JPH09295906A - Antimicrobial agent for industrial use and microbicidal method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a subject antimicrobial agent which can manifest efficacy with a reduced dose and is useful as an antiseptic agent or a microbicidal agent for water which is used in making paper in the pulp and paper industry or for water used as cooling and washing water in a variety of industries by formulating a specific component. SOLUTION: This antimicrobial agent for industrial use contains, as active ingredients, an o-phthalaldehyde of formula I and a compound of formula II (X1 is H, CHO; X2 is H, OH, CHO, F, Br, a 1-4C alkyl, methoxy, ethoxy or nitro) at a weight ratio of 9/1-1/9. The compound of formula I is at least one selected from p-phthalaldehyde and m-phthalaldehyde. The compounds of formula I and formula II are preferably dissolved in an organic solvent, for example, dimethylformamide and prepared in the form of solution.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an industrial antibacterial agent and a sterilization method, and more specifically, water for papermaking process in the paper and pulp industry, cooling water and washing water for various industries, heavy oil sludge, metalworking oil agent, The present invention relates to an industrial antibacterial agent and a sterilization method useful for preserving and sterilizing fiber oils, paints, paper coating liquids, latexes, sizing agents and the like.

[0002]

2. Description of the Related Art Conventionally, slimming due to bacteria and fungi occurs in cooling water systems in the paper making process in the paper and pulp industry and in various industries, and there are obstacles such as deterioration of product quality and production efficiency. It is known. In addition, many industrial products such as heavy oil sludge, metalworking oils, fiber oils, paints, various latexes, sizing agents, etc. may be rotted or contaminated by bacteria or fungi, which may stain the product and reduce its value. Are known.

Many antimicrobial agents have been used to prevent damage by these microorganisms. Traditionally, organic mercury compounds and chlorinated phenol compounds were used, but these drugs are highly toxic to humans and seafood,
Its use has come to be regulated because it causes environmental pollution. Therefore, recently, relatively low-toxicity organic nitrogen-sulfur compounds, organic halogen-based compounds, and organic sulfur-based compounds have been widely used as industrial antibacterial agents (Bacterial and Antifungal Dictionary (1986, Japan Antibacterial and Antifungal Agents). Published by the Society of Mold Research)).

Among these antibacterial agents, aldehyde compounds have also been developed as effective antibacterial agents having such a relatively low toxicity, and o-phthalaldehyde is also known as an industrial antibacterial agent (special feature). See Japanese Patent Laid-Open No. 63-313705 and Japanese Patent Laid-Open No. 6-23368).

[0005]

The above-mentioned various low-toxicity antibacterial agents have low toxicity, but it is desirable to reduce the use amount thereof as much as possible from the viewpoint of pollution, environment and treatment cost reduction. . Therefore, an antibacterial agent that exhibits an antibacterial effect for a longer period of time with a small addition amount is inevitably desired. From this point of view, for example,
Regarding o-phthalaldehyde, studies have been conducted to develop a synergistic bactericidal effect in combination with other organic antibacterial agents (JP-A-6-264397), but no sufficient effect can be expected.

In view of such circumstances, it is an object of the present invention to provide an industrial antibacterial agent and a sterilizing method which can exert a useful effect with a minimum addition amount.

[0007]

The first aspect of the present invention for solving the above-mentioned problems is characterized by containing o-phthalaldehyde and a compound represented by the following general formula (I) as active ingredients. It is an industrial antibacterial agent.

[0008]

Embedded image

Here, X ₁ represents H or CHO,
X ₂ represents H, OH, CHO, F, Br, an alkyl group having 1 to 4 carbon atoms, OCH ₃ , OC ₂ H ₅ or NO ₂ .

Here, the compound represented by the general formula (I) is, for example, at least one of p-phthalaldehyde and m-phthalaldehyde.

The ratio (weight ratio) of the combination of the o-phthalaldehyde and the compound represented by the general formula (I) is in the range of 100: 1 to 1: 100, for example.

A second aspect of the present invention is an industrial sterilization method characterized in that both o-phthalaldehyde and the compound represented by the general formula (I) are added simultaneously or separately to perform sterilization. It is in.

Here, the ratio (weight ratio) of the combination of the o-phthalaldehyde and the compound represented by the general formula (I) is, for example, in the range of 100: 1 to 1: 100.

The present invention relates to o-phthalaldehyde (hereinafter,
As a result of various investigations on organic compounds that exert a stronger synergistic effect than conventional active ingredients (also referred to as active ingredient (a)) and have low toxicity, the novel antibacterial agent represented by the general formula (I) is However, it has only a weak antibacterial activity that makes it unsuitable for use as an industrial antibacterial agent, but the present invention is based on the finding that a strong bactericidal effect is exhibited when used in combination with the active ingredient (a). Completed

That is, according to the present invention, by adding a compound represented by the above-mentioned general formula (I) as a second component to o-phthalaldehyde, a remarkable synergistic effect of the second component can be obtained. A stronger antibacterial effect is obtained than the antibacterial effect when used alone, in other words,
The same effect can be achieved with a fraction of the amount of the drug added when used alone.

