JPH0977616A - Industrial germicidal composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an industrial germicidal composition, excellent in immediate effect properties of germicidal effects and capable of manifesting the germicidal effects even in the presence of a reducing substance by blending 2-methyl-4,5- trimethylene-4-isothiazolin-3-one with a specific industrial germicide. SOLUTION: This industrial germicidal composition comprises 2-methyl-4,5- trimethylene-4-isothiazolin-3-one of the formula used in combination with an industrial germicide selected from among a halogenated oxime compound, a halogenated thiophene compound and a halogenated dithiol compound. The blending ratio of the compound to the industrial germicide is about (90:10) to (10:90) expressed in terms of weight ratio. The composition is preferably in a liquid form and converted into a one-part type for use. The composition is useful for carrying out the antiseptic or sterilizing treatment of papermaking process water in the paper pulp industry, cooling water, wash water, heavy oil sludges, metal working fluids, textile oil agents, paints, coating liquids for paper, latexes or sizing agents for various industrial uses.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an industrial fungicide composition. More specifically, the present invention relates to 2-methyl-
4,5-trimethylene-4-isothiazolin-3-one as an active ingredient, which is mixed with a specific industrial bactericide, papermaking process water in the paper and pulp industry, cooling water for various industries, and washing water , A heavy oil sludge, a metalworking oil, a fiber oil, a paint, a coating liquid for paper, a latex, and an industrial germicide composition useful for preserving and sterilizing pastes.

[0002]

2. Description of the Related Art Conventionally, slimes due to bacteria and fungi are generated in the papermaking process in the paper and pulp industry and in the cooling water system in various industries, which causes obstacles such as deterioration of product quality and production efficiency. It is known. Also,
Many industrial products such as heavy oil sludge, metalworking oils, fiber oils, paints, various latexes, and sizing agents are decomposed or contaminated by bacteria or fungi, which spoils the product and reduces its value. Many fungicides have been used to prevent damage by these microorganisms. Organic mercury compounds and chlorinated phenol compounds have been used for a long time, but these drugs are highly toxic to humans and seafood, and their use is regulated because they cause environmental pollution. Organic nitrogen-sulfur compounds, organic halogen-based compounds, and organic sulfur-based compounds, which have low toxicity, are widely used as industrial fungicides [Encyclopedia of antibacterial and antifungal agents (Showa 6
1 year, published by Japan Society for Antibacterial and Antifungal)]. Among these fungicides, isothiazolone compounds have also been developed as effective fungicides, and one of them is 2-methyl-4,5-
Trimethylene-4-isothiazolin-3-one (hereinafter,
It is abbreviated as MTI. ) (Japanese Patent Publication No. 2-349)
48, JP-A-3-145479, British Patent No. 2087388, British Patent No. 2208474.
No. specification). MTI exerts an excellent effect in preserving industrial products with neutral to alkaline pH and in sterilizing white water. It has also been found as the findings of the present inventors that MTI has excellent sustainability of effects. MTI is
Although it has such excellent performance, it has the following drawbacks and is limited in use. (1) The bactericidal effect is inferior in terms of fast-acting effect. Particularly when industrial water is reused, it is difficult to obtain a sufficient bactericidal effect by short-time treatment when the concentration of bacteria in the target water system is high. (2) When a reducing substance (aldehyde compound, sulfite, thiourea, etc.) is present in the applied industrial product or white water, it is chemically decomposed and the original bactericidal effect cannot be exhibited. (3) With the reuse of recovered water, contamination is caused by the appearance of various kinds of microorganisms, and therefore treatment with MTI alone is not sufficient.

[0003]

DISCLOSURE OF THE INVENTION The present invention has MTI as one of the active ingredients, has an excellent bactericidal effect in a quick effect, and exerts a bactericidal effect even in the presence of a reducing substance, and is effective against many kinds of microorganisms. The present invention has been made for the purpose of providing an effective industrial bactericide composition.

