JPH10139603A - Industrial antimicrobial - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an industrial antimicrobial effectively suppressing microbial lesions. SOLUTION: This industrial antimicrobial includes 2-(p-hydroxyphenyl) glyoxylohydroximoyl chloride and second components of one or more than two kinds selected from a group consisting of 4,5-dichloro-2-n-octylisothiazolin-3- one, 1,2-benzoisothiazolin-3-one, 2-bromo-2-nitropropan-1,3-diol, α- chlorobenzaldoxime acetate, 5-chloro-2,4,6-trifluoroisophthalonitrile and o- phthalaldehyde as active ingredients. By synergistic effect of remarkably excellent bactericidal activity due to combined use, microbial lesions in wide objective water systems can be effectively suppressed at a small amount of added medicine.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an industrial antibacterial agent, 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 working oil,
The present invention relates to an industrial antibacterial agent useful for preserving or sterilizing fiber oils, paints, coating liquids for paper, latex, paste and the like.

[0002]

2. Description of the Related Art In papermaking processes in the paper and pulp industry and in cooling water systems in various industries, slime is generated by bacteria and fungi, causing problems such as deterioration in quality of products and reduction in production efficiency. 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, thereby contaminating the products and reducing their commercial value.

Conventionally, various antibacterial agents have been used in order to prevent such damage by microorganisms.

As this antibacterial agent, organic mercury compounds, chlorinated phenol compounds and the like have long been used. However, these drugs are highly toxic to the human body and fish and shellfish and cause environmental pollution, so their use has been regulated.Recently, relatively low toxicity of organic nitrogen / sulfur compounds, organic halogen compounds, Organic sulfur compounds are used as industrial antibacterial agents (Encyclopedia of antibacterial and antifungal agents (published by the Japan Society of Antifungal and Antifungal Agents in 1986)). Oxime compounds have also been developed as industrial antibacterial agents having such relatively low toxicity and excellent slime adhesion preventing effect.
As a species, 2- (p-hydroxyphenyl) glyoxylohydroxymoyl chloride (hereinafter abbreviated as "HPGHC") is known (Japanese Patent Publication No. 51-9005).

The various low-toxic industrial antibacterial agents described above include:
Although it has low toxicity, it is desirable to minimize its use from the viewpoints of pollution prevention, environmental protection, and reduction of processing costs. Therefore, antibacterial agents that exhibit a long-lasting bactericidal effect with the smallest possible amount of addition are desired. From this viewpoint, for example, research has been conducted on HPGHC to exhibit a synergistic bactericidal effect in combination with other organic antibacterial agents. (JP-A-3-167101). In addition,
In JP-A-3-167101, HPGHC is described as "N, 4-dihydroxy-α-oxobenzeneethaneimidoyl chloride".

The present invention has been made in view of the above-mentioned conventional circumstances, and has a remarkably excellent synergistic bactericidal effect by using a first component of HPGHC in combination with another second component.
An object of the present invention is to provide an industrial antibacterial agent which exhibits an effective slime adhesion-preventing effect over a long period of time when used at a low concentration.

[0007]

The industrial antibacterial agent of the present invention comprises a first component of 2- (p-hydroxyphenyl) glyoxylohydroxymoyl chloride (HPGHC) represented by the following structural formula (A): 4,5-dichloro-2-n-octylisothiazolin-3-one represented by the structural formula (B), 1,2-benzoisothiazolin-3-one represented by the following structural formula (C), and the following structural formula (D ), 2-bromo-2-nitropropane-1,3-diol, α-chlorobenzaldoxime acetate represented by the following structural formula (E), and 5 represented by the following structural formula (F)
One or more second components selected from the group consisting of -chloro-2,4,6-trifluoroisophthalonitrile and o-phthalaldehyde represented by the following structural formula (G) as active ingredients; Things.

[0008]

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[0009]

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That is, the present inventors have conducted various studies on low-toxic organic compounds which exhibit a strong synergistic bactericidal effect when combined with HPGHC.
Although the compound of the present invention exhibits only a weak bactericidal activity as compared with HPGHC by itself, it has been found that the compound exhibits a strong synergistic bactericidal effect in combination with HPGHC, and the first component of HPGHC and the above ( The industrial antibacterial agent of the present invention comprising a novel combination composition of the components (B) to (G) with the second component has been found.

[0011]

Embodiments of the present invention will be described below in detail.

The industrial antibacterial agent of the present invention comprises HPGHC as the first component and the second component as active ingredients. The first component (H) in the industrial antibacterial agent of the present invention is used.
The mixing ratio of PGHC) and the second component is such that DOIT, BIT, B
In the case of one kind or two or more kinds selected from the group consisting of NP and CFIPN, the mixing ratio of the first component and the second component is 90:10 to 30:70 (weight ratio), and especially, the second component is In the case of BIT and / or BNP, the mixing ratio of the first component and the second component is 90:10 to 50:50 (weight ratio), and when the second component is CBAA and / or OPA, The mixing ratio of the first component and the second component is 9:10.
Preferably, the ratio is 10:90 (weight ratio).

The industrial antibacterial agent of the present invention basically comprises
It is prepared as a one-pack formulation in which the components HPGHC and the second component are uniformly mixed. Alternatively, individual compounds may be formulated and added simultaneously to the system to be treated.

When a one-part formulation of HPGHC and the second component is prepared, they may be dissolved in an organic solvent to form a solution,
It is preferably used as a water suspension.

When dissolved in an organic solvent to form a solution, examples of the organic solvent used include amides such as dimethylformamide and dimethylacetamide; glycols such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol and polyethylene glycol; Glycol esters such as cellosolve, phenyl cellosolve, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether, ethylene glycol diacetate, 2,2,4-trimethyl-1,3-pentanediol diisobutyrate; carbon Alcohols of number 8 or less; methyl acetate, ethyl acetate, butyl acetate, dimethyl maleate, diethyl adipate Ethyl lactate, dimethyl glutarate ester, succinic acid dimethyl ester, phthalic acid dimethyl ester, 1,2-dibutoxyethane, 3-methoxybutyl acetate, 3-methoxy-di-butyl acetate, 2
Esters such as ethoxymethyl acetate, 2-ethoxyethyl acetate and propylene carbonate; acetone, methyl ethyl ketone, methyl isobutyl ketone,
Ketones such as isophorone; toluene, xylene, 1,2
Aromatic solvents such as -dimethyl-4-ethylbenzene; and solvents such as dimethylsulfoxide, dioxane, and N-methylpyrrolidone. One of these solvents may be used alone, or two or more thereof may be used in combination.

When the industrial antibacterial agent of the present invention is used as a solution, the total concentration of HPGHC and the second component in the solution is preferably about 1 to 80% by weight.

In particular, when the system to be disinfected is an oil system such as heavy oil sludge, cutting oil, oil-based paint, etc., it is preferable to form a one-part preparation using a hydrocarbon solvent such as heavy oil, kerosene, or spindle oil. In some cases, various nonionic, anionic, cationic, or amphoteric surfactants may be added. In this case, the total concentration of HPGHC and the second component is preferably about 1 to 50% by weight, and when a surfactant is blended, the blending concentration is preferably about 0.1 to 60% by weight. .

In the case where the industrial antibacterial agent of the present invention is made into an aqueous suspension, the aqueous antibacterial agent is prepared by using a ball mill, an attritor or the like.
PGHC and the second component are wet-ground in water to form a uniform aqueous suspension. When producing an aqueous suspension, thickeners such as xanthan gum, ramzan gum, guar gum, nonionics,
A dispersant such as an anionic, cationic or amphoteric surfactant may be blended. In this case, the total concentration of HPGHC and the second component in the aqueous suspension is preferably about 1 to 50% by weight. Further, the compounding concentrations of the thickener and the dispersant are preferably about 0.01 to 1% by weight and about 0.1 to 10% by weight, respectively.