The industrial antibacterial agent of the present invention contains o-phthalaldehyde and a compound having a structure represented by the above general formula (I) as active ingredients, and o-phthalaldehyde is represented by the following formula ( It is a compound represented by II).

[0017]

Embedded image

As the compound having the structure represented by the above general formula (I), p-phthalaldehyde, m-phthalaldehyde, 2-fluorobenzaldehyde, 3-
Fluorobenzaldehyde, 4-fluorobenzaldehyde, 2-chlorobenzaldehyde, 3-chlorobenzaldehyde, 4-chlorobenzaldehyde, 2-bromobenzaldehyde, 3-bromobenzaldehyde, 4-
Bromobenzaldehyde, 2-methoxybenzaldehyde, 3-methoxybenzaldehyde, 4-methoxybenzaldehyde, 2-ethoxybenzaldehyde, 3-ethoxybenzaldehyde, 4-ethoxybenzaldehyde, 2-hydroxybenzaldehyde, 3-hydroxybenzaldehyde, 4-hydroxybenzaldehyde,
2-nitrobenzaldehyde, 3-nitrobenzaldehyde, 4-nitrobenzaldehyde, 2-methylbenzaldehyde, 3-methylbenzaldehyde, 4-methylbenzaldehyde, 2-ethylbenzaldehyde, 3-
Ethylbenzaldehyde, 4-ethylbenzaldehyde, 2-propylbenzaldehyde, 3-propylbenzaldehyde, 4-propylbenzaldehyde, 2-butylbenzaldehyde, 3-butylbenzaldehyde,
4-Butylbenzaldehyde and the like can be mentioned, but the present invention is not limited thereto.

The ratio (weight ratio) of the combination of the active ingredient (a) and the compound having the structure of the general formula (I) in the present invention is preferably 100: 1 to 1: 100, more preferably 9: 1. ˜1: 9. This is because a remarkable synergistic effect is exhibited in this range.

When the active ingredient (a) and the compound having the structure of the general formula (I) are used in combination for industrial sterilization, it is preferable that both are made into a one-part formulation and used simultaneously, but they are added separately. You may use.

In the present invention, the compounds having the structure of the above general formula (I) may be used in combination of two or more kinds.

When the active ingredient (a) and the compound of the above-mentioned general formula (I) are made into a one-pack formulation, they are usually dissolved in a solvent to make a formulation or used as an aqueous suspension. Is preferred.

Here, the solvent that can be used includes water or an organic solvent. That is, by using an organic solvent, the active ingredient (a) and the compound of the general formula (1) can be formulated as a solution in which the organic solvent is dissolved. Examples of the organic solvent that can be used in the present invention include amides such as dimethylformamide and dimethylacetamide; ethylene glycol,
Glycols such as propylene glycol, diethylene glycol, dipropylene glycol and polyethylene glycol, methyl cellosolve, phenyl cellosolve, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether, ethylene glycol diacetate, 2,2,4-trimethyl Glycol esters such as -1,3-pentanediol diisobutyrate;
Alcohols having up to 8 carbon atoms; methyl acetate, ethyl acetate, butyl acetate, dimethyl maleate, diethyl adipate, ethyl lactate, glutaric acid dimethyl ester, succinic acid dimethyl ester, phthalic acid dimethyl ester, 1,2-dibutoxyethane. , 3-methoxybutyl acetate, 3-methoxydibutyl acetate, 2-ethoxymethyl acetate, 2-ethoxyethyl acetate, esters of propylene carbonates; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, isophorone; toluene, xylene, Aromatic solvents such as 1,2-dimethyl-4-ethylbenzene; other solvents such as dimethyl sulfoxide, dioxane and N-methylpyrrolidone can be mentioned.

On the other hand, the active ingredient (a) and the compound of the above-mentioned general formula (I) can be wet-ground using a ball mill, an attritor or the like to be used as a water suspension agent. In the case of producing an aqueous suspension as described above, a thickener such as xanthan gum, rhamsan gum, guar gum and the like, and a nonionic, anionic, cationic or amphoteric surfactant as a dispersant can be used.

When the system to be sterilized is an oil system such as heavy oil sludge, cutting oil, oil paint, etc., it is preferable to prepare a one-pack formulation using a hydrocarbon solvent such as heavy oil, kerosene, spindle oil, etc. In this case, the above-mentioned various surfactants may be used.

The addition amount of the industrial antibacterial agent of the present invention varies depending on the object to be sterilized. For example, when it is added to the process water system of the papermaking process or the industrial cooling water system, it is 0.05 to water. -100 mg / l is suitable.

[0027]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described below with reference to Examples and Test Examples, but the present invention is not limited thereto.

(Examples) Formulation examples according to the examples of the present invention are shown below. All parts in the examples are parts by weight.

Formulation Example 1 o-phthalaldehyde 10 parts p-phthalaldehyde 10 parts propylene carbonate 80 parts (Formulation Example 2) o-phthalaldehyde 10 parts m-phthalaldehyde 10 parts propylene carbonate 80 parts (Comparative Formulation Example) 1) o-phthalaldehyde 20 parts propylene carbonate 80 parts (Comparative Preparation Example 2) p-phthalaldehyde 20 parts Propylene Carbonate 80 parts (Comparative Preparation Example 3) m-phthalaldehyde 20 parts Probylene Carbonate 80 parts

(Test Example 1) "Synergistic effect confirmation test by blending ratio of each component" 30 in liquid medium (pH 7.0) of peptone yeast extract
Pseudomonas aeruginosa that had been pre-cultured at 24 ° C for 24 hours was adjusted to a starting cell count of 1.0 x 10 ⁷ CFU / ml using a sterilized phosphate buffer solution (0.01 M, pH 7.0), and the mixing ratio of various active ingredients was adjusted. The drug that changed the
500 ppm was added and shaken at 30 ° C. for 30 minutes. After that, the number of viable bacteria is measured, and 99% or more is sterilized (1.0 ×
The viable cell count of 10 ⁵ CFU / ml or less) The minimum concentration was determined.

The additive agents are the comparative formulation examples 1 to 1 of the above examples.
3 in various proportions, and further diluted with pure water to 1%, 0.1
% And 0.01% were used and added to the test solution.

(Test Results) The test results are shown in FIGS. From these results, p-phthalaldehyde, m
It has been confirmed that -phthalaldehyde alone has a weaker bactericidal effect as compared with o-phthalaldehyde, but a synergistic bactericidal effect is exhibited by blending these with o-phthalaldehyde. 1 and 2
In, the broken line indicates the theoretical additive effect, and the solid line indicates the synergistic effect according to the test results.

(Test Example 2) "Synergistic effect confirmation test based on the blending ratio of each component" White water (pH 7.
To 2), add 5 ppm as the total amount of various active ingredients,
Shake for 30 minutes at 30 ° C. Then, the viable cell count was measured to determine the bactericidal rate (%) with respect to the initial cell count (7.73 × 10 ⁶ CFU / ml).

(Test Results) The test results are shown in Table 1. From this result, it was confirmed that the present invention further enhances the effect of the conventional industrial bactericide comprising o-phthalaldehyde. That is, it was confirmed that a remarkable effect is exhibited in white water of a paper mill by using A + B or A + C rather than using A, B and C alone.

[0035]

[Table 1]

(Test Example 3) Predetermined amounts of various formulation examples were added to the newspaper making process (acidic making, 40 ° C., pH 4.6) of a certain paper mill, and the viable cell count was measured immediately after the addition.

(Test Results) Table 2 shows the test results. From this result, the industrial antibacterial agent of Formulation Example 1 according to the present invention can exert a remarkably superior effect in practical use as compared with the effect as the bactericidal agent of o-phthalaldehyde in the actual papermaking white water system. It has become clear that it is possible to reduce the amount of drug added.

[0038]

[Table 2]

[0039]

INDUSTRIAL APPLICABILITY As described above, according to the present invention, the above-mentioned general formula (I) is added to o-phthalaldehyde as the second component.
By the addition of the compound represented by, due to the significant synergistic effect of the second component, a stronger antibacterial effect is obtained than the antibacterial effect when o-phthalaldehyde is used alone,
In other words, there is an effect that the same effect can be exhibited with a fraction of the drug addition amount when used alone.

[Brief description of drawings]

FIG. 1 is a diagram showing a synergistic effect of o-phthalaldehyde and p-phthalaldehyde according to the results of Test Example 1.

FIG. 2 is a diagram showing a synergistic effect of o-phthalaldehyde and m-phthalaldehyde in relation to the result of Test Example 1.

Claims (5)

[Claims] 1. An industrial antibacterial agent comprising o-phthalaldehyde and a compound represented by the following general formula (I) as active ingredients. Embedded image Here, X ₁ represents H or CHO, and X ₂ is H, O.
H, CHO, F, Br, alkyl group having 1 to 4 carbon atoms, O
Represents CH ₃ , OC ₂ H ₅ or NO ₂ . 2. The industrial antibacterial agent according to claim 1, wherein the compound represented by the general formula (I) is at least one of p-phthalaldehyde and m-phthalaldehyde. 3. The ratio (weight ratio) of the combination of the o-phthalaldehyde and the compound represented by the general formula (I) according to claim 1 or 2, is 100: 1 to 1: 1.
An industrial antibacterial agent characterized by being in the range of 00. 4. An industrial sterilization method comprising sterilizing by adding both o-phthalaldehyde and a compound represented by the following general formula (I) simultaneously or separately. Embedded image Here, X ₁ represents H or CHO, and X ₂ is H, O.
H, CHO, F, Br, alkyl group having 1 to 4 carbon atoms, O
Represents CH ₃ , OC ₂ H ₅ or NO ₂ . 5. The ratio (weight ratio) of the combination of the o-phthalaldehyde and the compound represented by the general formula (I) according to claim 4, in the range of 100: 1 to 1: 100. An industrial sterilization method characterized by: