JP7001955B2 - Industrial bactericidal composition - Google Patents

Description

INDUSTRIAL APPLICABILITY The present invention is effective as a paper-making agent in the pulp and paper industry, cooling water for various industries, metal processing oil, fiber oil, preservatives such as pastes and molds, and bactericides, and microorganisms such as bacteria and fungi. With respect to industrial bactericidal compositions capable of long-term protection from rot caused by.

Paper chemicals in the pulp and paper industry are water-based industrial water-based compositions such as paints, latexes, starch slurry liquids, paper coating colors, and paper strength agents, which are contaminated with bacteria. This causes rot, which causes odor, deterioration of physical properties such as viscosity decrease and pH fluctuation, and propagation of fungi causes clogging, coloring, and contamination of the strainer.

In addition, many industrial products such as metal processing oils such as cutting oil, casein, starch paste, sardines, adhesives, synthetic rubber, ink, resin products, concrete admixtures, mold coating agents, etc. Harmful microorganisms such as bacteria and fungi are prone to breed, which causes deterioration of productivity and quality, generation of foul odors, and the like. Therefore, industrial disinfectants are widely used to control the growth of such microorganisms.

As such an industrial bactericidal agent, glyoxime compounds, cyclic nitrogen-sulfur compounds, bromine compounds, thiosian compounds, quaternary ammonium salt compounds, thiophene compounds and the like have been used alone or in admixture thereof. ing. However, these compounds have various drawbacks in use, for example, decomposition by combining specific compounds, insufficient bactericidal effect of chemicals, and microorganisms when used for a long period of time. It may have drawbacks such as acquisition of resistance and foaming in the work environment.

As a sterilization technique in which a glycimme compound and a thiophene compound or a halogenated aliphatic nitroalcohol compound are mixed, industrial sterilization, antiseptic, and algae killing using a glycimme compound and at least one compound selected from the following compound group as an active ingredient are used. Agents have been found (Patent Document 1). The following compounds include the halogenated aliphatic nitroalcohol compound (a), 1,2-benzoisothiazole-3 (2H) -one (b), and 2-bromo-2- (bromomethyl) glutaronitrile (c). ), Methylenebisthiocyanate (d), 4,5-dichloro-3H-1,2-dithiol-3-one (e), 2,2-dibromo-2-cyanoacetamide (f), mucobromic acid (g). ), Halogenated acetate compound (h), 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide (i).

As a sterilizing technique in which a thiophene compound and a halogenated nitroalcohol compound are mixed, an industrial bactericidal agent containing a dibromonitroalcohol compound and 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide as active ingredients is used. It has been found (Patent Document 2).

Further, as a technique for mixing 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide and a halogenated aliphatic nitroalcohol compound, 2-n-octyl-4-isothiazolin-3-one, Found as an industrial bactericidal composition characterized by containing 2-bromo-2-nitropropane-1,3-diol and 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide. (Patent Document 3).

Further, as a technique for stabilizing a compound such as 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide, a technique for microencapsulation containing a microbial growth inhibitor has been found (Patent Document). 4).

In the case of a composition containing a glycim compound and 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide, the stability of each component is not sufficient, and the efficacy is reduced due to decomposition, the distribution process, and the site of use. There was a problem that it could not withstand storage. Further, as in Patent Document 4, there is an example of stabilizing by encapsulating a microbial growth inhibitor in a microcapsule, but it is difficult to easily put it into practical use in terms of equipment and cost for manufacturing the microcapsule. There are many points.

Japanese Unexamined Patent Publication No. 7-2606 Japanese Unexamined Patent Publication No. 1-102004 Japanese Patent Application Laid-Open No. 2003-192507 Japanese Unexamined Patent Publication No. 2001-247409

The present invention has been made in view of such circumstances, and is a glyoxime compound, 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide and a halogenated aliphatic compound, which are difficult to combine. The stable presence of each component in a formulation combining nitroalcohol compounds has a wide spectrum of efficacy, and the bactericidal and bacteriostatic powers allow microorganisms to be sterilized before they acquire resistance. It is an object of the present invention to provide an industrial bactericidal composition which is advantageous in the distribution process and storage at the site of use because of its excellent long-term stability.

