JP4813813B2 - Industrial antibacterial agent and industrial antibacterial method using the same - Google Patents

Description

The present invention relates to an industrial antibacterial agent and an industrial antibacterial method using the same. More specifically, the present invention relates to papermaking process water in the paper and pulp industry, various industrial cooling and washing waters, metalworking oils, fiber oils, paints, various latexes, antifouling paints, and paper coating liquids. Further, the present invention relates to an industrial antibacterial agent useful for sterilization / bacteriostatic and antiseptic / mold prevention of industrial products such as glue, starch slurry and wood, and an industrial antibacterial method using the same.
Antibacterial in the present invention means sterilization that kills microorganisms and bacteriostatic, antiseptic and fungicidal substances that inhibit the growth of microorganisms.

  Conventionally, slime due to bacteria and fungi has been generated in papermaking process water and various industrial cooling waters in the paper and pulp industry, and this slime can cause problems such as deterioration in product quality and production efficiency. Are known. In addition, many industrial products such as metalworking oils, textile oils, paints, various latexes, antifouling paints, paper coating fluids, glues, starch slurries, wood, etc., are spoiled and contaminated by bacteria and mold. , These are known to foul products and reduce product value.

  A number of fungicides have been used to prevent these microbial damage. In the past, organomercury compounds, chlorinated phenolic compounds and formalin were used, but these drugs are highly toxic to the human body and seafood, and their use has been regulated to cause environmental pollution. , Industrial disinfectants with relatively low toxicity are widely used.

  Among these industrial fungicides, compositions comprising combinations with various industrial fungicides are known for the oxathiazine compounds that are the active ingredients of the present invention. For example, a combination with a benzimidazole compound (JP-A-11-217308: Patent Document 1), a combination with an isothiazolone compound and / or a haloacetylene compound (JP-A 2000-53510, Patent Document 2), Combination of surfactant and aqueous solvent (JP 2000-302601 A: Patent Document 3), 1-[[(3-iodo-2-propynyl) oxy] methoxy] -4-methoxybenzene, 1-chloro- 4-[[(3-iodo-2-propynyl) oxy] methoxy] benzene, 2-pyridinethiol-1-oxide zinc salt, 2-pyridinethiol-1-oxide copper salt, 2-pyridinethiol-1-oxide sodium Salt, 2,2-dithio-bis (pyridine-1-oxide), 2-methylthio-4-tert-butyl Combinations of at least one member selected from amino-6-cyclopropylamino--s- triazine (JP 2002-265310 JP: Patent Document 4).

Moreover, about the bromine type industrial disinfectant which is an active ingredient of this invention, the composition which consists of various compounds and those combinations is known. For example, 1,4-bis (bromoacetoxy) -2-butene, 1,2-bis (bromoacetoxy) ethane, 1,2,3-tris (bromoacetoxy) propane and 1,2-bis (bromoacetoxy) propane Bromoacetate compounds such as 2,2-dibromo-3-nitrilopropionamide and bromocyano compounds such as 2-bromo-2-bromomethylglutaronitrile; 2-bromo-2-nitropropane-1,3- Diol, 1,1-dibromo-1-nitro-2-propanol, 2,2-dibromo-2-nitroethanol, 1,1-dibromo-1-nitro-2-acetoxyethane, 1,1-dibromo-1- Nitro-2-acetoxypropane, 2-bromo-2-nitro-1,3-diacetoxypropane, tribromonitromethane, - bromo-6-nitrostyrene, 5-bromo-5-nitro-1,3-dioxane, Buromonitoro compounds such as 5-bromo-2-methyl-5-nitro-1,3-dioxane.
These industrial disinfectants are described in, for example, JP-A-2-42007 (Patent Document 5).

However, for example, an industrial disinfectant described in JP 2000-53510 A (Patent Document 2), for example, a disinfectant comprising a combination of an oxathiazine compound and 5-chloro-2-methyl-4-isothiazolone-3-one When the agent is used in an antiseptic system such as wood, the number of viable bacteria before the addition of the chemical is low, and an effective antiseptic effect can be expected in an antiseptic target system that is not spoiled. Has a problem that a sufficient antiseptic effect cannot be expected.
Therefore, there is a need for a better industrial antibacterial agent that has an effective antibacterial effect against a wide range of microorganisms and that maintains the effect.

JP 11-217308 A JP 2000-53510 A JP 2000-302601 A JP 2002-265310 A Japanese Patent Laid-Open No. 2-42007

  It is an object of the present invention to provide an industrial antibacterial agent that has an effective antibacterial effect against a wide range of microorganisms such as bacteria, fungi, and yeast, and the effect is sustained.

