JP5680368B2 - Industrial disinfectant composition stabilized against light - Google Patents

Description

  The present invention is an industrial disinfectant composition used for industrial cooling water, papermaking process water in the pulp and paper industry, lubricating oil, metalworking oil, and the like, in particular, an isothiazolone compound and a halogenated aliphatic nitroalcohol sterilizer as active ingredients The present invention relates to an industrial disinfectant composition stabilized against light containing an active agent as an active ingredient and a method for stabilizing the same.

  Industrial water such as industrial circulating cooling water, papermaking process water in the pulp and paper industry, industrial oils such as lubricants and metalworking oils, various industrial products such as paints, adhesives, inks, sealing agents and cement admixtures Are prone to breeding pests such as bacteria, yeast, fungi, and algae that cause decreased productivity and bad odor, and many industrial disinfectants are used. Among them, isothiazolone fungicides and halogenated aliphatic nitroalcohol fungicides are known to show excellent effects in the field of industrial fungicides, and by combining them, a more synergistic effect can be shown. Known (for example, see Patent Documents 1 to 3). However, these active ingredients are generally unstable, and stabilization of the active ingredients is indispensable for fully exhibiting the effects. As a conventional technique for the stabilization, a method of adding glucuronic acid or a salt thereof as a stabilizer (for example, see Patent Document 4), a method of using a glycol solvent as a stabilizing solvent (for example, see Patent Document 5) It has been known. In addition, as a method for stabilizing an isothiazolone-based fungicide, a method in which the pH of a solution is in a range of 4 to 5.1 by using bromate as a stabilizer without containing metal nitrate (see, for example, Patent Document 6), A method in which bromate or iodate is used as a stabilizer and the pH of the solution is in the range of 3.5 to 4.5 (see, for example, Patent Document 7), metal nitrate and bromate, iodate, A method of adding an iodate or the like (for example, see Patent Document 8) and a method of using bromate to adjust the pH of the solution to a range of 2.6 to less than 3.5 (for example, see Patent Document 9) are known. It has been.

Japanese Patent Publication No.58-4682 Japanese Patent Laid-Open No. 7-277910 JP 2000-319113 A JP-A-5-201809 JP 2003-238318 A JP-A-8-319279 JP-A-9-263504 Japanese Patent Laid-Open No. 11-158013 JP 2009-66791 A

However, the industrial bactericide composition containing the isothiazolone bactericides and halogenated aliphatic nitroalcohol bactericides according to the prior art as active ingredients has sufficient storage stability, thermal stability, and light stability. There has been a desire to create a more stabilized industrial disinfectant composition.
In general, industrial disinfectant compositions containing these as active ingredients have the problem that precipitation that becomes an obstacle in use occurs, causing troubles in the cooling tower, and precipitates together with the stability of the active ingredients. It was desired to create an industrial disinfectant without precipitation. In particular, as isothiazolone fungicides, 2-methyl-4-isothiazolin-3-one and 5-chloro-2-methyl-4-isothiazolin-3-one and halogenated aliphatic nitroalcohol fungicides as 2-bromo Industrial use disinfectant composition containing 2-nitropropane-1,3-diol as an active ingredient is exposed to sunlight such as outdoors because the precipitation of precipitates is accelerated by sunlight when used outdoors. However, it has been desired to create an industrial disinfectant composition in which no precipitate is deposited.