[0004]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that a halogenated oxime compound, a halogenated thiophene compound or a halogenated dithiol compound is added to MTI. It was found that not only can the bactericidal agent be given a rapid effect, but also a synergistic effect on the bactericidal effect can be obtained.
Based on this finding, the present invention has been completed. That is, the present invention relates to (1) industrial use selected from 2-methyl-4,5-trimethylene-4-isothiazolin-3-one (MTI) and a halogenated oxime compound, a halogenated thiophene compound or a halogenated dithiol compound. An industrial bactericidal composition comprising a bactericide as an active ingredient. Furthermore, in a preferred embodiment of the present invention, the weight ratio of (2) MTI to the industrial bactericide selected from halogenated oxime compounds, halogenated thiophene compounds or halogenated dithiol compounds is 90:10.
The industrial bactericide composition according to item (1), which is 10:90, (3) MTI, and an industrial bactericide selected from halogenated oxime compounds, halogenated thiophene compounds or halogenated dithiol compounds as a solvent. (1) or (2) as a one-part formulation, and (4) MTI, a halogenated oxime compound, a halogenated thiophene compound, or a halogenated compound An industrial bactericidal composition according to item (1) or (2), which is obtained by suspending an industrial bactericidal agent selected from dithiol compounds in water to prepare a one-pack formulation.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The composition of the present invention contains MTI and an industrial fungicide selected from halogenated oxime compounds, halogenated thiophene compounds or halogenated dithiol compounds as active ingredients. The MTI used in the composition of the present invention has the formula [1]

Embedded image Is a compound represented by. MTI used in the composition of the present invention
There is no particular limitation on the method for synthesizing, and the compound can be synthesized by any known method. For example, N-methyl-2
MTI can be obtained by reacting -benzylsulfinyl-1-cyclopentene-1-carboxamide with phosgene or propionyl chloride and cyclizing. Alternatively, 2- (N-methylcarbamoyl) cyclopentanone is reacted with hydrogen sulfide to give 2- (N-methylcarbamoyl)
MTI can be obtained by making cyclopentanethione and further cyclizing by reacting with sodium metaperiodate. The composition of the present invention contains MTI and an industrial fungicide selected from halogenated oxime compounds, halogenated thiophene compounds or halogenated dithiol compounds as active ingredients. Examples of the halogenated oxime compound used in the composition of the present invention include dichloroglyoxime and α
-Chlorobenzaldoxime, α-chlorobenzaldoxime acetate, 4-hydroxyphenyl-α-ketoacetohydroxymedic acid chloride (also called paracrocs), and the like can be mentioned. Examples of the halogenated thiophene compound used in the composition of the present invention include 3,3,
4,4-tetrachlorotetrahydrothiophene-1,1-
Dioxide, 3,3,4,4-tetrabromotetrahydrothiophene-1,1-dioxide and the like can be mentioned. Examples of the halogenated dithiol compound used in the composition of the present invention include 4,5-dichloro-1,2-dithiol-3-one and 5-chloro-4-phenyl-1,2-
Examples thereof include dithiol-3-one.

In the composition of the present invention, one of the halogenated oxime compound, the halogenated thiophene compound and the halogenated dithiol compound can be blended into the MTI alone, or two or more of them can be blended into the MTI. it can. In the composition of the present invention, the compounding ratio of MTI and the industrial bactericide selected from halogenated oxime compounds, halogenated thiophene compounds or halogenated dithiol compounds is preferably 90:10 to 10:90 by weight. , 70:30 to 30:70 is more preferable. By setting the mixing ratio of MTI and these industrial germicides to 90:10 to 10:90 by weight, the germicidal effect can be improved. There is no particular limitation on the form of the industrial bactericidal composition of the present invention as a drug, powder, granules, tablets, solutions, emulsions, suspensions, and the like,
Although it can be used in any form, it is used by combining MTI with an industrial fungicide component selected from halogenated oxime compounds, halogenated thiophene compounds or halogenated dithiol compounds to prepare one liquid formulation in a liquid form. Is preferred. There is no particular limitation on the method for preparing a one-part formulation, and it can be dissolved in a solvent to form a one-part formulation, or suspended in water to form a one-part formulation.

When the composition of the present invention is dissolved in a solvent to prepare a one-part formulation, the solvent to be used is a variety of water systems such as process water in the papermaking process and factory cooling water. Water or a hydrophilic organic solvent is preferably used in consideration of dissolution and dispersibility of the active ingredient. Examples of the hydrophilic organic solvent include amides such as dimethylformamide,
Glycols such as ethylene glycol, propylene glycol, diethylene glycol and dipropylene glycol, methyl cellosolve, phenyl cellosolve, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, glycol ethers such as dipropylene glycol monomethyl ether, methyl acetate, ethyl acetate, 3- Examples thereof include esters such as methoxybutyl acetate, 2-methoxyethyl acetate, 2-ethoxyethyl acetate, propylene carbonate, alcohols having 8 or less carbon atoms, and the like. When the composition of the present invention is suspended in water to form a one-pack formulation, xanthan gum, rhamzan gum, guar gum, etc. are used as thickeners, and nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants are used as dispersants. An activator or the like can be used. In addition, in order to prepare a water suspension,
Wet grinding can be performed using a ball mill, an attritor, or the like. When the system to be sterilized is an oil system such as heavy oil sludge, cutting oil, oil paint, etc., the composition of the present invention is preferably made into a one-part formulation using a hydrocarbon solvent such as heavy oil, kerosene, spindle oil and the like. When preparing a one-pack formulation using a hydrocarbon solvent, a nonionic surfactant, an anionic surfactant,
A cationic surfactant, an amphoteric surfactant, etc. can be used. The addition amount of the composition of the present invention varies depending on the object to be sterilized, and can be appropriately selected according to the properties of the object to be sterilized. Generally, 0.1 to 50 g / m ³ is preferably added for slime control of paper / pulp process water system and cooling water system, and it is a preservative for industrial products such as synthetic resin emulsions, starch pastes, paints and metal working oils. Has 1 to 5,000
It is preferable to add 0 g / m ³ .

[0008]

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. Test Example 1 The synergistic effect between 2-methyl-4,5-trimethylene-4-isothiazolin-3-one (MTI) and other industrial fungicides was investigated. Other industrial fungicides include dichloroglyoxime, α-chlorobenzaldoxime and α-chlorobenzaldoxime acetate as halogenated oxime compounds and 3,3,4,4-tetrachlorotetrahydrol as halogenated thiophene compounds. Thiophene-
1,1-dioxide was used as the halogenated dithiol compound, 4,5-dichloro-1,2-dithiol-3-one, and methylenebisthiocyanate as a known industrial bactericide which is neither of these. The water used for the test was white water with a high bacterial count, which was collected from the paperboard making process of the paper mill. The basic unit of water used in this papermaking process is 8
m ³ / ton, pH of white water is 6.6, BOD is 1,40
The number of bacteria was 0 × 10 ⁸ cells / ml, and the bacterial flora consisted mainly of Bacillus, Pseudomonas, Flavobacterium, and Alcaligenes. MTI and other industrial germicides were added to this white water at a weight ratio of 0: 100, 10:90, 30:70, 50:50, 7.
Add 0:30, 90:10 and 100: 0 so that the total amount becomes 20 μg / ml, and add 30
Shake for 30 minutes at ° C. Then, the number of viable bacteria was measured, and the bactericidal rate (%) with respect to the initial bacterial concentration was determined. The number of bacteria was measured by the agar plate method using broth agar medium.
The test results are shown in Table 1. The numbers in the table are sterilization rates (%)
It is.

[0009]

[Table 1]

The sterilization rate when adding only MTI is 25
%, The sterilization rate is 5 to 5 when only an industrial bactericide selected from halogenated oxime compounds, halogenated thiophene compounds or halogenated dithiol compounds is added.
50%. The sterilization rate is remarkably improved in both cases where 10% by weight of these industrial bactericide components are replaced with MTI and 10% by weight of MTI is replaced with these industrial bactericides. Furthermore, when the weight ratio of MTI to these industrial germicides is 50:50, the germicidal rate is the highest. From this result, it can be seen that there is a significant synergistic effect on the bactericidal action between MTI and the industrial bactericide selected from halogenated oxime compounds, halogenated thiophene compounds or halogenated dithiol compounds. On the other hand, when methylenebisthiocyanate is used as another industrial bactericide, such synergistic effect is not observed, and the bactericidal rate only gradually increases as the compounding amount of MTI increases. INDUSTRIAL APPLICABILITY The industrial bactericidal composition of the present invention exhibits a remarkable bactericidal effect as compared with conventional industrial bactericides in a highly concentrated papermaking water system due to expansion of antibacterial spectrum and synergistic / additive action. . Test Example 2 In water containing a reducing substance assuming reducing white water,
The synergistic effect of MTI and other industrial fungicides against Pseudomonas was investigated. Other industrial fungicides used were dichloroglyoxime, α-chlorobenzaldoxime and α-chlorobenzaldoxime acetate.
Hydrosulfite as a reducing substance was added in an amount of 100 μg / ml to a phosphate buffer of pH 7.0, and Pseudomonas bacteria were inoculated at 2.0 × 10 ⁷ cells / ml to give a test solution. This test solution was mixed with MTI and other industrial sterilizing agents in a weight ratio of 0: 100, 10:90, 30: 7.
The mixture was added so that the total amount was 0, 50:50, 70:30 and 100: 0, and the total amount was 20 μg / ml, and the mixture was shaken at 30 ° C. for 60 minutes. Then, the viable cell count was measured to determine the sterilization rate (%). The number of bacteria was measured by the agar plate method using broth agar medium. Similar tests were conducted on test liquids containing no reducing substance, using dichloroglyoxime as another industrial bactericide. The test results are shown in Table 2. The numerical values in the table are sterilization rates (%).

[0011]

[Table 2]

In the test solution containing no reducing substance, dichloroglyoxime alone exhibits an excellent bactericidal effect, but in the test solution containing the reducing substance, sterilization of all the halogenated oxime compounds tested was carried out. The effect is lower than that of the test liquid containing no reducing substance.
On the other hand, the industrial germicidal composition of the present invention containing a halogenated oxime compound and MTI has an excellent germicidal effect even in a reduced water system, and shows a synergistic effect of MTI and a halogenated oxime compound. There is. Test Example 3 An anti-corruption test was performed on latex to examine the synergistic effect of MTI and other industrial fungicides. Other industrial fungicides include dichloroglyoxime, α-chlorobenzaldoxime and α-chlorobenzaldoxime acetate as halogenated oxime compounds and 3,3,4,4-tetrachlorotetrahydrol as halogenated thiophene compounds. Thiophene-1,1-dioxide was used as the halogenated dithiol compound 4,5-dichloro-1,2-dithiol-3-one. 100 μg / ml of a mixture of MTI and another industrial bactericide in a weight ratio of 50:50 was added to a styrene-butadiene emulsion latex having a pH of 9.0, and the putrefaction solution of the latex had a bacterial count of 1.0.
The cells were inoculated so that the concentration was × 10 ⁵ cells / ml. 30 this liquid
The mixture was left standing at 0 ° C., inoculated with the same amount of the spoilage solution once a week, and the viable cell count was measured 7 days later, and this operation was repeated. As for the anti-corruption effect, the number of bacteria in the test solution is 1.
If the effect is less than 0 × 10 ³ cells / ml,
The number of days to prevent corruption was calculated. For comparison, the same test was performed using MTI and other industrial fungicides each alone. The test results are shown in Table 3.

[0013]

[Table 3]

As compared with the case where MTI or other industrial bactericides are used alone, the number of days for preventing spoilage is longer when the industrial bactericidal composition of the present invention containing MTI and other industrial bactericides is used. Shows that the effect is long-lasting and cannot be obtained when the industrial fungicide is used alone. Example 1 15 parts by weight of MTI, 10 parts by weight of dichloroglyoxime and 75 parts by weight of diethylene glycol monomethyl ether were blended to prepare an industrial fungicide composition. 10 ml of open-circulation cooling water of a petrochemical plant was sampled in a test tube, 200 μg / ml of this industrial germicide composition was added, and the temperature was 30 ° C.
Shaken at. After shaking the test solution for 30 minutes and 24 hours, the number of bacteria was measured. The number of bacteria was measured by the agar plate method using broth agar medium. Viable count after 30 minutes is 5.0 × 10 ² cells / ml, and viable count after 24 hours is 1.0 ×
It was 10 ² cells / ml or less. Example 2 MTI 15 parts by weight, α-chlorobenzaldoxime 10
An industrial fungicide composition was prepared by blending 1 part by weight and 75 parts by weight of diethylene glycol monomethyl ether, and the same test as in Example 1 was conducted. The number of viable bacteria after 30 minutes is 3.0
× 10 ³ cells / ml, viable cell count after 24 hours is 1.0 × 10 ^2.
It was below cells / ml. Example 3 15 parts by weight of MTI, 10 parts by weight of α-chlorobenzaldoxime acetate and 75 parts by weight of diethylene glycol monomethyl ether were blended to prepare an industrial germicidal composition, and the same test as in Example 1 was conducted. The viable cell count after 30 minutes is 4.3 × 10 ³ cells / ml, and the viable cell count after 24 hours is 1.
It was 0 × 10 ² cells / ml or less. Example 4 15 parts by weight of MTI, 10 parts by weight of 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide and 75 parts by weight of diethylene glycol monomethyl ether were blended to prepare an industrial fungicide composition, and the composition was prepared. The same test as in Example 1 was performed. The number of viable cells after 30 minutes is 1.5 × 10 ⁴ cells
The viable cell count after 24 hours was 1.0 × 10 ² cells / ml or less. Example 5 15 parts by weight of MTI and 10 parts by weight of 4,5-dichloro-1,2-dithiol-3-one and 75 parts by weight of diethylene glycol monomethyl ether were mixed to prepare an industrial fungicide composition. The same test was done. The viable cell count after 30 minutes was 1.7 × 10 ³ cells / ml, and the viable cell count after 24 hours was 1.0 × 10 ² cells / ml or less. Comparative Example 1 An industrial fungicide composition was prepared by mixing 25 parts by weight of dichloroglyoxime and 75 parts by weight of diethylene glycol monomethyl ether, and the same test as in Example 1 was performed.
The viable cell count after 30 minutes was 8.3 × 10 ³ cells / ml, and the viable cell count after 24 hours was 3.0 × 10 ³ cells / ml. Comparative Example 2 An industrial fungicide composition was prepared by mixing 25 parts by weight of α-chlorobenzaldoxime and 75 parts by weight of diethylene glycol monomethyl ether, and the same test as in Example 1 was performed. After 30 minutes, the viable cell count was 3.5 × 10 ⁴ cells / ml,
The viable cell count after 24 hours was 5.2 × 10 ³ cells / ml. Comparative Example 3 An industrial fungicide composition was prepared by mixing 25 parts by weight of α-chlorobenzaldoxime acetate and 75 parts by weight of diethylene glycol monomethyl ether, and the same test as in Example 1 was performed. The number of viable bacteria after 30 minutes is 1.0 x 10 ⁴ ce
lls / ml, the number of viable cells after 24 hours is 1.9 × 10 ³ cells / ml
Met. Comparative Example 4 3,3,4,4-tetrachlorotetrahydrothiophene-
An industrial germicidal composition was prepared by mixing 25 parts by weight of 1,1-dioxide and 75 parts by weight of diethylene glycol monomethyl ether, and the same test as in Example 1 was performed. 3
The viable cell count after 0 minutes was 4.4 × 10 ⁴ cells / ml, and the viable cell count after 24 hours was 1.2 × 10 ⁴ cells / ml. Comparative Example 5 25 parts by weight of 4,5-dichloro-1,2-dithiol-3-one and diethylene glycol monomethyl ether 7
5 parts by weight was blended to prepare an industrial germicidal composition, and the same test as in Example 1 was conducted. The number of viable bacteria after 30 minutes is 2.3 ×
10 ⁵ cells / ml, viable cell count after 24 hours is 6.1 × 10 ⁴ ce
lls / ml. Comparative Example 6 An industrial fungicide composition was prepared by mixing 25 parts by weight of MTI and 75 parts by weight of diethylene glycol monomethyl ether, and the same test as in Example 1 was performed. The viable cell count after 30 minutes was 8.7 × 10 ⁵ cells / ml, and the viable cell count after 24 hours was 1.
It was 5 × 10 ⁴ cells / ml. Comparative Example 7 The same test as in Example 1 was performed without adding the industrial germicidal composition. The number of viable bacteria after 30 minutes is 2.3 × 10 ⁶ cells
The viable cell count after 24 hours was 6.1 × 10 ⁶ cells / ml. The results of Examples 1 to 5 and Comparative Examples 1 to 7 are summarized in Table 4.

[0015]

[Table 4]

From the results shown in Table 4, the industrial bactericidal composition of the present invention containing MTI and an industrial bactericide selected from halogenated oxime compounds, halogenated thiophene compounds or halogenated dithiol compounds as active ingredients was added. After 30 minutes, the tested liquid showed a remarkable decrease in the viable cell number and showed an excellent rapid-acting effect, and after 24 hours, the viable cell number was all 1.
It was 0 × 10 ² or less, showing an excellent bactericidal effect in terms of sustainability.

[0017]

Industrial bactericidal compositions containing the MTI of the present invention and other industrial bactericides exhibit a bactericidal effect excellent in fast-acting and long-lasting properties, and are particularly highly concentrated aqueous systems and reducing aqueous systems. In the above, it can be used as an excellent bactericidal agent which has never been obtained.

Claims (1)

[Claims] 1. 2-Methyl-4,5-trimethylene-4-
An industrial fungicide composition comprising an isothiazolin-3-one and an industrial fungicide selected from halogenated oxime compounds, halogenated thiophene compounds or halogenated dithiol compounds as active ingredients.