  As a result of intensive studies to solve the above problems, the inventors of the present invention have developed a specific oxathiazine-based compound and a bromine-based compound having either a bromine atom, a bromine atom and a cyano group, or a bromine atom and a nitro group. By combining with at least one industrial fungicide, an effective antibacterial effect was demonstrated against a wide range of microorganisms, and the surprising fact that the effect lasted was found, and the present invention was completed. .

（式中、Ｒ¹およびＲ²は、互いに同一または異なって、水素または低級アルキル基を示す）
で表わされるオキサチアジン系化合物と、１，４−ビス（ブロモアセトキシ）−２−ブテン、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−ジオールおよび２−ブロモ−２−ニトロ−１，３−ジアセトキシプロパンから選択される臭素系工業用殺菌剤の１種とを相乗効果を奏する割合で含有することを特徴とする工業用抗菌剤が提供される。 Thus, according to the present invention, the general formula (1):

(Wherein R ¹ and R ² are the same or different from each other and represent hydrogen or a lower alkyl group)
An oxathiazine compound represented by: 1,4-bis (bromoacetoxy) -2-butene, 2,2-dibromo-3-nitrilopropionamide, 2-bromo-2-nitropropane-1,3-diol and 2 - industrial antimicrobial agent characterized by containing in a proportion to achieve the one and the synergistic effect of the bromine-based industrial fungicide selected from bromo-2-nitro-1,3-diacetoxy-propane is provided .

  According to the invention, the industrial antibacterial agent is added to the antibacterial target system simultaneously or separately so that the total concentration of the active ingredients is 0.5 to 300 mg / liter. An antibacterial method is provided.

  The industrial antibacterial agent of the present invention comprises a combination of novel active ingredients, has a wide antibacterial spectrum, has an excellent antibacterial effect, and the effect continues. In addition, even when resistant bacteria (fungi, fungi) are generated by existing industrial antibacterial agents, the industrial antibacterial agents of the present invention can exert their effects and are extremely useful industrially.

  The industrial antibacterial agent of the present invention is at least one bromine-based industrial bactericidal agent having an oxathiazine-based compound represented by the general formula (1) and a bromine atom, a bromine atom and a cyano group, or a bromine atom and a nitro group. Contains seeds in a ratio that produces a synergistic effect.

The oxathiazine compound used in the present invention is represented by the general formula (1), in which R ¹ and R ² are the same or different from each other and represent hydrogen or a lower alkyl group.
Examples of the lower alkyl group for R ¹ and R ² include linear or branched alkyl groups having 1 to 4 carbon atoms, such as methyl, ethyl, n-propyl, and n-butyl. Examples include linear alkyl groups and branched alkyl groups such as isopropyl, isobutyl, sec-butyl, and tert-butyl.

When R ¹ is a lower alkyl group, either the 5-position or the 6-position, preferably the 6-position, of the oxathiazine ring is substituted with a lower alkyl group.
The most preferred embodiment of R ¹ is hydrogen.

When R ² is a lower alkyl group, any one of 4-position, 5-position, 6-position or 7-position, preferably 5-position, of the benzo [b] thien ring is substituted with a lower alkyl group. .
The most preferred embodiment of R ² is hydrogen.

Specific examples of such an oxathiazine compound represented by the formula (1) include, for example, 3-benzo [b] thien-2-yl-5,6-dihydro-1,4,2-oxathiazine 4-oxide, 3- (5-Methylbenzo [b] thien-2-yl) -5,6-dihydro-1,4,2-oxathiazine 4-oxide and 3-benzo [b] thien-2-yl-5-hydro-6 -Methyl-1,4,2-oxathiazine 4-oxide and the like.
Although not included in the formula (1), 5,6-dihydro-3- (2-thienyl) -1,4,2-oxathiazine 4-oxide should be used as an oxathiazine compound as in the above exemplary compounds. Can do.
In the present invention, these oxathiazine compounds may be used alone or in combination of two or more.

  Among the above oxathiazine-based compounds, 3-benzo [b] thien-2-yl-5,6-dihydro-1,4,2-oxathiazine 4-oxide is preferable in terms of antibacterial effect and availability. Particularly preferred. This compound is provided, for example, by Janssen Falmouth Utica NV (Belgium) under the product name “Betoxazine”.

  The bromine-based industrial disinfectant used in the present invention is a compound having either a bromine atom, a bromine atom and a cyano group, or a bromine atom and a nitro group. For example, a bromine acetate ester compound having a bromine atom, a bromine atom And a bromocyano compound having a cyano group and a bromonitro compound having a bromine atom and a nitro group.

  Examples of bromoacetate compounds include 1,4-bis (bromoacetoxy) -2-butene, 1,2-bis (bromoacetoxy) ethane, 1,2,3-tris (bromoacetoxy) propane, and 1,2- Bis (bromoacetoxy) propane is exemplified.

  Examples of the bromocyano compound include 2,2-dibromo-3-nitrilopropionamide, 2-bromo-2-bromomethylglutaronitrile and the like.

  Examples of bromonitro compounds include 2-bromo-2-nitropropane-1,3-diol, 1,1-dibromo-1-nitro-2-propanol, 2,2-dibromo-2-nitroethanol, 1,1- Dibromo-1-nitro-2-acetoxyethane, 1,1-dibromo-1-nitro-2-acetoxypropane, 2-bromo-2-nitro-1,3-diacetoxypropane, tribromonitromethane, 6-bromo- Examples include 6-nitrostyrene, 5-bromo-5-nitro-1,3-dioxane, and 5-bromo-2-methyl-5-nitro-1,3-dioxane.

  Among these bromine-based industrial fungicides, 1,4-bis (bromoacetoxy) -2-butene, 1,2-bis (bromoacetoxy) ethane, 1,2,3-tris ( Bromoacetoxy) propane, 1,2-bis (bromoacetoxy) propane, 2,2-dibromo-3-nitrilopropionamide, 2-bromo-2-nitropropane-1,3-diol, 2,2-dibromo-2 Nitroethanol and 2-bromo-2-nitro-1,3-diacetoxypropane are particularly preferred.

The industrial antibacterial agent of this invention contains an oxathiazine compound and a bromine-based industrial disinfectant in a proportion that exhibits a synergistic effect.
The blending ratio of the oxathiazine compound and the bromine industrial disinfectant is preferably 1: 100 to 10: 1 by weight. When this blending ratio is in the above range, a synergistic bactericidal effect is remarkably exhibited.

When the bromine industrial disinfectant is a bromoacetate compound, the blending ratio is particularly preferably 1:10 to 2: 1 by weight.
When the bromine industrial disinfectant is a bromocyano compound and / or a bromonitro compound, the blending ratio is particularly preferably 10: 1 to 2: 1 by weight.

  The industrial antibacterial agent of the present invention is preferably used in the form of a normal liquid preparation, and is preferably used as a one-part preparation. However, depending on the antibacterial target system and purpose of use, it may be formulated into a paste, powder, granule, etc. It may be used. In addition, when it is preferable to store each active ingredient separately in view of long-term storage stability of the preparation, the active ingredients may be separately formulated and used in combination.

  In the case where the antibacterial target system is a water system such as process water in the papermaking process or industrial cooling water, it is preferable to use a liquid agent containing an organic solvent and a dispersant in consideration of the solubility and dispersibility of the active ingredient.

  Examples of the organic solvent include alcohol solvents such as methanol, ethanol, n-propanol, iso-propanol, n-butanol, and tert-butanol; ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene Glycols such as glycol, 1,4-butanediol, 1,5-pentanediol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, tripropylene glycol monomethyl ether Solvent: acetone, methyl ethyl ketone, methyl isobutyl keto Ketone solvents such as dioxane, tetrahydrofuran and ethyl ether; ester solvents such as ethyl acetate, butyl acetate and isobutyl acetate; aromatic solvents such as benzene, toluene, xylene, methylnaphthalene and solvent naphtha; Halogenated hydrocarbon solvents such as carbon tetrachloride, chloroform, and methylene chloride; polar solvents such as dimethylformamide, dimethyl sulfoxide, acetonitrile, and the like. When the antibacterial target system is aqueous, hydrophilic ones are preferable, In the case of an oil system, a lipophilic one is preferable. These solvents may be used alone or in combination of two or more.

  As the dispersant, any of a cationic surfactant, an anionic surfactant, a nonionic surfactant or an amphoteric surfactant can be used, but a nonionic surfactant is preferred from the viewpoint of stability as a preparation.

  The blending ratio of these preparations is preferably such that the total amount of the active ingredients of the industrial antibacterial agent of the present invention is 1 to 60 parts by weight and the rest is an organic solvent with respect to 100 parts by weight of the preparation. Further, if necessary, the dispersant may be blended in at least 0.5 parts by weight with respect to 1 part by weight of the total active ingredients.

  In addition, when the antibacterial target system is an oil system such as heavy oil sludge, cutting oil, and oil paint, it is preferable to use a liquid agent using a hydrocarbon solvent such as kerosene, heavy oil, and spindle oil, and various surfactants are used. May be.