In order to solve the above-mentioned problems, the present inventors contain one or more isothiazolone fungicides, a halogenated aliphatic nitroalcohol fungicide, a pH buffer, a sulfonate, and water, Is an industrial disinfectant composition having a range of 2.3 or more and 4.0 or less, and that each active ingredient is present stably for a long period of time, and that there is no precipitation that becomes an obstacle in use due to sunlight. The headline and the present invention were completed.
That is, the present invention
[1] Contains one or more isothiazolone fungicides, a halogenated aliphatic nitroalcohol fungicide, a pH buffer, a sulfonate, and water, and has a pH in the range of 2.3 to 4.0. An industrial disinfectant composition which is
[2] The isothiazolone fungicide is 2-methyl-4-isothiazolin-3-one and / or 5-chloro-2-methyl-4-isothiazolin-3-one, and the halogenated aliphatic nitroalcohol fungicide is The industrial disinfectant composition according to the above [1], which is 2-bromo-2-nitropropane-1,3-diol;
[3] The industrial disinfectant composition according to [1] or [2], wherein the pH buffer is a polybasic acid salt;
[4] pH buffer is acetate, propionate, benzoate, glycine salt, phthalate, isophthalate, terephthalate, fumarate, maleate, succinate, citrate, tartaric acid The above-mentioned one or more selected from salts, malates, gluconates, glutarates, ethylenediaminetetraacetate (EDTA), aspartate, glutamate, polymaleate and polyacrylate Industrial disinfectant composition according to [1] or [2];
[5] The industrial disinfectant composition according to the above [3] or [4], wherein the pH buffer is trisodium citrate;
[6] The industry according to any one of [1] to [5], wherein the sulfonate is one or more selected from calcium lignin sulfonate, magnesium lignin sulfonate, and sodium lignin sulfonate. Disinfectant composition;
[7] 0.1 to 14% by mass of the isothiazolone fungicide with respect to the total amount of the industrial fungicide composition, and 0.1% by weight of the halogenated aliphatic nitroalcohol fungicide with respect to the total amount of the industrial fungicide composition. Industrial disinfectant composition as described in any one of said [1]-[6] containing 1-5 mass%;
[8] The industrial bactericidal composition according to any one of the above [1] to [6], which contains 0.01 to 5% by mass of a pH buffering agent based on the total amount of the industrial bactericidal composition;
[9] The industrial fungicide composition according to any one of the above [1] to [6], which contains 0.01 to 5% by mass of a sulfonate with respect to the total amount of the industrial fungicide composition;
[10] In an industrial fungicide composition containing one or more isothiazolone fungicides and a halogenated aliphatic nitroalcohol fungicide as active ingredients, a pH buffer and a sulfonate are included, And a method for stabilizing an industrial disinfectant composition, wherein the pH is adjusted to a range of 2.3 or more and 4.0 or less;
Etc.

  According to the present invention, it is excellent for aging stability and thermal stability, the active ingredient is stably present even when stored for a long period of time, and there is no precipitation of precipitates that become an obstacle in use due to sunlight. A disinfectant composition can be provided.

FIG. 1 is a photograph showing a state when the test is disclosed in the stability test. From the left, Comparative Example 1, Examples 3, 5 and 7 are shown. FIG. 2 is a photograph showing a state after storage for one week outdoors in a stability test. From the left, Comparative Example 1, Examples 3, 5 and 7 are shown.

  Examples of the isothiazolone fungicide which is an active ingredient of the present invention include 2-methyl-4-isothiazolin-3-one, 2-ethyl-4-isothiazolin-3-one, 2-propyl-4-isothiazoline-3- 2-alkyl-4-isothiazolin-3-one such as ON, 2-isopropyl-4-isothiazolin-3-one, 2-n-octyl-4-isothiazolin-3-one; 5-chloro-2-methyl-4 -Isothiazolin-3-one, 5-bromo-2-methyl-4-isothiazolin-3-one, 5-chloro-2-ethyl-4-isothiazolin-3-one, 5-bromo-2-ethyl-4-isothiazoline -3-one, 5-chloro-2-n-octyl-4-isothiazolin-3-one, 5-bromo-2-n-octyl-4-isothiazolin-3- 2-alkyl-5-halo-4-isothiazolin-3-one such as 2-methyl-4-isothiazolin-3-one and / or 5-chloro-2-methyl-4-isothiazoline -3-one. These may be used alone or in combination of two or more. In the present invention, 2-methyl-4-isothiazolin-3-one and 5-chloro-2-methyl-4- It is preferable to use a mixture of isothiazolin-3-one and the mixing ratio thereof is 5-chloro-2-methyl-4-isothiazoline-3 with respect to 1 part by mass of 2-methyl-4-isothiazolin-3-one. -The range of 1-5 mass parts is preferable, and in order to acquire a stable effect, the range of 1-3 mass parts is preferable.

  The blending ratio of the isothiazolone fungicide in the entire industrial fungicide composition is in the range of 0.1 to 14% by mass of the isothiazolone fungicide with respect to the total amount (100% by mass) of the industrial fungicide composition. Preferably, the range of 0.1-7 mass% is more preferable, Especially preferably, it is the range of 0.5-5 mass%. Usually, caisson WT, caisson LXplus, caisson LXplus-conc., Which are industrial bases containing isothiazolone fungicides, are used. (Made by Rohm and Haas), Sönen C, Sönen F (manufactured by Chemiclear) and the like are used.

Examples of the other halogenated aliphatic nitroalcohol fungicides that are active ingredients include 2,2-dichloro-2-nitroethanol, 2,2-dibromo-2-nitroethanol, and 2-bromo-2-chloro. -2-nitroethanol, 2-chloro-2-nitropropane-1,3-diol, 2-bromo-2-nitropropane-1,3-diol, and the like, and particularly preferably 2 known as bronopol. -Bromo-2-nitropropane-1,3-diol. As a compounding ratio of the halogenated aliphatic nitroalcohol-based fungicide in the entire industrial fungicide composition, the halogenated aliphatic nitroalcohol-based fungicide is 0 with respect to the total amount (100% by mass) of the industrial fungicide composition. The range of 0.1 to 5% by mass is preferable, and the range of 0.2 to 2% by mass is particularly preferable.
The blending ratio of the isothiazolone fungicide and the halogenated aliphatic nitro alcohol fungicide is in the range of 0.01 to 10 parts by mass of the halogenated aliphatic nitro alcohol fungicide per 1 part by mass of the isothiazolone fungicide. Is preferable, and the range of 0.1 to 1 part by mass is particularly preferable.

  The pH buffer used in the present invention is used to stabilize the pH of the industrial fungicide composition. The pH buffer is not particularly limited as long as it has the above action, and an organic acid salt is preferably used. Examples of the organic acid salt include monobasic acid salts such as formate, acetate, propionate, trifluoroacetate, benzoate, glycine salt, p-toluenesulfonate, and methanesulfonate; phthalic acid Salt, isophthalate, terephthalate, fumarate, maleate, succinate, citrate, oxalate, tartrate, malate, gluconate, glutarate, glutamate, aspartic acid Salts, polybasic acid salts such as ethylenediaminetetraacetate (EDTA), polymaleic acid salt, polyacrylic acid salt and the like. Examples of counter ions include alkali metals such as lithium, sodium and potassium, and amines such as ammonium and pyridinium. And alkaline earth metals such as calcium. Preferably acetate, propionate, benzoate, glycine salt, phthalate, isophthalate, terephthalate, fumarate, maleate, succinate, citrate, tartrate, malate , Gluconate, glutarate, ethylenediaminetetraacetate (EDTA), aspartate, glutamate, polymaleate or polyacrylate, and particularly preferred compounds include sodium hydrogen phthalate, sodium phthalate, Examples include polybasic acid salts such as disodium citrate, trisodium citrate, sodium fumarate, sodium tartrate, and trisodium citrate is more preferable. The blending ratio of the pH buffering agent is preferably in the range of 0.01 to 5% by mass, particularly preferably 0.05 to 3% by mass with respect to the total amount of industrial disinfectant composition (100% by mass). % Range. If the content of the pH buffering agent is less than this range, the pH of the fungicide composition tends to become unstable. Moreover, when there is more content of a pH buffer than this range, a disinfectant composition may discolor.

The sulfonate used in the present invention is used as a stabilizer. Examples of the sulfonate include alkylbenzene sulfonate, alkylnaphthalene sulfonate, polyoxyethylene distyrenated phenyl ether sulfate ammonium salt, alkylsulfosuccinate metal salt, lignin sulfonate, and the like. Examples of the metal salt include sodium salt, potassium salt, magnesium salt, calcium salt and the like. Preferred is lignin sulfonate, and particularly preferred is sodium lignin sulfonate, magnesium lignin sulfonate and / or calcium lignin sulfonate. Addition of sulfonate improves the stability of isothiazolone fungicides and halogenated aliphatic nitroalcohol fungicides. In particular, the improvement in the stability of halogenated aliphatic nitroalcohol-based fungicides is remarkable. Furthermore, precipitation of precipitates by sunlight can be remarkably improved by adding a sulfonate.
The blending ratio of the sulfonate is preferably 0.01 to 5% by mass, particularly preferably 0.05 to 3% by mass with respect to the total amount (100% by mass) of the industrial disinfectant composition. % Range. If the sulfonate content is less than this range, the light stability is insufficient and precipitates are likely to be formed. If the sulfonate content is higher than this range, the sulfonate may not be completely dissolved in the formulation, and the sulfonate itself may become a precipitate. May be counterproductive. In particular, when a high molecular weight sulfonate such as lignin sulfonate is used, the content is preferably 0.1% by mass or less.