（式中Ｘは水素又は塩素を示す）で表されるグリオキシム化合物、３，３，４，４－テトラクロロテトラヒドロチオフェン－１，１－ジオキシド及びハロゲン化脂肪族ニトロアルコール系化合物を有効成分とし、安定性を向上させるためエポキシ化植物油を加えることで、グリオキシム化合物、３，３，４，４－テトラクロロテトラヒドロチオフェン－１，１－ジオキシド及びハロゲン化脂肪族ニトロアルコール系化合物の分解が飛躍的に抑制させることを見出し、本発明に至った。 As a result of diligent studies to solve the above problems, the present inventor [1] general formula (1).

The active ingredients are a glyoxime compound represented by (X in the formula indicates hydrogen or chlorine), 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide and a halogenated aliphatic nitroalcohol compound. The addition of epoxidized vegetable oil to improve stability dramatically decomposes glyoxime compounds, 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide and halogenated aliphatic nitroalcohol compounds. We have found that it is suppressed, and have reached the present invention.

（式中Ｘは水素又は塩素を示す）で表されるグリオキシム化合物、３，３，４，４－テトラクロロテトラヒドロチオフェン－１，１－ジオキシド及びハロゲン化脂肪族ニトロアルコール系化合物を含有する組成物であって、さらにエポキシ化植物油を含有することを特徴とする工業用殺菌組成物。
［２］一般式（１）

（式中Ｘは水素又は塩素を示す）で表されるグリオキシム化合物が、ジクロログリオキシムである［１］に記載の工業用殺菌組成物。
［３］ハロゲン化脂肪族ニトロアルコール系化合物が、２，２－ジブロモ－２－ニトロエタノール、２－ブロモ－２－ニトロプロパン－１，３－ジオールからなる群より選択される一種以上である［１］又は［２］に記載の工業用殺菌組成物。
［４］エポキシ化植物油が、エポキシ化大豆油である［１］～［３］に記載の工業用殺菌組成物。
［５］エポキシ化植物油を、０．０５～０．５重量％の範囲で含有する［１］～［４］に記載の工業用殺菌組成物。 That is, the present invention relates to the following invention.
[1] General formula (1)

A composition containing a glycim compound represented by (X in the formula indicates hydrogen or chlorine), 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide and a halogenated aliphatic nitroalcohol compound. An industrial bactericidal composition, which further contains an epoxidized vegetable oil.
[2] General formula (1)

The industrial bactericidal composition according to [1], wherein the glycime compound represented by (X in the formula indicates hydrogen or chlorine) is dichloroglycime.
[3] The halogenated aliphatic nitroalcohol compound is one or more selected from the group consisting of 2,2-dibromo-2-nitroethanol and 2-bromo-2-nitropropane-1,3-diol []. The industrial bactericidal composition according to 1] or [2].
[4] The industrial bactericidal composition according to [1] to [3], wherein the epoxidized vegetable oil is epoxidized soybean oil.
[5] The industrial bactericidal composition according to [1] to [4], which contains epoxidized vegetable oil in the range of 0.05 to 0.5% by weight.

By using the industrial sterilizing composition of the present invention, bacteria, molds, etc. that cause deterioration of quality, generation of foul odor, etc. in papermaking chemicals in the paper and pulp industry, industrial water in various industries, and many industrial products. Propagation of yeast and the like can be prevented for a longer period of time and sterilized.

The glycime compound used in the present invention is a compound having HON = CC = NOH as a skeleton, and can be produced by a known technique, and examples thereof include monochloroglycime and dichloroglycime. Further, as the glycime compound, a compound generally commercially available as an industrial raw material can also be used, and for example, it is commercially available from Fuji Sangyo Co., Ltd. as "DCG / MDG" (10% by weight of dichloroglycome, a methyldiglycol solution). Can be used. As these glycime compounds, it is preferable to use dichloromethane.

The amount of the glycim compound used in the industrial sterilizing composition of the present invention is preferably in the concentration range of 0.1 to 20% by weight, more preferably in the concentration range of 1 to 10% by weight, and further 1. It is more preferable to contain it in a concentration range of about 5% by weight.

The 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide used in the industrial sterilizing composition of the present invention can be produced by a known technique, but is commercially available as a general reagent. Things can also be used.

The blending amount of 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide used in the industrial sterilizing composition of the present invention may be contained in a concentration range of 0.1 to 20% by weight. It is preferable that the concentration range is 1 to 10% by weight, more preferably 1 to 5% by weight, and more preferably 1 to 5% by weight.

The halogenated aliphatic nitroalcohol-based compound used in the present invention can be produced by a known technique, but commercially available general industrial raw materials can also be used. For example, "BRONOPOL" (2-bromo-2-nitropropane-1) commercially available from Chemicrea as "DBNE-75" (75% by weight of 2,2-dibromo-2-nitroethanol, diethylene glycol solution). , 99% by weight or more of 3-diol), which are commercially available from Chemicrea, etc. can be used. As these halogenated aliphatic nitroalcohol compounds, it is preferable to use 2,2-dibromo-2-nitroethanol and 2-bromo-2-nitropropane-1,3-diol.

The halogenated aliphatic nitroalcohol compound in the present invention is preferably contained in a concentration range of 0.1 to 60%, and more preferably contained in a concentration range of 5 to 40%.

Examples of the epoxidized vegetable oil used in the industrial sterilizing composition of the present invention include epoxidized drying oil, epoxidized semi-drying oil, and epoxidized non-drying oil. Specific examples of the epoxidized dry oil include epoxidized flaxseed oil, epoxidized millet oil, and epoxidized eno oil, and specific examples of the epoxidized semi-drying oil include epoxidized soybean oil, epoxidized cotton seed oil, and epoxidation. Examples of the epoxidized non-drying oil include epoxidized castor oil, epoxidized olive oil, epoxidized camellia oil, epoxidized lacquer oil, and epoxidized palm oil. Of these, epoxidized soybean oil is particularly preferable. The epoxidized vegetable oil can be produced by a known technique, but commercially available epoxidized vegetable oils can also be used as general industrial raw materials. For example, as the epoxidized soybean oil, those marketed by Takemoto Oil & Fat Co., Ltd. as "New Calgen 800" and those marketed by ADEKA Corporation as "ADEKA SIZER (registered trademark) O-130P" can be used. Is. As these epoxidized vegetable oils, it is preferable to use epoxidized soybean oil.

The content of the epoxidized vegetable oil used in the industrial sterilizing composition of the present invention is preferably 0.05 to 0.5% by weight, more preferably 0.2 to 0.5% by weight. preferable.

As the solvent used in the industrial sterilizing composition of the present invention, a glycol ether solvent, an alcohol solvent, a glycol solvent, an ester solvent and the like can be used as long as the stability of the preparation is not affected. These solvents may be used as a mixture of two or more kinds.

The glycol ether-based solvent is a compound in which at least one of the hydroxyl groups of the glycol is an ether bond of an alkyl group, and specific examples thereof include methyl diglycol, ethyl diglycol, butyl diglycol, hexyl diglycol, and isopropyl diglycol. , Isobutyl diglycol, phenyl diglycol, methyl propylene glycol, dimethyl diglycol, methyl ethyl diglycol and the like.

Specific examples of the alcohol solvent include methanol, ethanol, isopropyl alcohol, n-propyl alcohol, butanol, hexanol and the like.

Specific examples of the glycol-based solvent include ethylene glycol, diethylene glycol, propylene glycol, polyethylene glycol (polymerization degree 1000 or less), butylene glycol and the like.

Specific examples of the ester solvent include ethyl acetate, ethyl butyrate, γ-butyrolactone and the like.

The surfactant should not always be added when formulating the industrial bactericidal composition of the present invention, but it may be added for the purpose of improving solubility and miscibility during use. It is possible. The surfactant is not particularly limited, and examples thereof include nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants. Examples of the type of nonionic surfactant include polyoxyethylene alkyl phenyl ether, polyoxyethylene styryl phenyl ether, polyoxyethylene alkyl ether, polyoxyethylene alkenyl ether, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester and the like. Be done. Examples of the anionic surfactant include alkylbenzene sulfonate, polyoxyethylene alkyl phenyl ether sulfate, dialkyl sulfosuccinate and the like. Examples of the cationic surfactant include aliphatic amine salts and quaternary ammonium salts thereof, and examples of the amphoteric surfactant include betaine-type surfactants and aminocarboxylates. Further, these nonionic surfactants, anionic surfactants, cationic surfactants and amphoteric surfactants may be used alone or in combination of two or more.

The industrial bactericidal composition of the present invention contains a glycim compound, 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide, a halogenated aliphatic nitroalcohol compound, and an epoxidized vegetable oil. In addition to the above-mentioned solvent and surfactant, a pH adjuster, a chelating agent, a rust preventive agent, a defoaming agent, a viscosity adjusting agent and the like are blended in order to prepare a composition containing these compounds. Is possible.