  Furthermore, for the antibacterial target system in which the active ingredient of the industrial antibacterial agent of the present invention can be dissolved or dispersed directly, the active ingredient is directly or solid diluent (for example, kaolin, clay, bentonite, CMC, etc.) It may be used as a powder diluted with 1 or a combination of the above surfactants. Further, depending on the combination of active ingredients, only the active ingredients may be used without using a solvent or a surfactant.

  As the addition object of the industrial antibacterial agent of the present invention, papermaking process water in the paper and pulp industry, various industrial cooling water and washing water, metalworking oil, textile oil, paints, various latexes, antifouling paints, Examples include paper coating solutions, pastes, starch slurries, and wood.

The addition amount of the industrial antibacterial agent of the present invention may be set as appropriate depending on the combination of active ingredients and the type of antibacterial target system. Per liter, preferably 1 to 150 mg / liter, added simultaneously or separately.
When the total concentration of the active ingredients is in the above range, a synergistic bactericidal effect is remarkably exhibited.
For example, when the antibacterial target system is papermaking process water in the paper and pulp industry, and cooling water for various industries, the total concentration of active ingredients is 0.5 to 300 mg / liter, more preferably 1 to 150 mg / liter. Liters.
The industrial antibacterial agent of the present invention may be diluted with water as necessary when added to the antibacterial target system.

(Example)
The present invention is illustrated by the following formulation examples and test examples, but is not limited by these formulation examples and test examples.

Formulation examples can be prepared by mixing each active ingredient in various organic solvents and stirring and mixing.
Abbreviations of compounds used in formulation examples and test examples are shown below. In addition, the numerical value of the compound of a formulation example is all weight%.

Betoxazine: 3-benzo [b] thien-2-yl-5,6-dihydro-1,4,2-oxathiazine 4-oxide BBAB: 1,4-bis (bromoacetoxy) -2-butene BBAE: 1,2 -Bis (bromoacetoxy) ethane TBAP: 1,2,3-tris (bromoacetoxy) propane BBAP: 1,2-bis (bromoacetoxy) propane DBNPA: 2,2-dibromo-3-nitrilopropionamide BNPD: 2- Bromo-2-nitropropane-1,3-diol DBNE: 2,2-dibromo-2-nitroethanol BNDAP: 2-bromo-2-nitro-1,3-diacetoxypropane

DCOIT: 4,5-dichloro-2-octyl-4-isothiazolin-3-one NaPt: sodium pyrithione MDG: ethylene glycol monomethyl ether

Formulation Example 1
Betoxazine 3
BBAE 10
MDG 87
Formulation Example 2
Betoxazine 1
BBAE 30
MDG 69

Formulation Example 3
Betoxazine 3
TBAP 10
MDG 87
Formulation Example 4
Betoxazine 1
TBAP 30
MDG 69

Formulation Example 5
Betoxazine 3
BBAP 10
MDG 87
Formulation Example 6
Betoxazine 1
BBAP 30
MDG 69

Formulation Example 7
Betoxazine 3
DBNPA 10
MDG 87
Formulation Example 8
Betoxazine 1
DBNPA 30
MDG 69

Formulation Example 9
Betoxazine 3
DBNE 7
MDG 90
Formulation Example 10
Betoxazine 1
DBNE 15
MDG 84

Test Example 1 (Bactericidal effect confirmation test)
A test bacterium (Pseudomonas aeruginosa) was inoculated into a liquid broth medium and shaken at 30 ° C. for 18 hours to obtain a culture solution. The obtained culture broth was added to a fresh liquid broth medium at 1%, and further shaken for 6 hours to obtain a culture broth to be used as an inoculum for the test.
The obtained culture solution was added to 1.0% of sterilized pure water, and 10 ml was dispensed into an L-shaped test tube. Each drug (betoxazine and BNPD or BBAB) was added to the L-shaped test tube to a predetermined concentration, and shaken at 30 ° C. for 3 hours. After shaking, the number of viable bacteria in each L-shaped test tube was measured, and the bactericidal rate was calculated by the following formula. The same test was repeated, and the concentration of the active ingredient of each drug at which the bactericidal rate was 99.9% or more was determined. In addition, the number of viable bacteria to which no drug was added was 3.2 × 10 ⁶ cfu / ml.
The obtained results were plotted with the concentration of the active ingredient of each drug having a bactericidal rate of 99.9% or more, and FIGS. 1 and 2 were obtained.

  1 and 2 show that the industrial antibacterial agent of the present invention has an effective bactericidal power against bacteria.

