JP2000178105A - Industrial antibacterial composition and method for industrially exhibiting antibacterial action - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an industrial antibacterial composition and also a method for industrially exhibiting antibacterial action, having effect on both dispersed fungi in water and slime on the surface of a wall. SOLUTION: This industrial antibacterial composition is prepared by including at least one kind selected from the group consisting of (A) 1,2-dibromo-2,4- dicyanobutane, (B) 2,2-dibromo-3-nitrilopropionamide and (C) an isothiazolone- based compound and its metal-complex compound. The composition preferably includes the above ingredients in such a way that the content ratio (the ingredients A: the ingredient B) is (100:1)-(1:100) and the content ratio [(the ingredient A + the ingredient B): the ingredient C] is (1:10)-(10:1).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an industrial antibacterial composition and an industrial antibacterial method, and more particularly to papermaking process water in the paper and pulp industry, cooling water and washing water for various industries, heavy oil sludge, metal The present invention relates to an industrial antibacterial composition and an industrial antibacterial method useful for preserving and sterilizing processing oils, fiber oils, paints, paper coating liquids, latexes, and pastes. Here, the industrial antibacterial agent composition includes various industrial water-based slime control agents and various industrial products such as preservatives and bactericidal / bacteriostatic agents.

[0002]

2. Description of the Related Art Conventionally, bacteria and fungi generate slime in the paper making process in the paper and pulp industry and in cooling water systems in various industries, causing problems such as deterioration of product quality and production efficiency. It has been known. In addition, many industrial products such as heavy oil sludge, metalworking oils, fiber oils, paints, various latexes, sizing agents, and the like, cause decay and contamination by bacteria and fungi, and contaminate the products, lowering their commercial value. Many antibacterial agents have been used to prevent damage by these microorganisms.

[0003] In the past, organic mercury compounds and chlorinated phenol compounds were used, but these drugs are highly toxic to the human body and fish and shellfish and cause environmental pollution. In Japan, relatively low-toxic organic nitrogen-sulfur compounds, organic halogen compounds, and organic sulfur compounds are widely used as industrial antibacterial agents. [Encyclopedia of antibacterial and antifungal agents (Showa 61, published by Japan Society of Antifungal and Antifungal Agents) ]. However, these antibacterial agents have a small bactericidal activity against certain kinds of bacteria and fungi, and when applied to a real system, they need to be added at an extremely high concentration, resulting in problems such as poor economy.

In order to solve such a problem, it has been proposed to use a plurality of antibacterial agents in combination in order to expect a so-called synergistic effect. For example, Japanese Patent Publication No. 6-60083 discloses 2,2-dibromo-3-nitrilopropionamide (hereinafter abbreviated as DBNPA) and 1,2-dibromo-2,4-dicyanobutane (hereinafter abbreviated as DBDCB). )
Have been proposed. Further, a combination of DBDCB and an isothiazolone compound has been proposed.

[0005]

However, the antimicrobial composition of the combination described above is not enough to obtain a broad antimicrobial spectrum.

[0006] On the other hand, slime control agents belong to industrial antibacterial agents and are used for a very wide range of applications. However, there is a problem to be solved in the conventional methods for evaluating slime control agents. That is, the selection of the slime control agent from the past, the bactericidal effect of the drug on the bacteria dispersed in water,
It has been performed by evaluating the growth inhibitory effect. However, it has recently been shown that the effects of drugs on dispersing bacteria and slime are not always correlated (JC Nickel, I. Ruseska, JB Wright,
JW Costerton, Antimicrobial Agents and Chemothe
r., 27 (4) 619-624 ('85) Tobramycin Resistance of P
seudomonas aeruginosa Cells Growing as a Biofilm o
n Urinary Catheter Material). Therefore, it is necessary to evaluate the effect of the antibacterial agent on slime not only against dispersed bacteria but also against slime that grows on the wall surface in water.

Under these circumstances, there is a need for an industrial antibacterial agent which is effective at a low concentration for both disperse bacteria and slime.

The present invention relates to the preservation of papermaking process water in the paper and pulp industry, cooling water and washing water for various industries, heavy oil sludge, metalworking oil, fiber oil, paint, coating liquid for paper, latex and paste. It is an object of the present invention to provide an industrial antibacterial agent composition and an industrial antibacterial method which are useful for disinfection and sterilization, and exhibit an effect on slime on the wall surface as well as on bacteria dispersed in water.

[0009]

Means for Solving the Problems In order to solve the above-mentioned problems, the present inventors have conducted intensive studies using an evaluation device capable of evaluating the effect on slime adhered to a wall surface (hereinafter referred to as a slime adhesion monitor). As a result, it has been found that by combining the known antibacterial agents DBDCB and DBNPA with an isothiazolone-based compound, both the dispersing bacteria in water and the slime of the wall surface are synergistically effective in preventing the germs. The present invention has been completed based on the findings.

That is, the present invention relates to (A) 1,2-dibromo-2,4-dicyanobutane, (B) 2,2-dibromo-3-nitrilopropionamide, (C) an isothiazolone compound and the like. An industrial antibacterial composition comprising at least one selected from the group consisting of metal complex compounds.

The component (C) comprises an isothiazolone compound represented by the following general formula (I) and a compound represented by the following general formula (II)
At least one selected from isothiazolone metal complex compounds of

[0012]

Embedded image

[0013]

Embedded image

In the general formulas (I) and (II), R₁Is the hydrogen source
Alkyl, alkenyl, alkynyl or ara
Alkyl group, R_TwoAnd R_ThreeIs a hydrogen atom or a halogen
Atom, R_TwoAnd R_ThreeAre fused to form a benzene ring
May be formed. Where R _TwoAnd R_ThreeBoth are halogen sources
Excludes children. M is an alkali metal, alkaline earth gold
Cation selected from the group consisting of genus, heavy metals and amines
An atom or group, Z is sufficient to form a complex compound
Forming a compound with a cation M having high solubility
An on atom or a group, a is an integer of 1 or 2,
n is an integer in which the anion Z satisfies the valence of the cation M
is there.

Specifically, 5-chloro-2-methyl-3
-Isothiazolone, 2-methyl-3-isothiazolone,
2-ethyl-3-isothiazolone, 1,2-benzisothiazolone, 5-chloro-2-methyl-3-isothiazolone magnesium nitrate, 2-methyl-3-isothiazolone magnesium nitrate, 2-ethyl-3
-Isothiazolone calcium chloride and the like.

In a preferred embodiment, the ratio of the component (A) to the component (B) is 100: 1 to 100% by weight.
1: 100, and the ratio of the total amount of the components (A) and (B) to the component (C) is 1:10 to 10: 1 by weight. An antimicrobial composition.

The present invention also relates to (A) 1,2-dibromo-2,4-dicyanobutane, (B) 2,2-dibromo-3-nitrilopropionamide, (C) an isothiazolone-based compound and a compound thereof. At least one selected from the group consisting of metal complex compounds in a total concentration of 1 to 1,000
An industrial antibacterial method or a method for preventing the adhesion of microorganisms, characterized in that the method is added so that the amount becomes milligram / liter.

Here, the component (C) is as described above, and the suitable combination ratio of each component is also as described above.

The form of the industrial antimicrobial composition of the present invention is not particularly limited, and may be, for example, a one-part composition containing the three components (A), (B) and (C). Or
Each may be a two- or three-part type containing any of the components (A), (B) and (C), and the three-part form of (A), (B) and (C) may be added. It is only necessary that the person exists. Among these, a liquid one-part antibacterial agent containing the component (A), the component (B), and the component (C) is easy to handle and can be suitably used.

The one-part antibacterial agent can be prepared by dissolving the components (A), (B) and (C) in an organic solvent or a mixture of water and an organic solvent, or
It can be formulated as an aqueous suspension containing the component (A), the component (B), and the component (C).

When the components (A), (B) and (C) are dissolved in an organic solvent or a mixture of water and an organic solvent to prepare a formulation, the organic solvent to be used depends on whether the system to be sterilized is in the papermaking process. In the case of various aqueous systems such as process water and factory cooling water, a hydrophilic organic solvent is preferable in consideration of dispersibility and solubility of the active ingredient.