The industrial antibacterial agent of the present invention exhibits a remarkable bactericidal effect and an effect of preventing the growth of microorganisms in various industrial target systems.
It is effective for various industrial cooling water systems.

Although the amount of the industrial antibacterial agent of the present invention varies depending on the target system, it is usually intermittent or continuous in such an amount that the active ingredient concentration becomes about 0.05 to 100 mg / L with respect to industrial water. It is appropriate to add to the mixture, and with such an added amount, microbial damage can be effectively suppressed by a synergistic effect of a remarkable bactericidal effect of HPGHC and the second component.

[0021]

The present invention will be described more specifically below with reference to examples and comparative examples.

Examples 1 to 6 and Comparative Examples 1 to 5 (HPGHC
Of synergistic effect of sterilization effect by the combined use of various ingredients and various second components) Gram negative found in process water in the pulp and paper industry, cooling water for various industries, paint, coating liquid for paper, latex, and paste Pseudomonasaeruginosa, a representative strain of bacteria
, A test for confirming the bactericidal effect in the case where various second components shown in Table 1 were combined with HPGHC.

A bacterial solution pre-cultured in a bouillon medium was added to sterile water (0.1 M phosphate buffer, pH 7.0) so that the number of viable bacteria was 1 × 10 ⁷ CFU / mL, and various compounding agents were added. 3 ppm was added as the total amount of the active ingredients, and the mixture was shaken at 30 ° C. for 30 minutes. Then, the viable cell count was measured, and the bactericidal rate (%) with respect to the initial cell count (7.73 × 10 ⁶ CFU / mL) was determined. Table 1 shows the results.

The following is clear from Table 1.

That is, according to the present invention, DOIT, BIT, BNP, CBA
When A, CFIPN or OPA is combined, a remarkably superior bactericidal effect is recognized as compared with the use of each of them alone. On the other hand, when the other second components shown as comparative examples are combined, although some synergistic effects due to the combination are recognized, the effects are very weak.

It should be noted from Table 1 that the preferred mixing ratio of HPGHC and the second component is that the second component is DOIT or CFIP.
In the case of N, HPGHC: second component = 90: 10-3
0:70, and HPGHC when the second component is BIT or BNP: 9:10 to 50:50, and HPGH when the second component is CBAA or OPA.
It can be seen that C: the second component = 90: 10 to 10:90.

[0027]

[Table 1]

Examples 7 to 12 (test for confirming synergistic effect of slime adhesion preventing effect of industrial antibacterial agent of the present invention) A temperature controller, a stirrer, and a thermometer are attached to a 165 mm diameter, 3000 mL water holding tank made of vinyl chloride. Along with a slime measuring plate, width 2.5cm, length 4c
A stainless steel plate having a thickness of 0.2 mm and a thickness of 0.2 mm was immersed in water and attached. To this aquarium, 1% by weight of LBKP pulp and 0.1 mL / L of a white water culture solution (a culture solution of white water collected from a newsprint papermaking process in a bouillon liquid medium) were added to a 1000-fold diluted broth liquid medium. After doing
9 artificial white water adjusted to pH 5.0 with aluminum sulfate
L / hr was supplied, and the same amount of artificial white water was discharged.

HPGHC (the first component) and the second component shown in Table 2 were added to the test water in the aquarium three times a day by a pump at different mixing ratios for 30 minutes each time. The drug was added intermittently, and the amount added was such that the total concentration of the first and second components was maintained at 5 ppm or more for 15 minutes. Stirring was continued while the temperature of the test water was kept at 30 ° C., and seven days after the start of the test, the effect of preventing slime adhesion was evaluated.

The effect of preventing slime adhesion was evaluated by measuring the slime adhesion thickness (μm) using a wet gauge (manufactured by Kett Co., Ltd .: for measuring the thickness of wet paint), and the results are shown in Table 2. Was.

For comparison, Table 1 also shows the results when no drug was added (blank).

From Table 2, it can be seen that the industrial antibacterial agent of the present invention, H
PGHC and DOIT, BIT, BN as the second component
In combination with P, CBAA, CFIPN or OPA, a slime adhesion-preventing effect, which is an important effect as an industrial antibacterial agent, is remarkably recognized. The effect is particularly high when the blending ratio is HPGHC: second component = 70: 30. ~ 30: 70
(Weight ratio) was found to be significantly higher than when each was added alone.

[0033]

[Table 2]

Examples 13 to 18 and Comparative Examples 6 to 12 (HP
Test for synergistic effect of paper white water disinfection effect by combined use of GHC and various second components) White water (Bacillus, Pseudomonas, Flavobacterium, Alcaligenes) collected from a paper machine at A, B, C paper mill with the following water quality Genus) and H in the formulation shown in Table 3.
A drug prepared by dissolving PGHC and the second component in an organic solvent (diethylene glycol monomethyl ether) to form a one-part formulation (however, in Comparative Examples 6 to 12, HPGHC or only the second component alone) is added, and the temperature is raised to 30 ° C. And shaken for 30 minutes.

A paper mill water quality pH: 7.1 Initial bacteria count: 8.6 × 10 ⁸ CFU / mL B paper mill water quality pH: 5.6 Initial bacteria count: 7.5 × 10 ⁷ CFU / mL C paper mill Water pH: 4.4 Initial bacterial count: 1.2 × 10 ⁶ CFU / mL Then, the number of surviving bacteria is measured, and the minimum bactericidal concentration (ppm) in terms of the active ingredient at which 99% or more of the initial bacterial count is killed is determined. The results are shown in Table 3.

As the co-reagent, DOIT, BIT, B
For NPs, at a ratio of 70:30, CBAA, C
FIPN and OPA were formulated at a ratio of 50:50 and used as a final active ingredient concentration of 20% by weight. Further, in Comparative Examples 6 to 12, each drug was used as a single formulation formulated so as to have a final active ingredient concentration of 20% by weight.

As shown in Table 3, the industrial antibacterial agent of the present invention is HP
GHC is used in combination with a specific second component to broaden the antibacterial spectrum, and due to the synergistic effect of the bactericidal action, it is significantly more bactericidal in industrial systems with a wide pH range and bacterial level than when used alone. It can be seen that the effect is exhibited.

[0038]

[Table 3]

[0039]

As described in detail above, according to the industrial antibacterial agent of the present invention, the synergistic effect of the excellent antibacterial and slime adhesion-preventing effects by using low toxicity HPGHC in combination with the specific second component. Thus, microbial damage in a wide range of target water systems can be effectively suppressed with a small amount of drug added.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI A01N 43:80) (A01N 35/08 33:20) (A01N 35/08 37:16) (A01N 35/08 37:34) (A01N 35/08 35:04)

Claims (3)

[Claims] A first component of 2- (p-hydroxyphenyl) glyoxylohydroxymoyl chloride;
5-dichloro-2-n-octylisothiazoline-3-
On, 1,2-benzisothiazolin-3-one, 2-
Bromo-2-nitropropane-1,3-diol, α-
Chlorobenzaldoxime acetate, 5-chloro-
2,4,6-trifluoroisophthalonitrile and o-
An industrial antibacterial agent comprising, as an active ingredient, one or more second components selected from the group consisting of phthalaldehyde. 2. The method according to claim 1, wherein the second component is 4,5-
Dichloro-2-n-octylisothiazolin-3-one, 1,2-benzoisothiazolin-3-one, 2-bromo-2-nitropropane-1,3-diol and 5-
One or more selected from the group consisting of chloro-2,4,6-trifluoroisophthalonitrile;
The mixing ratio of the component and the second component is 1st component: 2nd component = 9
An industrial antibacterial agent characterized by a ratio of 0:10 to 30:70 (weight ratio). 3. The method according to claim 1, wherein the second component is α-chlorobenzaldoxime acetate and / or o-phthalaldehyde, and the mixing ratio of the first component and the second component is the first component: the second component. = 90:10 to 10:90 (weight ratio).