In addition to the glycime compound, 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide and the halogenated aliphatic nitroalcohol compound which are the bactericidal components of the industrial bactericidal composition of the present invention, the formulation is stable. It is also possible to use other bactericidal components at the same time as long as it does not affect the sex. Such bactericidal components are not particularly limited, but are, for example, methylene bisthiocyanate, glutaraldehyde, iodopropynylbutylcarbamate, zinc salt of pyridinethiol-N-oxide, 1,2-benzoisothiazolone, 1,2-. Dibromo-2,4-dicyanobutane, Nn-butylbenzoisothiazolone, N-octylisothiazolone, 2- (4-thiazolyl) benzimidazole, 2-benzimidazolylcarbamate methyl, tetrachloroisophthalonitrile, diiodomethylpara Trill sulfone, parachlorophenyl-3-iodopropagilformal, 2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine, o-phenylphenol, isopropylmethylphenol, parachloromethoxylenol, p-oxybenzo Examples thereof include acid alkyl esters and fatty acid glycerin esters.

The dosage form of the industrial bactericidal composition of the present invention is not particularly limited, and examples thereof include emulsions, solubilizers, flowable formulations, and suspo emulsion formulations. Of these dosage forms, a solubilizer in which the bactericidal component is dissolved in a solvent is suitable.

Next, the present invention will be described with reference to Examples and Comparative Examples, but the present invention is not limited thereto. The compounding ratios shown below are all by weight. Further, the industrial bactericidal compositions of each Example and Comparative Example were prepared by mixing each component at room temperature and dissolving it with a solvent. Unless otherwise specified, the following commercially available raw materials were used as the bactericidal component and the solvent. In addition, the indications of bactericidal components and solvents are indicated by the following abbreviations.

DCG / MDG: 10% by weight of dichloroglycime, methyldiglycol solution DBNE-75: 2,2-dibromo-2-nitroethanol 75% by weight, diethylene glycol solution BRONOPOL: 2-bromo-2-nitropropane-1, 3-Diol Newcalgen 800: Epoxidized soybean oil ADEKA Sizer O-130P: Epoxidized soybean oil

DCG: Dichloroglycime TCS: 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide (manufactured by Tokyo Chemical Industry Co., Ltd.)
DBNE: 2,2-dibromo-2-nitroethanol BNP: 2-bromo-2-nitropropane-1,3-diol MDG: methyldiglycol (manufactured by Tokyo Chemical Industry Co., Ltd.)
BDG: Butyl diglycol (manufactured by Wako Pure Chemical Industries, Ltd.)
DEF: Diethylene glycol (manufactured by Tokyo Chemical Industry Co., Ltd.)

Examples 1 to 17 Comparative Examples 1 to 5
A preparation containing a glycime compound, 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide and a halogenated aliphatic nitroalcohol-based compound is prepared with the formulations shown in Tables 1 to 4, and has an industrial bactericidal composition. I got a thing.

Stability test Examples 1 to 17 and Comparative Examples 1 to 5 were allowed to stand in a thermostat at 45 ° C. for 4 weeks, and these samples were analyzed by high performance liquid chromatography (manufactured by Hitachi High-Tech Fielding Corporation). The residual rate (%) with respect to the initial values of DCG, DBNE and BNP was calculated. Similarly, analysis was performed using gas chromatography (manufactured by Shimadzu Corporation), the residual rate (%) with respect to the initial value of TCS was calculated, and the results are shown in Table 5.

The industrial bactericidal composition of the present invention has excellent long-term stability, exhibits reliable bactericidal activity and bacteriostatic effect against bacteria, molds, yeasts, etc., and therefore does not need to be stored in a low-temperature warehouse or the like, so that it is cost effective. There are merits, such as paper chemicals in the field of paper and pulp industry, metal processing oils such as cutting oil, casein, starch paste, sardines, adhesives, synthetic rubber, ink, resin products, concrete admixtures, mold coating agents, etc. It is suitably used as a preservative and a bactericidal agent.

Claims (3)

General formula (1)

A composition containing a glycim compound represented by (X in the formula indicates hydrogen or chlorine), 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide and a halogenated aliphatic nitroalcohol compound. And also contains epoxidized vegetable oil ,
The halogenated aliphatic nitroalcohol compound is one or more selected from the group consisting of 2,2-dibromo-2-nitroethanol and 2-bromo-2-nitropropane-1,3-diol.
An industrial bactericidal composition comprising an epoxidized vegetable oil in the range of 0.05 to 0.5% by weight . General formula (1)

The industrial bactericidal composition according to claim 1, wherein the glycime compound represented by (X in the formula indicates hydrogen or chlorine) is dichloroglycime. The industrial bactericidal composition according to claim 1 or 2, wherein the epoxidized vegetable oil is epoxidized soybean oil.