Test Example 2 (Slime adhesion prevention effect confirmation test in paper making process)
In the paper making process of corrugated cardboard at the Sakai Paper Mill, the slime adhering to the bottom of the bat was collected and tested using this. When this slime was observed with a microscope, it was confirmed that bacterial slime and fungal hyphae were mixed.
0.5% w / v slime was added to the papermaking process water, and the slime was crushed using a mixer to prepare a sample. The species and number of viable bacteria contained in the sample and the pH of the sample are shown below.

Species (Bacteria): Psedomonas sp, Sphingomonas sp, Burkholderia sp,
Vibrio sp, Ralstonia sp
(Mold): Cladosporium sp, Fusarium sp, Aureobasidium sp
Viable count (bacteria): 3.4 × 10 ⁶ cfu / ml
(Mold): 2.7 × 10 ⁴ cfu / ml
pH: 6.4

A plastic wire was wound around the inner wall surface of a beaker having a capacity of 500 ml (outer diameter: φ85 mm × 90 mm), and 400 ml of the prepared sample was placed in the beaker. The beaker was installed in a jar tester equipped with a thermostatic bath, and the sample was kept at 30 ° C. while stirring at a rotation speed of 70 rpm.
Subsequently, each chemical | medical agent shown in Table 1 was added so that it might become a predetermined | prescribed density | concentration, and after contacting the sample and the chemical | medical agent for 30 minutes, the sample was thrown away slowly. Thereafter, 400 ml of a newly prepared sample was placed in a beaker. This operation was repeated twice a day for 7 days. A blank test was also conducted in the same manner as above except that no drug was added.

  After the test was completed, the sample was discarded, the slime adhering to the plastic wire was observed with a microscope, the ratio (adhesion rate) of the slime adhering to the wire was calculated according to the following formula, and evaluated according to the criteria in Table 2. The obtained results are shown in Table 3.

  From the results of Table 2, it can be seen that the industrial antibacterial agent of the present invention has an effective anti-adhesion effect on slime and mold generated in the papermaking process of a paper mill.

Test Example 3 (Sterilization and fungicidal effect confirmation test for emulsion products)
The test was conducted using a spoiled product and a normal product of a certain emulsion product. The number of bacteria and fungi contained in each product and the pH of each product are shown below.
Septic product Viable count (bacteria): 3.5 × 10 ⁶ cfu / ml
(Mold): 3.2 × 10 ⁵ cfu / ml
pH: 6.8
Normal product Viable count (bacteria): <10 ² cfu / ml
(Mold): <10 ² cfu / ml
pH: 6.9

10% by weight of the spoiled product was added to the normal product and stirred, and 20 g of the resulting mixture was dispensed into a 30 ml capacity plastic bottle. The viable counts of bacteria and mold immediately after stirring were 4.2 × 10 ⁵ cfu / ml and 2.6 × 10 ⁴ cfu / ml, respectively.
Subsequently, each chemical | medical agent shown in Table 4 was added to each plastic bottle so that it might become a predetermined | prescribed density | concentration, and stationary culture was carried out at 30 degreeC for 8 days, and the viable cell count was measured for every day. In addition, after the measurement of the number of viable bacteria on the first day and the fourth day, 1% by weight of a spoiled product was added as an inoculum. A blank test was also conducted in the same manner as above except that no chemical was added. The results obtained are shown in Table 5.

  From the results of Table 4, it can be seen that the industrial antibacterial agent of the present invention has effective antibacterial and antifungal properties against bacteria and fungi, and the effect is sustained.

It is a figure which shows the result of the bactericidal effect confirmation test by a chemical | medical agent (Betoxazine + BNPD) (Test Example 1). It is a figure which shows the result of the bactericidal effect confirmation test by a chemical | medical agent (Betoxazine + BBAB) (Test Example 1).

Claims (3)

General formula (1):

(Wherein R ¹ and R ² are the same or different from each other and represent hydrogen or a lower alkyl group)
An oxathiazine compound represented by: 1,4-bis (bromoacetoxy) -2-butene, 2,2-dibromo-3-nitrilopropionamide, 2-bromo-2-nitropropane-1,3-diol and 2 -Industrial antibacterial agent characterized by containing 1 type of bromine type industrial disinfectant selected from bromo- 2-nitro- 1, 3- diacetoxypropane in the ratio which has a synergistic effect. The industrial antibacterial agent according to claim 1, wherein a blending ratio of the oxathiazine-based compound and the bromine-based industrial disinfectant is 1: 100 to 10: 1 by weight. An industrial antibacterial agent characterized in that the industrial antibacterial agent according to claim 1 or 2 is added to an antibacterial target system simultaneously or separately so that the total concentration of active ingredients is 0.5 to 300 mg / liter. Method.

Images