In the stabilization of industrial disinfectants containing different active ingredients as in the industrial disinfectant composition of the present invention, it is not easy to search for conditions that can satisfy the stability of all active ingredients. Even in the region, if the stabilization of one active ingredient is pursued, phenomena such as significant degradation of the other active ingredient occur. The pH range is particularly important for achieving stabilization of the active ingredients of both isothiazolone fungicides and halogenated aliphatic nitroalcohol fungicides. In the present invention, the pH range is particularly preferably 2.3 or more and 4.0 or less, more preferably 2.6 or more and 3.4 or less, and particularly preferably 2.8 or more and 3.4 or less. If the pH is higher than this range, the halogenated aliphatic nitroalcohol-based fungicide tends to decompose, and if it is lower than this range, the isothiazolone-based fungicide tends to decompose.
An acid can be used to adjust the pH to an appropriate range. Examples of the acid that can be used include citric acid, hydrochloric acid, and nitric acid, and these can be used in combination of two or more. Citric acid is preferable.

  The water used in the present invention is used as a diluent for industrial disinfectant compositions, and any water may be used as long as the effects of the present invention are not impaired. Examples thereof include purified water such as tap water and distilled water, ion exchange water, and the like, and purified water and ion exchange water are preferred. Water may be used in such an amount that the active ingredient, pH buffer, and sulfonate of the industrial bactericide composition of the present invention have a predetermined content.

  The manufacturing method of the industrial disinfectant composition of this invention can be manufactured by a normal method. For example, bulk, sulfonate, pH buffer, and halogenated aliphatic nitroalcohol-based disinfectant containing isothiazolone-based disinfectants such as zonen C and zonen MT are dissolved in water, citric acid, hydrochloric acid, nitric acid, etc. It can manufacture by adjusting pH to an appropriate range with the acid of this.

  Moreover, the industrial disinfectant composition of this invention can also contain an antifoamer in the range which does not inhibit the outstanding effect of the industrial disinfectant composition of this invention. Examples of the antifoaming agent include organic antifoaming agents such as silicone antifoaming agents, surfactants, polyethers, and higher alcohols, and silicone antifoaming agents are preferable.

  Furthermore, the industrial fungicide composition of the present invention is a range that does not inhibit the excellent effects of the industrial fungicide composition of the present invention from other conventional components known to those skilled in the art as additives. In, it can contain suitably. Examples of the additive include a thickener, a stabilizer, a fragrance, a dispersant, a colorant, a discoloration preventing stabilizer, a complexing agent, and the like.

  The industrial disinfectant composition of the present invention is effective for the genus Sphaerotilis often found in an open-circulation cooling water system, as well as the genus Escherichia such as Escherichia coli, Staphylococcus aureus ( Staphylococcus (genus Staphylococcus aureus), etc. Zub It has antibacterial activity against bacteria of the genus Enterobacter such as Bacilus subtilis and the like, and Enterobacter aerogenes, and the effects of existing drugs In addition to the above, it also has an effect on these reduced fungi.In addition to the above, as an additive in the pulp production process, industrial oils such as lubricating oils, especially metalworking oils, paints, adhesives, inks, sealing agents, It can also be used in the field of various industrial products such as cement admixtures.

  Although the manufacture example of the industrial disinfectant composition of this invention, the stability test example of an active ingredient, the presence or absence of a deposit and coloring, and the effect test example are shown below, this application is not limited to these. In the following production examples and test examples, CMT represents 5-chloro-2-methyl-4-isothiazolin-3-one, MT represents 2-methyl-4-isothiazolin-3-one, and BP represents 2- Represents bromo-2-nitropropane-1,3-diol.

Example 1
0.1 part by mass of sodium lignin sulfonate is dissolved in 70.0 parts by mass of ion-exchanged water, 14.37 parts by mass of Zonen C (CMT: about 10.5% by mass, MT: about 3.5% by mass, manufactured by Chemclair), Bronopol (BP; purity 99.8%, manufactured by Chemicrea) 0.3 parts by weight and trisodium citrate dihydrate 1 part by weight were dissolved in order, and the pH was adjusted to 2.3 using citric acid. , Ion exchange water was added to make the whole 100 parts by mass, test No. 1 containing about 1.5% by mass of CMT, about 0.5% by mass of MT, and about 0.3% by mass of BP. 1 (Example 1) of an industrial disinfectant composition was obtained.

Examples 2-7
In the same manner as in Example 1, sodium lignin sulfonate and trisodium citrate were blended so as to have the contents shown in Table 1, adjusted to the pH shown in Table 1, and the test no. 2-7 industrial disinfectant compositions were obtained.