Examples of the hydrophilic organic solvent include methyl cellosolve, ethyl cellosolve, phenyl cellosolve,
Glycol ethers such as diethylene glycol monomethyl ether and dipropylene glycol monomethyl ether; glycols such as ethylene glycol, propylene glycol, diethylene glycol and dipropylene glycol; alcohols such as methanol, ethanol, propanol, butanol, hexanol and 2-ethylhexanol; Examples include esters such as methyl acetate, ethyl acetate, 3-methoxydibutyl acetate, 2-ethoxymethyl acetate, 2-ethoxyethyl acetate, and propylene carbonate, and amides such as dimethylformamide and dimethylacetamide.

When formulated as an aqueous suspension containing the components (A), (B) and (C),
Component (A) using a ball mill or attritor, etc.,
The component (B) and the component (C) can be wet-pulverized to obtain an aqueous suspension. When producing an aqueous suspension, xanthan gum, ramzan gum, thickeners such as guar gum,
As a dispersant, a nonionic surfactant, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, or the like can be used.

When the system to be sterilized is an oil system such as heavy oil sludge, cutting oil, oil-based paint, etc., a liquid one-part antibacterial agent is prepared by using a hydrocarbon solvent such as heavy oil, kerosene, or spindle oil. Is preferred. When a one-component antibacterial agent is formed using a hydrocarbon-based solvent, the various surfactants described above can be used.

The amount of the industrial antibacterial composition of the present invention is as follows:
The total concentration of the component (A), the component (B), and the component (C) is preferably from 1 to 1,000 mg / L, more preferably from 5 to 100 mg / L.

The components (A), (B) and (C) of the present invention
Industrial antibacterial agent composition containing the component, in various industrial target systems, shows a function of significantly preventing the growth and adhesion of microorganisms, especially slime control agent for papermaking process,
It is extremely useful as an antibacterial agent such as a paper coating liquid or a sizing agent.

In the industrial antibacterial method of the present invention, the respective components may be added simultaneously or separately or may be added completely separately. What is necessary is just to add in the state made.

[0028]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the present invention.

[Formulation Examples 1 to 8 and Comparative Formulation Examples 1 to 1
0] The formulations of Formulation Examples 1 to 8 and Comparative Formulation Examples 1 to 10 according to Examples of the present invention are shown in Tables 1 and 2. All parts in the table indicate parts by weight. Each of Comparative Formulation Examples 1 to 10 is a formulation example comprising one or two compounds of the active ingredient used in the present invention.

In this test example, 5-chloro-2
As a mixture of -methyl-3-isothiazolone and 2-methyl-3-isothiazolone, Zonene F (11.7% of active ingredient) manufactured by Ichikawa Gosei Kagaku Co., Ltd. was added to 5-chloro-3-isothiazolone magnesium nitrate and 2-chloro-3-isothiazolone. Methyl-
As a mixture with 3-isothiazolone magnesium nitrate, Rohm and Haas Caisson WT (active ingredient 13.7%) and 1,2-benzisothiazolone (BIT) include a product of Zeneca (active ingredient 70% powder). ) Was used for each. In addition, diethylene glycol monomethyl ether (DEGME) was used as a solvent.

[0031]

[Table 1] (The numbers in the table indicate the weight% of the active ingredient)

[0032]

[Table 2] (The numbers in the table indicate the weight% of the active ingredient)

Test Example 1 An antibacterial agent composition comprising (A) DBDCB, (B) DBNPA, (C) an isothiazolone compound and its metal complex compound in combination, and the synergistic effect of the combination ratio were as follows. Was tested.

[Test Method and Test Conditions] The slime adhesion preventing effect was evaluated by the following slime adhesion prevention test using artificial white water. In addition, artificial white water (pH 7.0, 3
0 ° C) was prepared so that the BOD was 100 milligrams / liter (mg / l) using starch as a nutrient source, and 1.3 × 10 5 Continuous addition was performed so as to be ⁷ cells / ml. The antimicrobial compositions (Formulation Examples and Comparative Formulation Examples) were intermittently injected three times a day, ie, every eight hours, so that the total amount of the active ingredient was maintained at 30 mg / l in the system every time for 15 minutes. In addition, when the test was performed without adding the antibacterial agent composition to this artificial white water, the slime adhesion start time was 40 hours, and this was used as a blank.

(Slime adhesion prevention test method) SUS30
A slime adhesion monitor in which an external cylinder made of 4 and having an inner cylinder of 100 mm in diameter and a volume of 488 ml and an internal cylinder made of SUS304 having a diameter of 36 mm are combined (Japanese Patent Laid-Open No. 9-750).
No. 65). The white water or artificial white water is continuously led to an external cylinder so as to have a residence time of 20 minutes,
By rotating the internal cylinder at 255 rpm, a Brookfield type torque meter [Toki Sangyo Co., Ltd., RE500H
Mold], the rotational torque of the internal cylinder was measured.

When slime adheres to and grows on the internal cylinder over time, the frictional resistance on the surface of the internal cylinder increases, and the value of the rotational torque increases. Using this principle, the time is plotted on a personal computer every minute with the horizontal axis representing time and the vertical axis representing torque.
The time at which the value of the rotational torque began to rise was defined as the slime deposition start time. The value obtained by subtracting the slime adhesion start time when using white water without adding an antimicrobial agent (blank) from the slime adhesion start time when using white water to which an antimicrobial agent is added is defined as the delay time. Was used as an index of the effect of preventing slime adhesion.

[Test Results] Tables 3 and 4 show the test results. The numerical values in the table indicate the delay time for the blank.

[0038]

[Table 3]

From the results shown in Table 3, the antibacterial agent compositions of the formulation examples according to the examples were compared with the industrial antibacterial agent of the comparative formulation example in the artificial white water target system by the synergistic and additive actions of the three components. In comparison, it was confirmed that a remarkable slime adhesion preventing effect was exhibited. That is, the component (A) and the component (B)
Combination with components, combination of components (B) and (C),
Compared with the combination of the component (A) and the component (C), by blending the component (C) with the component (A) and the component (B), a remarkable effect of preventing slime adhesion in an artificial white water system is exhibited. It was confirmed that.

[Test Example 2] An antibacterial agent composition using the components (A), (B) and (C) in combination and a test for confirming the synergistic effect of the combination ratio were carried out from a paperboard machine at a certain paper mill. Collected white water (pH 5.6, water consumption unit: about 4 m3
/ Ton, BOD: 150 mg / l, major bacterial species: Bacillus, Pseudomonas, Flavobacterium, Alcaligenes.

[Test Method and Test Conditions] The same test method as in Test Example 1 was used except that the artificial white water in Test Example 1 was changed to white water collected from a paperboard machine. The antimicrobial composition was added so that the total amount of each active ingredient was maintained at 30 mg / l in the system every time for 15 minutes. The conditions of the supplied white water were the same as those in Test Example 1 at 30 ° C. and the residence time was 20 minutes. When tested without the addition of the antimicrobial composition, the onset time of slime deposition was 32 hours.

[Test Results] Table 4 shows the test results. The numerical values in the table indicate the delay time for the blank.

[0043]

[Table 4]

From the results shown in Table 4, the antibacterial agent compositions of the preparation examples according to the examples show the synergistic and additive effects of the industrial antibacterial agents of the comparative preparation examples in white water collected from a paper machine at a paper mill. As a result, it was confirmed that a remarkable slime adhesion preventing effect was exhibited. That is, as compared to each of the components (A), (B), and (C) or the combination of the components (A) and (B), the components (A) and (B) are added to the component (C). By blending the components, it was recognized that the slime adhesion delay time on the blank was sharply increased even in the white water system collected from the paperboard machine, and a remarkable slime adhesion prevention effect was exhibited.

[Test Example 3] An antibacterial agent composition using the components (A), (B) and (C) in combination and a test for confirming the synergistic effect of the combination ratio thereof were carried out on a high quality paper machine of a paper mill. The test was performed by a bacterial growth prevention test on the starch coating solution for papermaking collected from the above.

