（ブロモアセトキシ）エタン、１，２－ジブロモ－２，４－ジシアノブタン等、ヨード系化合物、例えば、３－ヨード－２－プロピニル－Ｎ－ブチルカーバメート、ジヨードメチル－ｐ－トリルスルホン、４－クロロフェニル－３－ヨードプロパルギルホルマール、３－エトキシカルボニルオキシ－１－ブロモ－１，２－ジヨード－１－プロペン、２，３，３－トリヨードアリルアルコール等、ピリジン化合物、例えば、亜鉛ピリチオン、銅ピリチオン、ナトリウムピリチオン、メチルスルホニルテトラクロルピリジン等が挙げられる。
In the preservative composition of the present invention, 2-methyl-4,5-trimethylene-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, represented by the above general formula (1) In addition to the compound, it may contain one or more other antibacterial active substances selected depending on the field of application. Examples of antibacterial active substances are as follows. That is, isothiazoline-based compounds such as 5-chloro-2-methyl-4-isothiazolin-3-one, 4,5-dichloro-2-methylisothiazolin-3-one, 2-n-octylisothiazolin-3-one, Cationic compounds such as 1,2-benzisothiazolin-3-one, N-methyl-1,2-benzisothiazolin-3-one, 2-n-butyl-1,2-benzisothiazolin-3-one, such as N-alkyl-N, N′-dimethylbenzylammonium chloride, di-n-decyldimethylammonium chloride, benzethonium chloride, cetylpyridinium chloride, didecyldiammonium propionate, didecyldimethylammonium carbonate, chlorohexidine (hydrochloride, glucone) Acid salt, acetate salt) Bromine compounds such as hexamethylene biguanide (hydrochloride, phosphate, stearate), polyhexamethylene guanidine (hydrochloride, phosphate), such as 2,2-dibromo-3-nitrilopropionamide, 2- Bromo-2-nitropropane-1,3-diol, 2,2-dibromo-2-nitromethanol, 1,4-bis (bromoacetoxy) -2-butene, 1,2-bis (bromoacetoxy) ethane, , 2-dibromo-2,4-dicyanobutane, etc., iodo compounds such as 3-iodo-2-propynyl-N-butylcarbamate, diiodomethyl-p-tolylsulfone, 4-chlorophenyl-3-iodopropargyl formal, 3 -Ethoxycarbonyloxy-1-bromo-1,2-diiodo-1-propene, 2,3,3-triyo De allyl alcohol, pyridine compounds, for example, zinc pyrithione, copper pyrithione, sodium pyrithione, and the like davicil.
本発明の工業用防腐剤組成物を製造する方法としては、２－メチル－４，５－トリメチレン－４－イソチアゾリン－３－オンと２－メチル－４－イソチアゾリン－３－オンおよび／または上記一般式（１）で表される化合物とを有効成分とする防腐剤組成物に、必要に応じて水を加え攪拌混合する方法が一般的である。このようにして得た工業用防腐剤組成物を、対象となる一般工業水系品に添加する方法が一般的であるが、対象となる一般工業水系品によっては２－メチル－４，５－トリメチレン－４－イソチアゾリン－３－オンと２－メチル－４－イソチアゾリン－３－オン、一般式（１）で表される化合物は別々に添加することも可能である。
The process for producing the industrial preservative composition of the present invention includes 2-methyl-4,5-trimethylene-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one and / or the above-mentioned general A general method is to add water to the preservative composition containing the compound represented by the formula (1) as an active ingredient and stir and mix as necessary. A method of adding the industrial preservative composition thus obtained to the target general industrial water-based product is general, but depending on the target general industrial water-based product, 2-methyl-4,5-trimethylene -4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, and the compound represented by the general formula (1) can be added separately.
本発明の防腐剤組成物は一般工業水系品、例えばエマルション、ラテックス、水性塗料、水性インキ、紙用コーティング剤、澱粉糊、顔料スラリー、コンクリート混和剤、クーリングウォーター、水処理、水系一般家庭用品、化粧品、農薬等に使用されるが、その添加量は対象となる一般工業水系品に対して本願発明に係る有効成分（２－メチル－４，５－トリメチレン－４－イソチアゾリン－３－オン、２－メチル－４－イソチアゾリン－３－オン、一般式（１）で表される化合物）濃度が０．００１重量％～１．０重量％になるように添加するのが好ましく、より好ましくは０．００５重量％～０．５重量％程度に添加する。添加する方法としては、例えば滴下法、塗布法、噴霧法、浸漬法等の公知の方法を使用することができる。
The preservative composition of the present invention is a general industrial water-based product such as emulsion, latex, water-based paint, water-based ink, paper coating agent, starch paste, pigment slurry, concrete admixture, cooling water, water treatment, water-based general household products, It is used in cosmetics, agricultural chemicals, etc., but the amount added is the active ingredient (2-methyl-4,5-trimethylene-4-isothiazolin-3-one, 2 -Methyl-4-isothiazolin-3-one, a compound represented by the general formula (1)) is preferably added so that the concentration is 0.001 wt% to 1.0 wt%, more preferably 0. Add to about 005 wt% to 0.5 wt%. As a method for addition, for example, a known method such as a dropping method, a coating method, a spraying method, or a dipping method can be used.
２－メチル－４，５－トリメチレン－４－イソチアゾリン－３－オンは、公知の製造方法により作製できる。２－メチル－４－イソチアゾリン－３－オンはケミクレア社からＺＯＮＥＮ－ＭＴの商品名で市販されている。また上記一般式（１）で表される化合物、例えばビス（アミノプロピル）ドデシルアミンは、ロンザ社からＬｏｎｚａｂａｃ １２の商品名で市販されている。
2-Methyl-4,5-trimethylene-4-isothiazolin-3-one can be produced by a known production method. 2-Methyl-4-isothiazolin-3-one is commercially available from Chemicrea under the trade name ZONEN-MT. A compound represented by the above general formula (1), for example, bis (aminopropyl) dodecylamine, is commercially available from Lonza Corporation under the trade name Lonzabac 12.
本発明の防腐剤組成物は、２－メチル－４，５－トリメチレン－４－イソチアゾリン－３－オンと２－メチル－４－イソチアゾリン－３－オンおよび／または上記一般式（１）との組み合わせが、これらの各化合物を単独で使用したときに示される抗菌活性よりも大きく、相乗効果が期待できる。
The preservative composition of the present invention comprises 2-methyl-4,5-trimethylene-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one and / or a combination of the above general formula (1) However, it is larger than the antibacterial activity exhibited when each of these compounds is used alone, and a synergistic effect can be expected.
以下、製剤例、実施例、比較例により本発明を具体的に説明するが、本発明はこれらの例によって制限されるものではない。実施例、比較例中の「％」は「重量％」を表す。
Hereinafter, the present invention will be specifically described with reference to formulation examples, examples and comparative examples, but the present invention is not limited to these examples. “%” In Examples and Comparative Examples represents “% by weight”.
以下の実施例は、本発明の防腐剤組成物における２つの抗菌活性物質の相乗作用を示すものである。また、以下の比較例は、防腐剤組成物における単独での抗菌活性および他のイソチアゾリン系化合物の組み合わせによる抗菌活性を示すものである。
The following examples show the synergistic action of two antibacterial active substances in the preservative composition of the present invention. Moreover, the following comparative examples show the antibacterial activity of the preservative composition alone and the antibacterial activity of a combination of other isothiazoline compounds.
製剤１－６の調製
（製剤例１）
２－メチル－４，５－トリメチレン－４－イソチアゾリン－３－オン（以下ＭＴＩと略す）を５グラム計量し、９３グラムの精製水を加え撹拌・溶解した。更に２－メチル－４－イソチアゾリン－３－オン（ケミクレア社製Ｚｏｎｅｎ ＭＴ、有効成分濃度５０％、以下ＭＩＴと略す）を２グラム添加し撹拌してＭＴＩ ５．０％、ＭＩＴ １．０％の防腐組成物１を得た。 Preparation of Formulation 1-6 (Formulation Example 1)
5 grams of 2-methyl-4,5-trimethylene-4-isothiazolin-3-one (hereinafter abbreviated as MTI) was weighed, and 93 grams of purified water was added and stirred and dissolved. Further, 2 grams of 2-methyl-4-isothiazolin-3-one (Zonen MT manufactured by Chemicrea Co., Ltd., active ingredient concentration: 50%, hereinafter abbreviated as MIT) was added and stirred, and MTI was 5.0% and MIT was 1.0%. An antiseptic composition 1 was obtained.
（製剤例１）
２－メチル－４，５－トリメチレン－４－イソチアゾリン－３－オン（以下ＭＴＩと略す）を５グラム計量し、９３グラムの精製水を加え撹拌・溶解した。更に２－メチル－４－イソチアゾリン－３－オン（ケミクレア社製Ｚｏｎｅｎ ＭＴ、有効成分濃度５０％、以下ＭＩＴと略す）を２グラム添加し撹拌してＭＴＩ ５．０％、ＭＩＴ １．０％の防腐組成物１を得た。 Preparation of Formulation 1-6 (Formulation Example 1)
5 grams of 2-methyl-4,5-trimethylene-4-isothiazolin-3-one (hereinafter abbreviated as MTI) was weighed, and 93 grams of purified water was added and stirred and dissolved. Further, 2 grams of 2-methyl-4-isothiazolin-3-one (Zonen MT manufactured by Chemicrea Co., Ltd., active ingredient concentration: 50%, hereinafter abbreviated as MIT) was added and stirred, and MTI was 5.0% and MIT was 1.0%. An antiseptic composition 1 was obtained.
（製剤例２）
製剤例１と同様の方法でＭＴＩ ３．０％、ＭＩＴ ３．０％の防腐剤組成物２を得た。 (Formulation example 2)
In the same manner as in Formulation Example 1, an antiseptic composition 2 having MTI 3.0% and MIT 3.0% was obtained.
製剤例１と同様の方法でＭＴＩ ３．０％、ＭＩＴ ３．０％の防腐剤組成物２を得た。 (Formulation example 2)
In the same manner as in Formulation Example 1, an antiseptic composition 2 having MTI 3.0% and MIT 3.0% was obtained.
（製剤例３）
ＭＴＩを５グラム計量し、９４グラムの精製水を加え撹拌・溶解した。更にＬｏｎｚａｂａｃ １２を１％加え、撹拌してＭＴＩ ５．０％、Ｌｏｎｚａｂａｃ １２ １．０％の防腐剤組成物３を得た。 (Formulation example 3)
5 grams of MTI was weighed and 94 grams of purified water was added and stirred and dissolved. Further, 1% of Lonzabac 12 was added and stirred to obtain a preservative composition 3 having MTI of 5.0% and Lonzabac 12 of 1.0%.
ＭＴＩを５グラム計量し、９４グラムの精製水を加え撹拌・溶解した。更にＬｏｎｚａｂａｃ １２を１％加え、撹拌してＭＴＩ ５．０％、Ｌｏｎｚａｂａｃ １２ １．０％の防腐剤組成物３を得た。 (Formulation example 3)
5 grams of MTI was weighed and 94 grams of purified water was added and stirred and dissolved. Further, 1% of Lonzabac 12 was added and stirred to obtain a preservative composition 3 having MTI of 5.0% and Lonzabac 12 of 1.0%.
（製剤例４）
ＭＴＩをそのまま使用し有効成分濃度６．０％の防腐剤組成物４を得た。 (Formulation example 4)
By using MTI as it is, an antiseptic composition 4 having an active ingredient concentration of 6.0% was obtained.
ＭＴＩをそのまま使用し有効成分濃度６．０％の防腐剤組成物４を得た。 (Formulation example 4)
By using MTI as it is, an antiseptic composition 4 having an active ingredient concentration of 6.0% was obtained.
（製剤例５）
ＭＩＴをそのまま使用し有効成分濃度６．０％の防腐剤組成物５を得た。 (Formulation example 5)
By using MIT as it is, an antiseptic composition 5 having an active ingredient concentration of 6.0% was obtained.
ＭＩＴをそのまま使用し有効成分濃度６．０％の防腐剤組成物５を得た。 (Formulation example 5)
By using MIT as it is, an antiseptic composition 5 having an active ingredient concentration of 6.0% was obtained.
（製剤例６）
Ｌｏｎｚａｂａｃ １２をそのまま使用し有効成分濃度６．０％の防腐剤組成物６を得た。 (Formulation Example 6)
Lonzabac 12 was used as it was to obtain a preservative composition 6 having an active ingredient concentration of 6.0%.
Ｌｏｎｚａｂａｃ １２をそのまま使用し有効成分濃度６．０％の防腐剤組成物６を得た。 (Formulation Example 6)
Lonzabac 12 was used as it was to obtain a preservative composition 6 having an active ingredient concentration of 6.0%.
菌液の調製
Ｐｓｅｕｄｏｍｏｎａｓ ａｅｒｕｇｉｎｏｓａ ＮＢＲＣ １２６８９
Ｃａｎｄｉｄａ ａｌｂｉｃａｎｓ ＮＢＲＣ １５９４
Ａｓｐｅｒｇｉｌｌｕｓ ｎｉｇｅｒ ＮＢＲＣ ６３４２
以上の細菌、酵母、カビを各栄養培地にて培養、細菌は普通ブイヨン液体培地、酵母、カビは麦芽液体培地に加えて、菌液及び胞子懸濁液を作成した。各菌液及び胞子懸濁液の細胞密度は１０６個／ｍｌに調整したものを試験液とした。 Preparation of bacterial solution Pseudomonas aeruginosa NBRC 12589
Candida albicans NBRC 1594
Aspergillus niger NBRC 6342
The above bacteria, yeast, and mold were cultured in each nutrient medium. Bacteria were added to a normal bouillon liquid medium, yeast and mold were added to a malt liquid medium, and a bacterial solution and a spore suspension were prepared. The cell density of each bacterial solution and spore suspension was adjusted to 10 6 cells / ml as a test solution.
Ｐｓｅｕｄｏｍｏｎａｓ ａｅｒｕｇｉｎｏｓａ ＮＢＲＣ １２６８９
Ｃａｎｄｉｄａ ａｌｂｉｃａｎｓ ＮＢＲＣ １５９４
Ａｓｐｅｒｇｉｌｌｕｓ ｎｉｇｅｒ ＮＢＲＣ ６３４２
以上の細菌、酵母、カビを各栄養培地にて培養、細菌は普通ブイヨン液体培地、酵母、カビは麦芽液体培地に加えて、菌液及び胞子懸濁液を作成した。各菌液及び胞子懸濁液の細胞密度は１０６個／ｍｌに調整したものを試験液とした。 Preparation of bacterial solution Pseudomonas aeruginosa NBRC 12589
Candida albicans NBRC 1594
Aspergillus niger NBRC 6342
The above bacteria, yeast, and mold were cultured in each nutrient medium. Bacteria were added to a normal bouillon liquid medium, yeast and mold were added to a malt liquid medium, and a bacterial solution and a spore suspension were prepared. The cell density of each bacterial solution and spore suspension was adjusted to 10 6 cells / ml as a test solution.
（試験方法）
９６ウェル細胞培養用プレートに１０６個／ｍｌに調整した菌液、胞子懸濁液を分注し、評価用に前記載の各製剤が最高添加濃度３０００ｐｐｍ、２０００ｐｐｍになるよう添加し、ピペッティングをして混合する。混合後、カラム１～１１まで、同作業を繰り返し行い混合し、カラム１２はブランクとする。９６ウェル細胞培養用プレートを細菌は、３７℃の恒温器で２４時間、酵母は３０℃で４８時間、カビについては２８℃で４８時間培養して最小発育阻止濃度（以下ＭＩＣと略す）を測定した。 (Test method)
Dispense the bacterial solution and spore suspension adjusted to 10 6 cells / ml to a 96-well cell culture plate, add each preparation described above for evaluation to a maximum addition concentration of 3000 ppm and 2000 ppm, and pipette. And mix. After mixing, the same operation is repeated for columns 1 to 11 to mix, and column 12 is blank. The minimum growth inhibitory concentration (hereinafter abbreviated as MIC) is measured by culturing 96-well cell culture plates in a 37 ° C incubator for 24 hours, yeast for 30 hours at 30 ° C, and mold for 28 hours at 28 ° C. did.
９６ウェル細胞培養用プレートに１０６個／ｍｌに調整した菌液、胞子懸濁液を分注し、評価用に前記載の各製剤が最高添加濃度３０００ｐｐｍ、２０００ｐｐｍになるよう添加し、ピペッティングをして混合する。混合後、カラム１～１１まで、同作業を繰り返し行い混合し、カラム１２はブランクとする。９６ウェル細胞培養用プレートを細菌は、３７℃の恒温器で２４時間、酵母は３０℃で４８時間、カビについては２８℃で４８時間培養して最小発育阻止濃度（以下ＭＩＣと略す）を測定した。 (Test method)
Dispense the bacterial solution and spore suspension adjusted to 10 6 cells / ml to a 96-well cell culture plate, add each preparation described above for evaluation to a maximum addition concentration of 3000 ppm and 2000 ppm, and pipette. And mix. After mixing, the same operation is repeated for columns 1 to 11 to mix, and column 12 is blank. The minimum growth inhibitory concentration (hereinafter abbreviated as MIC) is measured by culturing 96-well cell culture plates in a 37 ° C incubator for 24 hours, yeast for 30 hours at 30 ° C, and mold for 28 hours at 28 ° C. did.
（評価基準）
対照試料と各製剤添加試料の濁度を比較して、ＭＩＣを測定する。
濁りが全く確認できない場合を「－」、濁りが確認できる場合を「＋」と評価した。 (Evaluation criteria)
The MIC is measured by comparing the turbidity of the control sample and each preparation-added sample.
The case where no turbidity could be confirmed was evaluated as “−”, and the case where turbidity could be confirmed was evaluated as “+”.
対照試料と各製剤添加試料の濁度を比較して、ＭＩＣを測定する。
濁りが全く確認できない場合を「－」、濁りが確認できる場合を「＋」と評価した。 (Evaluation criteria)
The MIC is measured by comparing the turbidity of the control sample and each preparation-added sample.
The case where no turbidity could be confirmed was evaluated as “−”, and the case where turbidity could be confirmed was evaluated as “+”.
（実施例１）
製剤１の評価結果を表１に示す。 Example 1
The evaluation results of Formulation 1 are shown in Table 1.
製剤１の評価結果を表１に示す。 Example 1
The evaluation results of Formulation 1 are shown in Table 1.
製剤２の評価結果を表１に示す。
The evaluation results of Formulation 2 are shown in Table 1.
製剤３の評価結果を表１に示す。
The evaluation results of Formulation 3 are shown in Table 1.
製剤４の評価結果を表１に示す。
The evaluation results of formulation 4 are shown in Table 1.
製剤５の評価結果を表１に示す。
The evaluation results of Formulation 5 are shown in Table 1.
評価結果を下記に示す。
Evaluation results are shown below.
菌液の調製
Ｐｓｅｕｄｏｍｏｎａｓ ａｅｒｕｇｉｎｏｓａ ＮＢＲＣ １２６８９
Ｅｓｃｈｅｒｉｃｈｉａ ｃｏｌｉ ＮＢＲＣ ３９７２
Ｅｎｔｅｒｏｂａｃｔｏｒ ｃｌｏａｃａｅ ＮＢＲＣ １３５３５
以上の細菌を普通寒天培地にて培養、普通ブイヨン液体培地に加え、細菌混合液を作成した。細菌混合液の密度は１０８個／ｍｌに調整したものを接種菌とした。 Preparation of bacterial solution Pseudomonas aeruginosa NBRC 12589
Escherichia coli NBRC 3972
Enterobacter cloacae NBRC 13535
The above bacteria were cultured in a normal agar medium and added to a normal broth liquid medium to prepare a bacterial mixture. The inoculum was prepared by adjusting the density of the bacterial mixture to 10 8 cells / ml.
Ｐｓｅｕｄｏｍｏｎａｓ ａｅｒｕｇｉｎｏｓａ ＮＢＲＣ １２６８９
Ｅｓｃｈｅｒｉｃｈｉａ ｃｏｌｉ ＮＢＲＣ ３９７２
Ｅｎｔｅｒｏｂａｃｔｏｒ ｃｌｏａｃａｅ ＮＢＲＣ １３５３５
以上の細菌を普通寒天培地にて培養、普通ブイヨン液体培地に加え、細菌混合液を作成した。細菌混合液の密度は１０８個／ｍｌに調整したものを接種菌とした。 Preparation of bacterial solution Pseudomonas aeruginosa NBRC 12589
Escherichia coli NBRC 3972
Enterobacter cloacae NBRC 13535
The above bacteria were cultured in a normal agar medium and added to a normal broth liquid medium to prepare a bacterial mixture. The inoculum was prepared by adjusting the density of the bacterial mixture to 10 8 cells / ml.
水性エマルションを評価用サンプルとした。
評価用サンプルに前記載の製剤１～６を有効成分濃度で２５ｐｐｍ、５０ｐｐｍ、１００ｐｐｍになるよう添加した。各サンプルに接種液４％を接種して３０℃恒温器に保管した。接種後７日後に画線塗抹法により微生物の残存状態を確認した。これを計４回繰り返した。 An aqueous emulsion was used as a sample for evaluation.
Formulations 1 to 6 described above were added to the evaluation samples so that the active ingredient concentrations were 25 ppm, 50 ppm, and 100 ppm. Each sample was inoculated with 4% inoculum and stored in a 30 ° C incubator. Seven days after the inoculation, the remaining state of microorganisms was confirmed by a smear painting method. This was repeated a total of 4 times.
評価用サンプルに前記載の製剤１～６を有効成分濃度で２５ｐｐｍ、５０ｐｐｍ、１００ｐｐｍになるよう添加した。各サンプルに接種液４％を接種して３０℃恒温器に保管した。接種後７日後に画線塗抹法により微生物の残存状態を確認した。これを計４回繰り返した。 An aqueous emulsion was used as a sample for evaluation.
Formulations 1 to 6 described above were added to the evaluation samples so that the active ingredient concentrations were 25 ppm, 50 ppm, and 100 ppm. Each sample was inoculated with 4% inoculum and stored in a 30 ° C incubator. Seven days after the inoculation, the remaining state of microorganisms was confirmed by a smear painting method. This was repeated a total of 4 times.
（評価基準）
微生物の残存状態は普通寒天培地上に残存する微生物の量に応じて表２に示した基準により判定した。 (Evaluation criteria)
The remaining state of the microorganism was determined according to the criteria shown in Table 2 according to the amount of the microorganism remaining on the normal agar medium.
微生物の残存状態は普通寒天培地上に残存する微生物の量に応じて表２に示した基準により判定した。 (Evaluation criteria)
The remaining state of the microorganism was determined according to the criteria shown in Table 2 according to the amount of the microorganism remaining on the normal agar medium.
（実施例２）
評価用サンプルに防腐剤組成物１を有効成分濃度で２５ｐｐｍ、５０ｐｐｍ、１００ｐｐｍ添加した添加したサンプルの評価結果を表３に示す。 (Example 2)
Table 3 shows the evaluation results of the samples to which the preservative composition 1 was added to the sample for evaluation at an active ingredient concentration of 25 ppm, 50 ppm, and 100 ppm.
評価用サンプルに防腐剤組成物１を有効成分濃度で２５ｐｐｍ、５０ｐｐｍ、１００ｐｐｍ添加した添加したサンプルの評価結果を表３に示す。 (Example 2)
Table 3 shows the evaluation results of the samples to which the preservative composition 1 was added to the sample for evaluation at an active ingredient concentration of 25 ppm, 50 ppm, and 100 ppm.
（実施例３）
評価用サンプルに防腐剤組成物２を有効成分濃度で２５ｐｐｍ、５０ｐｐｍ、１００ｐｐｍ添加した添加したサンプルの評価結果を表３に示す。 Example 3
Table 3 shows the evaluation results of the samples in which the preservative composition 2 was added to the evaluation samples at 25 ppm, 50 ppm, and 100 ppm as active ingredient concentrations.
評価用サンプルに防腐剤組成物２を有効成分濃度で２５ｐｐｍ、５０ｐｐｍ、１００ｐｐｍ添加した添加したサンプルの評価結果を表３に示す。 Example 3
Table 3 shows the evaluation results of the samples in which the preservative composition 2 was added to the evaluation samples at 25 ppm, 50 ppm, and 100 ppm as active ingredient concentrations.
（実施例４）
評価用サンプルに防腐剤組成物３を有効成分濃度で２５ｐｐｍ、５０ｐｐｍ、１００ｐｐｍ添加した添加したサンプルの評価結果を表３に示す。 Example 4
Table 3 shows the evaluation results of the samples to which the preservative composition 3 was added to the evaluation samples at 25 ppm, 50 ppm, and 100 ppm as active ingredient concentrations.
評価用サンプルに防腐剤組成物３を有効成分濃度で２５ｐｐｍ、５０ｐｐｍ、１００ｐｐｍ添加した添加したサンプルの評価結果を表３に示す。 Example 4
Table 3 shows the evaluation results of the samples to which the preservative composition 3 was added to the evaluation samples at 25 ppm, 50 ppm, and 100 ppm as active ingredient concentrations.
（比較例１）
評価用サンプルに工業用防腐剤組成物４を有効成分濃度で２５ｐｐｍ、５０ｐｐｍ、１００ｐｐｍ添加したサンプルの評価結果を表３に示す。 (Comparative Example 1)
Table 3 shows the evaluation results of samples obtained by adding the industrial preservative composition 4 to the evaluation samples at 25 ppm, 50 ppm, and 100 ppm as active ingredient concentrations.
評価用サンプルに工業用防腐剤組成物４を有効成分濃度で２５ｐｐｍ、５０ｐｐｍ、１００ｐｐｍ添加したサンプルの評価結果を表３に示す。 (Comparative Example 1)
Table 3 shows the evaluation results of samples obtained by adding the industrial preservative composition 4 to the evaluation samples at 25 ppm, 50 ppm, and 100 ppm as active ingredient concentrations.
（比較例２）
評価用サンプルに工業用防腐剤組成物５を有効成分濃度で２５ｐｐｍ、５０ｐｐｍ、１００ｐｐｍ添加したサンプルの評価結果を表３に示す。 (Comparative Example 2)
Table 3 shows the evaluation results of the samples in which the industrial preservative composition 5 was added to the evaluation samples at 25 ppm, 50 ppm, and 100 ppm as active ingredient concentrations.
評価用サンプルに工業用防腐剤組成物５を有効成分濃度で２５ｐｐｍ、５０ｐｐｍ、１００ｐｐｍ添加したサンプルの評価結果を表３に示す。 (Comparative Example 2)
Table 3 shows the evaluation results of the samples in which the industrial preservative composition 5 was added to the evaluation samples at 25 ppm, 50 ppm, and 100 ppm as active ingredient concentrations.
（比較例３）
１，２－ベンゾイソチアゾリン－３－オンを６グラム計量し、ジメチルエタノールアミン２０グラム、精製水７４グラムを加え、撹拌・溶解して工業用防腐剤組成物７を得た。評価用サンプルに工業用防腐剤組成物７を有効成分濃度で２５ｐｐｍ、５０ｐｐｍ、１００ｐｐｍ添加したサンプルの評価結果を表３に示す。 (Comparative Example 3)
6 grams of 1,2-benzisothiazolin-3-one was weighed, 20 grams of dimethylethanolamine and 74 grams of purified water were added, stirred and dissolved to obtain industrial preservative composition 7. Table 3 shows the evaluation results of the samples obtained by adding the industrial preservative composition 7 to the evaluation samples at 25 ppm, 50 ppm, and 100 ppm as active ingredient concentrations.
１，２－ベンゾイソチアゾリン－３－オンを６グラム計量し、ジメチルエタノールアミン２０グラム、精製水７４グラムを加え、撹拌・溶解して工業用防腐剤組成物７を得た。評価用サンプルに工業用防腐剤組成物７を有効成分濃度で２５ｐｐｍ、５０ｐｐｍ、１００ｐｐｍ添加したサンプルの評価結果を表３に示す。 (Comparative Example 3)
6 grams of 1,2-benzisothiazolin-3-one was weighed, 20 grams of dimethylethanolamine and 74 grams of purified water were added, stirred and dissolved to obtain industrial preservative composition 7. Table 3 shows the evaluation results of the samples obtained by adding the industrial preservative composition 7 to the evaluation samples at 25 ppm, 50 ppm, and 100 ppm as active ingredient concentrations.
以下の実施例は、本発明の防腐剤組成物における相乗作用を示すものである。
The following examples show synergistic effects in the preservative composition of the present invention.
製剤１１－１３の調製
（製剤例１１）
２－メチル－４，５－トリメチレン－４－イソチアゾリン－３－オン（以下ＭＴＩと略
す）を５．０グラム計量し、９５．０グラムの精製水を加え撹拌・溶解してＭＴＩ ５．０％の防腐剤防腐組成物１１を得た。 Preparation of Formulation 11-13 (Formulation Example 11)
Weigh 5.0 g of 2-methyl-4,5-trimethylene-4-isothiazolin-3-one (hereinafter abbreviated as MTI), add 95.0 g of purified water, stir and dissolve, and add 5.0% of MTI Antiseptic preservative composition 11 was obtained.
（製剤例１１）
２－メチル－４，５－トリメチレン－４－イソチアゾリン－３－オン（以下ＭＴＩと略
す）を５．０グラム計量し、９５．０グラムの精製水を加え撹拌・溶解してＭＴＩ ５．０％の防腐剤防腐組成物１１を得た。 Preparation of Formulation 11-13 (Formulation Example 11)
Weigh 5.0 g of 2-methyl-4,5-trimethylene-4-isothiazolin-3-one (hereinafter abbreviated as MTI), add 95.0 g of purified water, stir and dissolve, and add 5.0% of MTI Antiseptic preservative composition 11 was obtained.
（製剤例１２）
２－メチル－４－イソチアゾリン－３－オン（ケミクレア社製Ｚｏｎｅｎ ＭＴ、有効成分濃度５０％、以下ＭＩＴと略す）を１０．０グラム計量し、９０．０グラムの精製水を加え撹拌してＭＩＴ ５．０％の防腐剤組成物１２を得た。 (Formulation example 12)
10.0 grams of 2-methyl-4-isothiazolin-3-one (Zonen MT manufactured by Chemicrea Co., Ltd., active ingredient concentration: 50%, hereinafter abbreviated as MIT) is weighed, and 90.0 grams of purified water is added and stirred to MIT. A 5.0% preservative composition 12 was obtained.
２－メチル－４－イソチアゾリン－３－オン（ケミクレア社製Ｚｏｎｅｎ ＭＴ、有効成分濃度５０％、以下ＭＩＴと略す）を１０．０グラム計量し、９０．０グラムの精製水を加え撹拌してＭＩＴ ５．０％の防腐剤組成物１２を得た。 (Formulation example 12)
10.0 grams of 2-methyl-4-isothiazolin-3-one (Zonen MT manufactured by Chemicrea Co., Ltd., active ingredient concentration: 50%, hereinafter abbreviated as MIT) is weighed, and 90.0 grams of purified water is added and stirred to MIT. A 5.0% preservative composition 12 was obtained.
（製剤例１３）
塩酸を使ってＬｏｎｚａｂａｃ １２のｐＨ調整を行い、ｐＨ６．４のビス（アミノプロピル）ドデシルアミン５．０％の防腐剤組成物１３を得た。 (Formulation Example 13)
The pH of Lonzabac 12 was adjusted using hydrochloric acid to obtain a preservative composition 13 having a pH of 6.4 bis (aminopropyl) dodecylamine of 5.0%.
塩酸を使ってＬｏｎｚａｂａｃ １２のｐＨ調整を行い、ｐＨ６．４のビス（アミノプロピル）ドデシルアミン５．０％の防腐剤組成物１３を得た。 (Formulation Example 13)
The pH of Lonzabac 12 was adjusted using hydrochloric acid to obtain a preservative composition 13 having a pH of 6.4 bis (aminopropyl) dodecylamine of 5.0%.
防腐剤組成物１１、１２、１３を使って、単剤および各混合割合でのＭＩＣ値を測定し相乗効果を評価した。
Using the preservative compositions 11, 12, and 13, the MIC values at the single agent and each mixing ratio were measured to evaluate the synergistic effect.
菌液の調製
Ｐｓｅｕｄｏｍｏｎａｓ ａｅｒｕｇｉｎｏｓａ ＮＢＲＣ １２６８９
Ｃａｎｄｉｄａ ａｌｂｉｃａｎｓ ＮＢＲＣ １５９４
Ａｓｐｅｒｇｉｌｌｕｓ ｎｉｇｅｒ ＮＢＲＣ ６３４２
以上の細菌、酵母、カビを各栄養培地にて培養、細菌は普通ブイヨン液体培地、酵母、カビは麦芽液体培地に加えて、菌液及び胞子懸濁液を作成した。各菌液及び胞子懸濁液の細胞密度は１０６個／ｍｌに調整したものを試験液とした。 Preparation of bacterial solution Pseudomonas aeruginosa NBRC 12589
Candida albicans NBRC 1594
Aspergillus niger NBRC 6342
The above bacteria, yeast, and mold were cultured in each nutrient medium. Bacteria were added to a normal bouillon liquid medium, yeast and mold were added to a malt liquid medium, and a bacterial solution and a spore suspension were prepared. The cell density of each bacterial solution and spore suspension was adjusted to 10 6 cells / ml as a test solution.
Ｐｓｅｕｄｏｍｏｎａｓ ａｅｒｕｇｉｎｏｓａ ＮＢＲＣ １２６８９
Ｃａｎｄｉｄａ ａｌｂｉｃａｎｓ ＮＢＲＣ １５９４
Ａｓｐｅｒｇｉｌｌｕｓ ｎｉｇｅｒ ＮＢＲＣ ６３４２
以上の細菌、酵母、カビを各栄養培地にて培養、細菌は普通ブイヨン液体培地、酵母、カビは麦芽液体培地に加えて、菌液及び胞子懸濁液を作成した。各菌液及び胞子懸濁液の細胞密度は１０６個／ｍｌに調整したものを試験液とした。 Preparation of bacterial solution Pseudomonas aeruginosa NBRC 12589
Candida albicans NBRC 1594
Aspergillus niger NBRC 6342
The above bacteria, yeast, and mold were cultured in each nutrient medium. Bacteria were added to a normal bouillon liquid medium, yeast and mold were added to a malt liquid medium, and a bacterial solution and a spore suspension were prepared. The cell density of each bacterial solution and spore suspension was adjusted to 10 6 cells / ml as a test solution.
（試験方法）
９６ウェル細胞培養用プレートに１０６個／ｍｌに調整した菌液、胞子懸濁液を分注し、評価用に前記載の各製剤が最高添加濃度３０００ｐｐｍ、２０００ｐｐｍ又は５０００ｐｐｍ、４０００ｐｐｍになるよう添加し、ピペッティングをして混合する。混合後、カラム１～１１まで、同作業を繰り返し行い混合し、カラム１２はブランクとする。９６ウェル細胞培養用プレートを細菌は、３７℃の恒温器で２４時間、酵母は３０℃で４８時間、カビについては２８℃で４８時間培養して最小発育阻止濃度（以下ＭＩＣと略す）を測定した。 (Test method)
Dispense the bacterial solution and spore suspension adjusted to 10 6 cells / ml to a 96-well cell culture plate, and add each preparation described above for evaluation to a maximum additive concentration of 3000 ppm, 2000 ppm, 5000 ppm, or 4000 ppm. And mix by pipetting. After mixing, the same operation is repeated for columns 1 to 11 to mix, and column 12 is blank. The minimum growth inhibitory concentration (hereinafter abbreviated as MIC) is measured by culturing 96-well cell culture plates in a 37 ° C incubator for 24 hours, yeast for 30 hours at 30 ° C, and mold for 28 hours at 28 ° C. did.
９６ウェル細胞培養用プレートに１０６個／ｍｌに調整した菌液、胞子懸濁液を分注し、評価用に前記載の各製剤が最高添加濃度３０００ｐｐｍ、２０００ｐｐｍ又は５０００ｐｐｍ、４０００ｐｐｍになるよう添加し、ピペッティングをして混合する。混合後、カラム１～１１まで、同作業を繰り返し行い混合し、カラム１２はブランクとする。９６ウェル細胞培養用プレートを細菌は、３７℃の恒温器で２４時間、酵母は３０℃で４８時間、カビについては２８℃で４８時間培養して最小発育阻止濃度（以下ＭＩＣと略す）を測定した。 (Test method)
Dispense the bacterial solution and spore suspension adjusted to 10 6 cells / ml to a 96-well cell culture plate, and add each preparation described above for evaluation to a maximum additive concentration of 3000 ppm, 2000 ppm, 5000 ppm, or 4000 ppm. And mix by pipetting. After mixing, the same operation is repeated for columns 1 to 11 to mix, and column 12 is blank. The minimum growth inhibitory concentration (hereinafter abbreviated as MIC) is measured by culturing 96-well cell culture plates in a 37 ° C incubator for 24 hours, yeast for 30 hours at 30 ° C, and mold for 28 hours at 28 ° C. did.
（評価基準）
対照試料と各製剤添加試料の濁度を比較して、ＭＩＣを測定する。
濁りが全く確認できない場合を「－」、濁りが確認できる場合を「＋」と評価した。 (Evaluation criteria)
The MIC is measured by comparing the turbidity of the control sample and each preparation-added sample.
The case where no turbidity could be confirmed was evaluated as “−”, and the case where turbidity could be confirmed was evaluated as “+”.
対照試料と各製剤添加試料の濁度を比較して、ＭＩＣを測定する。
濁りが全く確認できない場合を「－」、濁りが確認できる場合を「＋」と評価した。 (Evaluation criteria)
The MIC is measured by comparing the turbidity of the control sample and each preparation-added sample.
The case where no turbidity could be confirmed was evaluated as “−”, and the case where turbidity could be confirmed was evaluated as “+”.
表４～表６にＭＴＩ，ＭＩＴおよびＬｏｎｚａｂａｃ－１２単剤及び各剤組み合わせ系での各混合比率でのＰｓｕｄｏｍｏｎａｓ ａｅｒｕｇｉｎｏｓａ ＮＢＲＣ １２６８９、Ｃａｎｄｉｄａ ａｌｂｉｃａｎｓ ＮＢＲＣ １５９４、Ａｓｐｅｒｇｉｌｌｕｓ ｎｉｇｅｒ ＮＢＲＣ ６３４２に対するＭＩＣ値およびＦＩＣ指数を示す。
Tables 4 to 6 show the Psudomonas aeruginosa NBRC 12589, Candida albicans NBRC 1594, Aspergillus niger NBRC 6143 index and the NBRC 6342 index for the MTI, MIT, and Lonzabac-12 single agents and each agent combination system.
ＦＩＣ指数（Ｆｒａｃｔｉｏｎａｌ Ｉｎｈｉｂｉｔｏｒｙ Ｃｏｎｃｅｎｔｒａｔｉｏｎ Ｉｎｄｅｘ）は、下記（１）式によって算出した。
ＦＩＣ指数＝Ｑａ／ＱＡ＋Ｑｂ／ＱＢ ・・・ （１）
（式中、
Ｑａは、Ａ成分とＢ成分を併用した時のＡ成分のＭＩＣ値を、
ＱＡは、Ａ成分単独でのＭＩＣ値を、
Ｑｂは、Ａ成分とＢ成分を併用した時のＢ成分のＭＩＣ値を、
ＱＢは、Ｂ成分単独でのＭＩＣ値を
それぞれ表す）
ＦＩＣ指数は、Ａ成分とＢ成分の併用による効果を表す。ＦＩＣ指数が１である場合はＡ成分とＢ成分の併用によって相加的作用があることを示す。ＦＩＣ指数が１より大きい場合はＡ成分とＢ成分の併用によって拮抗的作用があることを示す。ＦＩＣ指数が１より小さい場合はＡ成分とＢ成分の併用によって相乗的作用があることを示す。 The FIC index (Fractional Inhibition Concentration Index) was calculated by the following equation (1).
FIC index = Qa / QA + Qb / QB (1)
(Where
Qa is the MIC value of the A component when the A component and the B component are used in combination.
QA is the MIC value of A component alone,
Qb is the MIC value of the B component when the A component and the B component are used together.
QB represents the MIC value of the B component alone)
The FIC index represents the effect of the combined use of the A component and the B component. When the FIC index is 1, it indicates that there is an additive action by the combined use of the A component and the B component. When the FIC index is greater than 1, it indicates that there is an antagonistic action by the combined use of the A component and the B component. When the FIC index is less than 1, it indicates that there is a synergistic effect by the combined use of the A component and the B component.
ＦＩＣ指数＝Ｑａ／ＱＡ＋Ｑｂ／ＱＢ ・・・ （１）
（式中、
Ｑａは、Ａ成分とＢ成分を併用した時のＡ成分のＭＩＣ値を、
ＱＡは、Ａ成分単独でのＭＩＣ値を、
Ｑｂは、Ａ成分とＢ成分を併用した時のＢ成分のＭＩＣ値を、
ＱＢは、Ｂ成分単独でのＭＩＣ値を
それぞれ表す）
ＦＩＣ指数は、Ａ成分とＢ成分の併用による効果を表す。ＦＩＣ指数が１である場合はＡ成分とＢ成分の併用によって相加的作用があることを示す。ＦＩＣ指数が１より大きい場合はＡ成分とＢ成分の併用によって拮抗的作用があることを示す。ＦＩＣ指数が１より小さい場合はＡ成分とＢ成分の併用によって相乗的作用があることを示す。 The FIC index (Fractional Inhibition Concentration Index) was calculated by the following equation (1).
FIC index = Qa / QA + Qb / QB (1)
(Where
Qa is the MIC value of the A component when the A component and the B component are used in combination.
QA is the MIC value of A component alone,
Qb is the MIC value of the B component when the A component and the B component are used together.
QB represents the MIC value of the B component alone)
The FIC index represents the effect of the combined use of the A component and the B component. When the FIC index is 1, it indicates that there is an additive action by the combined use of the A component and the B component. When the FIC index is greater than 1, it indicates that there is an antagonistic action by the combined use of the A component and the B component. When the FIC index is less than 1, it indicates that there is a synergistic effect by the combined use of the A component and the B component.
（実施例１１）
ＭＴＩ、ＭＩＴ単剤および各混比率でのＭＩＣ値とＦＩＣ指数を表４に示す。
(Example 11)
Table 4 shows the MIC value and FIC index for MTI, MIT single agent and each mixing ratio.
ＭＴＩ、ＭＩＴ単剤および各混比率でのＭＩＣ値とＦＩＣ指数を表４に示す。
Table 4 shows the MIC value and FIC index for MTI, MIT single agent and each mixing ratio.
（実施例１２）
ＭＴＩ、Ｌｏｎｚａｂａｃ １２（ｐＨ６．４に調整）単剤および各混合比率でのＭＩＣ値とＦＩＣ指数を表５に示す。
Example 12
Table 5 shows the MIC value and FIC index of MTI, Lonzabac 12 (adjusted to pH 6.4) alone and each mixing ratio.
ＭＴＩ、Ｌｏｎｚａｂａｃ １２（ｐＨ６．４に調整）単剤および各混合比率でのＭＩＣ値とＦＩＣ指数を表５に示す。
Table 5 shows the MIC value and FIC index of MTI, Lonzabac 12 (adjusted to pH 6.4) alone and each mixing ratio.
（実施例１３）
ＭＴＩとＭＩＴの混合品（ＭＴＩ／ＭＩＴ比率１：１）とＬｏｎｚａｂａｃ１２（ｐＨを６．４に調整）を各混合比率で組み合わせた時のＭＩＣ値とＦＩＣ指数を表６に示す。
表４、表５，表６から、２－メチル－４，５－トリメチレン－４－イソチアゾリン－３－オン（ＭＴＩ）と２－メチル－４－イソチアゾリン－３－オン（ＭＩＴ）および／または上記一般式（１）で表される化合物を有効成分とする防腐剤組成物は、各単剤を有効成分とする防腐剤組成物に比べて相乗効果が期待できる。 (Example 13)
Table 6 shows the MIC value and FIC index when a mixed product of MTI and MIT (MTI / MIT ratio 1: 1) and Lonzabacl 12 (pH adjusted to 6.4) were combined at each mixing ratio.
From Table 4, Table 5, and Table 6, 2-methyl-4,5-trimethylene-4-isothiazolin-3-one (MTI) and 2-methyl-4-isothiazolin-3-one (MIT) and / or the above general The preservative composition containing the compound represented by the formula (1) as an active ingredient can be expected to have a synergistic effect as compared with the preservative composition containing each single agent as an active ingredient.
ＭＴＩとＭＩＴの混合品（ＭＴＩ／ＭＩＴ比率１：１）とＬｏｎｚａｂａｃ１２（ｐＨを６．４に調整）を各混合比率で組み合わせた時のＭＩＣ値とＦＩＣ指数を表６に示す。
表４、表５，表６から、２－メチル－４，５－トリメチレン－４－イソチアゾリン－３－オン（ＭＴＩ）と２－メチル－４－イソチアゾリン－３－オン（ＭＩＴ）および／または上記一般式（１）で表される化合物を有効成分とする防腐剤組成物は、各単剤を有効成分とする防腐剤組成物に比べて相乗効果が期待できる。 (Example 13)
Table 6 shows the MIC value and FIC index when a mixed product of MTI and MIT (MTI / MIT ratio 1: 1) and Lonzabacl 12 (pH adjusted to 6.4) were combined at each mixing ratio.
From Table 4, Table 5, and Table 6, 2-methyl-4,5-trimethylene-4-isothiazolin-3-one (MTI) and 2-methyl-4-isothiazolin-3-one (MIT) and / or the above general The preservative composition containing the compound represented by the formula (1) as an active ingredient can be expected to have a synergistic effect as compared with the preservative composition containing each single agent as an active ingredient.
次に本発明をより具体的に示すために、水性アクリルエマルション、ノニオン界面活性剤、リグニン系コンクリート混和剤での各防腐剤組成物の評価結果を示すが、本発明はこれらの例によって制限されるものではない。実施例、比較例中の「％」は「重量％」を表す。
Next, in order to show the present invention more specifically, the evaluation results of each preservative composition with an aqueous acrylic emulsion, a nonionic surfactant, and a lignin-based concrete admixture are shown, but the present invention is limited by these examples. It is not something. “%” In Examples and Comparative Examples represents “% by weight”.
（製剤例１４）
防腐剤組成物１１を８０.０グラムに防腐剤組成物１２を２０．０グラム加え撹拌してＭＴＩ ４．０％、ＭＩＴ １．０％の防腐組成物１４を得た。 (Formulation Example 14)
Preservative composition 11 was added to 80.0 grams and 20.0 grams of preservative composition 12 was added and stirred to obtain a preservative composition 14 having an MTI of 4.0% and an MIT of 1.0%.
防腐剤組成物１１を８０.０グラムに防腐剤組成物１２を２０．０グラム加え撹拌してＭＴＩ ４．０％、ＭＩＴ １．０％の防腐組成物１４を得た。 (Formulation Example 14)
Preservative composition 11 was added to 80.0 grams and 20.0 grams of preservative composition 12 was added and stirred to obtain a preservative composition 14 having an MTI of 4.0% and an MIT of 1.0%.
（製剤例１５）
防腐剤組成物１１を５０.０グラムに防腐剤組成物１２を５０．０グラム加え撹拌してＭＴＩ ２．５％、ＭＩＴ ２．５％の防腐組成物１５を得た。 (Formulation Example 15)
Preservative composition 11 was added to 50.0 grams and 50.0 grams of preservative composition 12 was added and stirred to obtain preservative composition 15 having an MTI of 2.5% and an MIT of 2.5%.
防腐剤組成物１１を５０.０グラムに防腐剤組成物１２を５０．０グラム加え撹拌してＭＴＩ ２．５％、ＭＩＴ ２．５％の防腐組成物１５を得た。 (Formulation Example 15)
Preservative composition 11 was added to 50.0 grams and 50.0 grams of preservative composition 12 was added and stirred to obtain preservative composition 15 having an MTI of 2.5% and an MIT of 2.5%.
（製剤例１６）
防腐剤組成物１１を５０.０グラムに防腐剤組成物１３を５０．０グラム加え撹拌してＭＴＩ ２．５％、ビス（アミノプロピル）ドデシルアミン２．５％の防腐剤組成物１６を得た。 (Formulation Example 16)
50.0 grams of preservative composition 11 was added to 50.0 grams of preservative composition 11 and stirred to obtain preservative composition 16 of 2.5% MTI and 2.5% bis (aminopropyl) dodecylamine. It was.
防腐剤組成物１１を５０.０グラムに防腐剤組成物１３を５０．０グラム加え撹拌してＭＴＩ ２．５％、ビス（アミノプロピル）ドデシルアミン２．５％の防腐剤組成物１６を得た。 (Formulation Example 16)
50.0 grams of preservative composition 11 was added to 50.0 grams of preservative composition 11 and stirred to obtain preservative composition 16 of 2.5% MTI and 2.5% bis (aminopropyl) dodecylamine. It was.
（製剤例１７）
防腐剤組成物１１、防腐剤組成物１２、更に防腐剤組成物１３を同量加え撹拌してＭＴＩ、ＭＩＴおよびビス（アミノプロピル）ドデシルアミンが１：１：１、有効成分濃度５．０％の防腐剤組成物１７を得た。 (Formulation Example 17)
Preservative composition 11, preservative composition 12, and preservative composition 13 were added in the same amount and stirred, and MTI, MIT and bis (aminopropyl) dodecylamine were 1: 1: 1, and the active ingredient concentration was 5.0%. Of antiseptic composition 17 was obtained.
防腐剤組成物１１、防腐剤組成物１２、更に防腐剤組成物１３を同量加え撹拌してＭＴＩ、ＭＩＴおよびビス（アミノプロピル）ドデシルアミンが１：１：１、有効成分濃度５．０％の防腐剤組成物１７を得た。 (Formulation Example 17)
Preservative composition 11, preservative composition 12, and preservative composition 13 were added in the same amount and stirred, and MTI, MIT and bis (aminopropyl) dodecylamine were 1: 1: 1, and the active ingredient concentration was 5.0%. Of antiseptic composition 17 was obtained.
（製剤例１８）
１,２－ベンゾイソチアゾリン－３－オンを５．０グラム計量し、ジメチルエタノールアミン２０グラム、精製水７５グラムを加え、撹拌・溶解して防腐剤組成物１８を得た。 (Formulation Example 18)
5.0 grams of 1,2-benzisothiazolin-3-one was weighed, 20 grams of dimethylethanolamine and 75 grams of purified water were added, and stirred and dissolved to obtain an antiseptic composition 18.
１,２－ベンゾイソチアゾリン－３－オンを５．０グラム計量し、ジメチルエタノールアミン２０グラム、精製水７５グラムを加え、撹拌・溶解して防腐剤組成物１８を得た。 (Formulation Example 18)
5.0 grams of 1,2-benzisothiazolin-3-one was weighed, 20 grams of dimethylethanolamine and 75 grams of purified water were added, and stirred and dissolved to obtain an antiseptic composition 18.
（製剤例１９）
防腐剤組成物１２を５０．０グラムに防腐剤組成物１３を５０．０グラム加え撹拌してＭＩＴ ２．５％、ビス（アミノプロピル）ドデシルアミン２．５％の防腐剤組成物１９を得た。 (Formulation Example 19)
50.0 grams of preservative composition 12 and 50.0 grams of preservative composition 13 were added and stirred to obtain preservative composition 19 having MIT 2.5% and bis (aminopropyl) dodecylamine 2.5%. It was.
防腐剤組成物１２を５０．０グラムに防腐剤組成物１３を５０．０グラム加え撹拌してＭＩＴ ２．５％、ビス（アミノプロピル）ドデシルアミン２．５％の防腐剤組成物１９を得た。 (Formulation Example 19)
50.0 grams of preservative composition 12 and 50.0 grams of preservative composition 13 were added and stirred to obtain preservative composition 19 having MIT 2.5% and bis (aminopropyl) dodecylamine 2.5%. It was.
菌液の調製
Ｐｓｅｕｄｏｍｏｎａｓ ａｅｒｕｇｉｎｏｓａ ＮＢＲＣ １２６８９
Ｅｓｃｈｅｒｉｃｈｉａ ｃｏｌｉ ＮＢＲＣ ３９７２
Ｅｎｔｅｒｏｂａｃｔｏｒ ｃｌｏａｃａｅ ＮＢＲＣ １３５３５
以上の細菌を普通寒天培地にて培養、普通ブイヨン液体培地に加え、細菌混合液を作成した。細菌混合液の密度は１０８個／ｍｌに調整したものを接種菌とした。 Preparation of bacterial solution Pseudomonas aeruginosa NBRC 12589
Escherichia coli NBRC 3972
Enterobacter cloacae NBRC 13535
The above bacteria were cultured in a normal agar medium and added to a normal broth liquid medium to prepare a bacterial mixture. The inoculum was prepared by adjusting the density of the bacterial mixture to 10 8 cells / ml.
Ｐｓｅｕｄｏｍｏｎａｓ ａｅｒｕｇｉｎｏｓａ ＮＢＲＣ １２６８９
Ｅｓｃｈｅｒｉｃｈｉａ ｃｏｌｉ ＮＢＲＣ ３９７２
Ｅｎｔｅｒｏｂａｃｔｏｒ ｃｌｏａｃａｅ ＮＢＲＣ １３５３５
以上の細菌を普通寒天培地にて培養、普通ブイヨン液体培地に加え、細菌混合液を作成した。細菌混合液の密度は１０８個／ｍｌに調整したものを接種菌とした。 Preparation of bacterial solution Pseudomonas aeruginosa NBRC 12589
Escherichia coli NBRC 3972
Enterobacter cloacae NBRC 13535
The above bacteria were cultured in a normal agar medium and added to a normal broth liquid medium to prepare a bacterial mixture. The inoculum was prepared by adjusting the density of the bacterial mixture to 10 8 cells / ml.
（実施例１４）
水性アクリルエマルションに前記載の防腐剤組成物１４、１５、１６、１７を有効成分濃度で２５ｐｐｍ、５０ｐｐｍ、１００ｐｐｍになるよう添加した。各サンプルに接種液４％を接種して３０℃恒温器に保管した。接種後７日後に画線塗抹法により微生物の残存状態を普通寒天培地にて確認した。これを計４回繰り返した。 (Example 14)
Preservative compositions 14, 15, 16, and 17 described above were added to the aqueous acrylic emulsion so that the active ingredient concentrations were 25 ppm, 50 ppm, and 100 ppm. Each sample was inoculated with 4% inoculum and stored in a 30 ° C incubator. Seven days after the inoculation, the remaining state of the microorganism was confirmed on a normal agar medium by a streak smearing method. This was repeated a total of 4 times.
水性アクリルエマルションに前記載の防腐剤組成物１４、１５、１６、１７を有効成分濃度で２５ｐｐｍ、５０ｐｐｍ、１００ｐｐｍになるよう添加した。各サンプルに接種液４％を接種して３０℃恒温器に保管した。接種後７日後に画線塗抹法により微生物の残存状態を普通寒天培地にて確認した。これを計４回繰り返した。 (Example 14)
Preservative compositions 14, 15, 16, and 17 described above were added to the aqueous acrylic emulsion so that the active ingredient concentrations were 25 ppm, 50 ppm, and 100 ppm. Each sample was inoculated with 4% inoculum and stored in a 30 ° C incubator. Seven days after the inoculation, the remaining state of the microorganism was confirmed on a normal agar medium by a streak smearing method. This was repeated a total of 4 times.
（比較例１４）
水性アクリルエマルションに前記載の防腐剤組成物１１、１２、１３、１８、１９を有効成分濃度で２５ｐｐｍ、５０ｐｐｍ、１００ｐｐｍになるよう添加した。各サンプルに接種液２％を接種して３０℃恒温器に保管した。接種後７日後に画線塗抹法により微生物の残存状態を普通寒天培地にて確認した。これを計４回繰り返した。 (Comparative Example 14)
Preservative compositions 11, 12, 13, 18, and 19 described above were added to the aqueous acrylic emulsion so that the active ingredient concentrations were 25 ppm, 50 ppm, and 100 ppm. Each sample was inoculated with 2% inoculum and stored in a 30 ° C incubator. Seven days after the inoculation, the remaining state of the microorganism was confirmed on a normal agar medium by a streak smearing method. This was repeated a total of 4 times.
水性アクリルエマルションに前記載の防腐剤組成物１１、１２、１３、１８、１９を有効成分濃度で２５ｐｐｍ、５０ｐｐｍ、１００ｐｐｍになるよう添加した。各サンプルに接種液２％を接種して３０℃恒温器に保管した。接種後７日後に画線塗抹法により微生物の残存状態を普通寒天培地にて確認した。これを計４回繰り返した。 (Comparative Example 14)
Preservative compositions 11, 12, 13, 18, and 19 described above were added to the aqueous acrylic emulsion so that the active ingredient concentrations were 25 ppm, 50 ppm, and 100 ppm. Each sample was inoculated with 2% inoculum and stored in a 30 ° C incubator. Seven days after the inoculation, the remaining state of the microorganism was confirmed on a normal agar medium by a streak smearing method. This was repeated a total of 4 times.
（評価基準）
微生物の残存状態は普通寒天培地上に残存する微生物の量に応じて表７に示した基準に
より判定した。 (Evaluation criteria)
The remaining state of the microorganism was determined according to the criteria shown in Table 7 according to the amount of the microorganism remaining on the normal agar medium.
微生物の残存状態は普通寒天培地上に残存する微生物の量に応じて表７に示した基準に
より判定した。 (Evaluation criteria)
The remaining state of the microorganism was determined according to the criteria shown in Table 7 according to the amount of the microorganism remaining on the normal agar medium.
水性アクリルエマルションでの評価結果を表８に示す。
Table 8 shows the evaluation results of the aqueous acrylic emulsion.
菌液の調整は、段落番号００７３と同じように実施した。
The bacterial solution was prepared in the same manner as in paragraph 0073.
（実施例１５）
ノニオン界面活性剤（ポリオキシエチレンモノラウレート１％水溶液）に前記載の防腐剤組成物１５、１６、１７、１８を有効成分濃度で２５ｐｐｍ、５０ｐｐｍ、１００ｐｐｍになるよう添加した。各サンプルに接種液１％を接種して３０℃恒温器に保管した。接種後７日後に画線塗抹法により微生物の残存状態を普通寒天培地にて確認した。これを計３回繰り返した。 (Example 15)
Preservative compositions 15, 16, 17, and 18 described above were added to the nonionic surfactant (polyoxyethylene monolaurate 1% aqueous solution) so that the active ingredient concentrations were 25 ppm, 50 ppm, and 100 ppm. Each sample was inoculated with 1% inoculum and stored in a 30 ° C incubator. Seven days after the inoculation, the remaining state of the microorganism was confirmed on a normal agar medium by a streak smearing method. This was repeated a total of 3 times.
ノニオン界面活性剤（ポリオキシエチレンモノラウレート１％水溶液）に前記載の防腐剤組成物１５、１６、１７、１８を有効成分濃度で２５ｐｐｍ、５０ｐｐｍ、１００ｐｐｍになるよう添加した。各サンプルに接種液１％を接種して３０℃恒温器に保管した。接種後７日後に画線塗抹法により微生物の残存状態を普通寒天培地にて確認した。これを計３回繰り返した。 (Example 15)
Preservative compositions 15, 16, 17, and 18 described above were added to the nonionic surfactant (polyoxyethylene monolaurate 1% aqueous solution) so that the active ingredient concentrations were 25 ppm, 50 ppm, and 100 ppm. Each sample was inoculated with 1% inoculum and stored in a 30 ° C incubator. Seven days after the inoculation, the remaining state of the microorganism was confirmed on a normal agar medium by a streak smearing method. This was repeated a total of 3 times.
（比較例１５）
ノニオン界面活性剤（ポリオキシエチレンモノラウレート１％水溶液）に前記載の防腐剤組成物１１、１２、１３、１８を有効成分濃度で２５ｐｐｍ、５０ｐｐｍ、１００ｐｐｍになるよう添加した。各サンプルに接種液１％を接種して３０℃恒温器に保管した。接種後７日後に画線塗抹法により微生物の残存状態を普通寒天培地にて確認した。これを計３回繰り返した。 (Comparative Example 15)
Preservative compositions 11, 12, 13, and 18 described above were added to the nonionic surfactant (polyoxyethylene monolaurate 1% aqueous solution) so that the active ingredient concentrations were 25 ppm, 50 ppm, and 100 ppm. Each sample was inoculated with 1% inoculum and stored in a 30 ° C incubator. Seven days after the inoculation, the remaining state of the microorganism was confirmed on a normal agar medium by a streak smearing method. This was repeated a total of 3 times.
ノニオン界面活性剤（ポリオキシエチレンモノラウレート１％水溶液）に前記載の防腐剤組成物１１、１２、１３、１８を有効成分濃度で２５ｐｐｍ、５０ｐｐｍ、１００ｐｐｍになるよう添加した。各サンプルに接種液１％を接種して３０℃恒温器に保管した。接種後７日後に画線塗抹法により微生物の残存状態を普通寒天培地にて確認した。これを計３回繰り返した。 (Comparative Example 15)
Preservative compositions 11, 12, 13, and 18 described above were added to the nonionic surfactant (polyoxyethylene monolaurate 1% aqueous solution) so that the active ingredient concentrations were 25 ppm, 50 ppm, and 100 ppm. Each sample was inoculated with 1% inoculum and stored in a 30 ° C incubator. Seven days after the inoculation, the remaining state of the microorganism was confirmed on a normal agar medium by a streak smearing method. This was repeated a total of 3 times.
（評価基準）
段落番号００７６、００７７の記載と同様に実施した。 (Evaluation criteria)
It carried out similarly to description of the paragraph numbers 0076 and 0077.
段落番号００７６、００７７の記載と同様に実施した。 (Evaluation criteria)
It carried out similarly to description of the paragraph numbers 0076 and 0077.
ノニオン界面活性剤（ポリオキシエチレンモノラウレート１％水溶液）での評価結果を表９に示す。
Table 9 shows the evaluation results with a nonionic surfactant (polyoxyethylene monolaurate 1% aqueous solution).
段落番号００７３の菌液を調製し、リグニン系コンクリート混和剤に添加して１０の６乗ＣＦＵ／ｍｌ以上に腐敗させた。
A bacterial solution of paragraph 0073 was prepared and added to a lignin-based concrete admixture to cause it to decay to 10 6 CFU / ml or more.
（実施例１６）
腐敗したリグニン系コンクリート混和剤に前記載の防腐剤組成物１５、１６、１７を有効成分濃度で５０ｐｐｍ、１００ｐｐｍになるよう添加し、防腐剤添加１日後、３日後、７日後に画線塗抹法により微生物の残存状態を普通寒天培地にて確認した。 (Example 16)
The preservative composition 15, 16, 17 described above is added to the rotten lignin-based concrete admixture so that the active ingredient concentration is 50 ppm and 100 ppm, and the image smearing method is performed 1 day, 3 days, and 7 days after the addition of the preservative. Thus, the remaining state of the microorganism was confirmed on a normal agar medium.
腐敗したリグニン系コンクリート混和剤に前記載の防腐剤組成物１５、１６、１７を有効成分濃度で５０ｐｐｍ、１００ｐｐｍになるよう添加し、防腐剤添加１日後、３日後、７日後に画線塗抹法により微生物の残存状態を普通寒天培地にて確認した。 (Example 16)
The preservative composition 15, 16, 17 described above is added to the rotten lignin-based concrete admixture so that the active ingredient concentration is 50 ppm and 100 ppm, and the image smearing method is performed 1 day, 3 days, and 7 days after the addition of the preservative. Thus, the remaining state of the microorganism was confirmed on a normal agar medium.
（比較例１６）
腐敗したリグニン系コンクリート混和剤に前記載の防腐剤組成物１１、１２、１３、１９を有効成分濃度で５０ｐｐｍ、１００ｐｐｍになるよう添加し、防腐剤添加１日後、３日後、７日後に画線塗抹法により微生物の残存状態を普通寒天培地にて確認した。 (Comparative Example 16)
The preservative composition 11, 12, 13, 19 described above is added to the rotten lignin-based concrete admixture so that the active ingredient concentration is 50 ppm and 100 ppm, and the line is drawn 1 day, 3 days, and 7 days after the addition of the preservative. The remaining state of the microorganism was confirmed on a normal agar medium by a smearing method.
腐敗したリグニン系コンクリート混和剤に前記載の防腐剤組成物１１、１２、１３、１９を有効成分濃度で５０ｐｐｍ、１００ｐｐｍになるよう添加し、防腐剤添加１日後、３日後、７日後に画線塗抹法により微生物の残存状態を普通寒天培地にて確認した。 (Comparative Example 16)
The preservative composition 11, 12, 13, 19 described above is added to the rotten lignin-based concrete admixture so that the active ingredient concentration is 50 ppm and 100 ppm, and the line is drawn 1 day, 3 days, and 7 days after the addition of the preservative. The remaining state of the microorganism was confirmed on a normal agar medium by a smearing method.
（評価基準）
段落番号００７６、００７７の記載と同様に実施した。 (Evaluation criteria)
It carried out similarly to description of the paragraph numbers 0076 and 0077.
段落番号００７６、００７７の記載と同様に実施した。 (Evaluation criteria)
It carried out similarly to description of the paragraph numbers 0076 and 0077.
リグニン系コンクリート混和剤での評価結果を表１０に示す。
Table 10 shows the evaluation results with the lignin-based concrete admixture.
本発明の防腐剤は２－メチル－４，５－トリメチレン－４－イソチアゾリン－３－オンと２－メチル－４－イソチアゾリン－３－オンおよび／または上記一般式（１）で表される化合物とを有効成分として含有するため、低濃度で微生物汚染による腐敗を著しく回避できるものである。
The preservative of the present invention includes 2-methyl-4,5-trimethylene-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one and / or a compound represented by the above general formula (1). As an active ingredient, rot due to microbial contamination can be significantly avoided at low concentrations.
The preservative of the present invention includes 2-methyl-4,5-trimethylene-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one and / or a compound represented by the above general formula (1). As an active ingredient, rot due to microbial contamination can be significantly avoided at low concentrations.
Claims (3)
- （Ａ）２－メチル－４，５－トリメチレン－４－イソチアゾリン－３－オンと（Ｂ）２－メチル－４－イソチアゾリン－３－オンおよび／または一般式（１）で表される化合物とを有効成分として含有することを特徴とする防腐剤組成物。
（式中、Ｒは炭素数８から２２のアルキル基またはアリル基を表し、ｎ＋ｍは２～１２、好ましくは３～１０の数を表す） (A) 2-methyl-4,5-trimethylene-4-isothiazolin-3-one and (B) 2-methyl-4-isothiazolin-3-one and / or a compound represented by the general formula (1) An antiseptic composition, which is contained as an active ingredient.
(In the formula, R represents an alkyl group or an allyl group having 8 to 22 carbon atoms, and n + m represents a number of 2 to 12, preferably 3 to 10.) - （Ａ）２－メチル－４，５－トリメチレン－４－イソチアゾリン－３－オンと（Ｂ）２－メチル－４－イソチアゾリン－３－オンおよび／または一般式（１）で表される化合物との混合割合（Ａ）：（Ｂ）が重量比５０：１～１：５０であり、全有効成分が組成物全体の１重量％以上４０重量％以下の範囲であることを特徴とする請求項１に記載の防腐剤組成物。 (A) 2-methyl-4,5-trimethylene-4-isothiazolin-3-one and (B) 2-methyl-4-isothiazolin-3-one and / or a compound represented by the general formula (1) 2. The mixing ratio (A) :( B) is a weight ratio of 50: 1 to 1:50, and all active ingredients are in the range of 1 wt% to 40 wt% of the entire composition. The preservative composition according to 1.
- （Ａ）２－メチル－４，５－トリメチレン－４－イソチアゾリン－３－オンと（Ｂ）２－メチル４－イソチアゾリン－３－オンおよび／または一般式（１）で表される化合物の有効成分が、一般工業水系製品中に０．００１重量％以上１．０重量％以下の割合で配合されることを特徴とする請求項１、２記載の防腐剤組成物。
（式中、Ｒは炭素数８から２２のアルキル基またはアリル基を表し、ｎ＋ｍは２～１２、好ましくは３～１０の数を表す）
(A) 2-methyl-4,5-trimethylene-4-isothiazolin-3-one and (B) 2-methyl-4-isothiazolin-3-one and / or an active ingredient of a compound represented by the general formula (1) The preservative composition according to claim 1 or 2, characterized in that it is blended in a general industrial water-based product in a proportion of 0.001 wt% or more and 1.0 wt% or less.
(In the formula, R represents an alkyl group or an allyl group having 8 to 22 carbon atoms, and n + m represents a number of 2 to 12, preferably 3 to 10.)
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| WO2017010505A1 (en) * | 2015-07-14 | 2017-01-19 | ロンザ リミテッド | Preservative composition |
| CN107712438A (en) * | 2017-09-20 | 2018-02-23 | 无为县农园螃蟹养殖专业合作社 | A kind of non-toxic, environmental friendly crab feed preservative |
| KR20190024968A (en) * | 2016-06-30 | 2019-03-08 | 다우 글로벌 테크놀로지스 엘엘씨 | Synergistic combination of carbamic acid 3-iodo-2-propynyl-butyl and diamines |
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| CN107125249B (en) * | 2017-05-05 | 2019-11-01 | 奎克化学（中国）有限公司 | A kind of compound disinfectant and the metalworking fluid and preparation method thereof containing it |
| CN107384086A (en) * | 2017-09-22 | 2017-11-24 | 苏州振振好新型建材科技有限公司 | A kind of long acting antibiotic type coating and its preparation and application process |
| CN114767560B (en) * | 2022-05-20 | 2024-02-02 | 常州瑞昊环保科技有限公司 | Antibacterial composition and application thereof |
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| JP2010095517A (en) * | 2008-09-18 | 2010-04-30 | Permachem Asia Ltd | Industrial microbicide |
| WO2014175139A1 (en) * | 2013-04-26 | 2014-10-30 | 日本曹達株式会社 | Bactericidal composition |
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| WO2017010505A1 (en) * | 2015-07-14 | 2017-01-19 | ロンザ リミテッド | Preservative composition |
| KR20190024968A (en) * | 2016-06-30 | 2019-03-08 | 다우 글로벌 테크놀로지스 엘엘씨 | Synergistic combination of carbamic acid 3-iodo-2-propynyl-butyl and diamines |
| JP2019527195A (en) * | 2016-06-30 | 2019-09-26 | ダウ グローバル テクノロジーズ エルエルシー | Synergistic combination of 3-iodo-2-propynyl-butylcarbamate and diamine |
| KR102529483B1 (en) | 2016-06-30 | 2023-05-08 | 다우 글로벌 테크놀로지스 엘엘씨 | Synergistic combination of 3-iodo-2-propynyl-butyl carbamate and diamine |
| CN107712438A (en) * | 2017-09-20 | 2018-02-23 | 无为县农园螃蟹养殖专业合作社 | A kind of non-toxic, environmental friendly crab feed preservative |
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| Publication number | Publication date |
|---|---|
| JPWO2015107934A1 (en) | 2017-03-23 |
| CN105916380A (en) | 2016-08-31 |
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