Comparative Example 1
It manufactured according to the manufacturing method disclosed by Unexamined-Japanese-Patent No. 2009-67771. That is, 0.1 part by mass of potassium bromate was dissolved in 70.0 parts by mass of ion-exchanged water, and Zonen C (CMT about 10.5% by mass, MT about 3.5% by mass, manufactured by Chemclere) 14.2 parts by mass , 0.1 part by weight of trisodium citrate dihydrate, 0.06 part by weight of maleic anhydride, 0.3 part by weight of bronopol (BP; purity 99.8%, manufactured by Chemicrea) are dissolved in order, and ion exchange is performed. Water was added to make the whole 100 parts by mass. The pH after production was 3.4.

Stability test example 1
The industrial fungicide composition produced in the formulation examples and comparative examples was filled in a colorless glass test tube and stored outdoors for one week, and then the residual ratio of CMT, MT, and BP was measured by liquid chromatography. The occurrence of precipitation was visually evaluated. The results are shown in Tables 1 and 2, and photographs of the appearances of Tables 1 and 2 and Examples 3, 5 and 7, and Comparative Examples are shown in FIGS.

Evaluation criteria for the residual rate of active ingredients;
A: Residual rate 90% or more B: Residual rate 80-99%
C: Residual rate 70-79%
D: Residual rate 60-69%
E: Residual rate of 59% or less In the above evaluation criteria, C or more has no problem as a product effect, but D or less has a problem in effect and cannot be made into a product.

Evaluation criteria for sediments;
A: Sediment generation is low and not settled B: Sediment is clearly generated visually C: Generation of a lot of sediment is observed In the above evaluation criteria, A is no problem in use of the product, Below B, there is a problem and it cannot be made into a product.

  From the results shown in Tables 1 and 2 and FIGS. 1 and 2, trisodium citrate, which is a pH buffering agent, and lignin sulfonate, which is a stabilizer, are blended, and the pH is 2.3 or higher. In the range of 0 or less, it can be seen that the active ingredient is stable, the amount of precipitate is small, the particle does not settle, and there is no practical problem. On the other hand, in the sample compared, the stability of BP was poor and a large amount of precipitate was deposited.

Claims (9)

2-methyl-4-isothiazolin-3-one and / or 5-chloro-2-methyl-4-isothiazolin-3-one , 2-bromo-2-nitropropane-1,3-diol , pH buffer, lignin An industrial disinfectant composition containing a sulfonate and water and having a pH in the range of 2.3 to 4.0. The industrial disinfectant composition according to claim 1 , wherein the pH buffer is a polybasic acid salt. pH buffer is acetate, propionate, benzoate, glycine salt, phthalate, isophthalate, terephthalate, fumarate, maleate, succinate, citrate, tartrate, apple The acid salt, gluconate, glutarate, ethylenediaminetetraacetate (EDTA), aspartate, glutamate, polymaleate and polyacrylate are one or more kinds selected from claim 1 Industrial disinfectant composition as described. The industrial disinfectant composition according to claim 2 or 3 , wherein the pH buffer is trisodium citrate. Lignin sulfonate calcium lignin sulfonate, an industrial fungicide composition according to any one of claims 1-4 is one or more selected from lignin magnesium sulfonate and sodium lignin sulfonate . 2-methyl-4-isothiazolin-3-one and / or 5-chloro-2-methyl-4-isothiazolin-3-one in an amount of 0.1 to 14% by mass relative to the total amount of the industrial fungicide composition, 2 Industrial sterilization as described in any one of Claims 1-5 which contains 0.1-5 mass% of bromo- 2-nitropropane- 1, 3-diol with respect to the whole quantity of an industrial disinfectant composition. Agent composition. The industrial bactericidal composition according to any one of claims 1 to 5 , wherein the pH buffer is contained in an amount of 0.01 to 5 % by mass based on the total amount of the industrial bactericidal composition. The industrial bactericidal composition according to any one of claims 1 to 5 , wherein the sulfonic acid salt is contained in an amount of 0.01 to 5 mass% based on the total amount of the industrial bactericidal composition. Contains 2-methyl-4-isothiazolin-3-one and / or 5-chloro-2-methyl-4-isothiazolin-3-one and 2-bromo-2-nitropropane-1,3-diol as active ingredients An industrial disinfectant composition comprising a pH buffer and a lignin sulfonate, and having a pH adjusted to a range of 2.3 to 4.0. Method.