[Test Method and Test Conditions] The collected starch coating solution for papermaking had a pH of 9.6 and a viable cell count of 8.5 × 10 ^5.
Per ml (agar plate dilution method), and the main constituent bacterial species were Pseudomonas, Alcaligenes, and Flavobacterium. A part of this was put into a pre-warmer in advance to sufficiently rot, and this was added as a seed fungus to the starch coating solution (the number of viable bacteria was 6.0 × 10 ⁸ / ml), then dispensed into test tubes, Each composition of the working formulation example and the comparative formulation example was added so that the total amount was 100 mg / l. 30 ℃
After storage in a thermostat for 5 days, the number of surviving bacteria was measured by an agar plate dilution method.

[Test Results] Table 5 shows the test results. The numerical values shown in Table 5 indicate the number of surviving bacteria.

[0048]

[Table 5] Initial bacterial count 5.0 × 10 ⁸ Final bacterial count (9.0 × 10 ⁹ without drug)

As shown in Table 5, the antibacterial agent compositions of the preparation examples according to the examples of the present invention exhibited a synergistic / additive effect in a starch coating solution for papermaking collected from a high-quality papermaking machine of a paper mill. It was found to have a remarkable effect of preventing bacterial growth as compared with the industrial antibacterial agents of Comparative Formulation Examples. That is,
When the component (C) is used in combination with the component (A) and the component (B),
Compared with the component (A), the component (B), the component (C), and the combined composition of the component (A) and the component (B), the paper-making paper coating machine collected from a high-quality paper machine at a paper mill has a higher Thus, it was confirmed that the composition had an excellent effect of preventing bacterial growth.

[0050]

As described above, according to the present invention,
1,2-dibromo-2,4-dicyanobutane (DBDC
B) and 2,2-dibromo-3-nitrilopropionamide (DBNPA) further combined with an isothiazolone-based compound or a metal complex compound thereof, thereby synergizing both the bacteria dispersed in water and the slime on the wall surface. An industrial antibacterial agent composition and an industrial antibacterial method capable of effectively exhibiting a preventive effect can be provided.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (Reference) C02F 1/50 532 C02F 1/50 532D 532J 540 540B

Claims (5)

[Claims] 1. A method comprising: (A) 1,2-dibromo-2,4-dicyanobutane; (B) 2,2-dibromo-3-nitrilopropionamide; (C) an isothiazolone compound and a metal complex compound thereof. An industrial antimicrobial composition comprising at least one selected from the group consisting of: 2. The composition according to claim 1, wherein the component (C) is represented by the following general formula (I):
Isothiazolone compounds and isothiazolones of the following general formula (II)
At least one selected from azolone metal complex compounds
The industrial antimicrobial composition according to claim 1, wherein
object. Embedded imageEmbedded imageIn the general formulas (I) and (II), R₁Is the hydrogen element, alkyl
Group, alkenyl group, alkynyl group or aralkyl group, R
_TwoAnd R_ThreeIs a hydrogen atom or a halogen atom, and R
_TwoAnd R_ThreeCan be condensed to form a benzene ring
is there. Where R _TwoAnd R_ThreeExcept when both are halogen atoms
Good. M is an alkali metal, an alkaline earth metal, a heavy metal,
A cation atom or group selected from the group consisting of
And Z has sufficient solubility to form a complex compound.
An anion atom forming a compound with the cation M
A is an integer of 1 or 2, and n is an anion
Z is an integer satisfying the valence of the cation M. 3. The weight ratio of the component (A) to the component (B) is 100: 1 to 1: 100, and the total amount of the component (A) and the component (B) is The ratio with the component (C) is 1:10 to 10: 1 by weight.
The industrial antibacterial agent composition according to claim 1, wherein: 4. A method comprising: (A) 1,2-dibromo-2,4-dicyanobutane; (B) 2,2-dibromo-3-nitrilopropionamide; (C) an isothiazolone compound and a metal complex compound thereof. An industrial antibacterial method comprising adding at least one selected from the group consisting of a total concentration of 1 to 1,000 mg / liter. 5. The weight ratio of the component (A) to the component (B) is 100: 1 to 1: 100, and the total amount of the component (A) and the component (B) is The ratio with the component (C) is 1:10 to 10: 1 by weight.
The industrial antibacterial method according to claim 4, wherein: