JPH0812505A - Industrial antimicrobial agent and method for suppressing proliferation of microorganism - Google Patents

Abstract

PURPOSE:To obtain an antimicrobial agent exhibiting remarkable synergistic effect, effective against bacteria, fungi, etc., in alkaline region at a small amount and keeping the effect over a long period by using an N-substituted N- hydroxymethylamine or its polycondensate in combination with a substituted phenol compound. CONSTITUTION:This industrial antimicrobial agent contains at least one kind of N-substituted N-hydroxymethylamine of formula I (R is an alkyl; (n) is 1-3) or its polycondensate (including the compound of formula II when n=3) in combination with at least one kind of a substituted phenol compound selected from the compound of formula III ((m) is 1 or 2) and the compound of formula IV (R<1> and R<2> are each H or a halogen; R<2> is H or OH; X is a bond, an alkylene or S). The compounding ratio of the compound of formula I or its polycondensate to the compound of formula III or formula IV is especially preferably 9:1 to 1:9. The system to be treated with the industrial antimicrobial agent preferably contains water and its pH is preferably alkaline side, especially >=9.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an industrial antimicrobial agent and a method for inhibiting the growth of microorganisms. More specifically, industrial products such as metalworking oils (cutting oils), fiber oils, paper coating liquids (coating colors, calcium carbonate slurries), paints, latexes, sizing agents, etc. are rotted by microorganisms such as bacteria and fungi, The present invention relates to an industrial antimicrobial agent for preventing deterioration and a method for inhibiting the growth of microorganisms.

[0002]

2. Description of the Related Art The industrial products mentioned above are prone to spoilage and mold formation due to fungi such as bacteria, fungi and yeasts, and many industrial antibacterial agents have been used so far. In addition, it was necessary to add a large amount of drug to obtain these effects.

Of the above industrial products, the target system contains water and its pH is alkaline, for example, metal working oils (cutting oils), fiber oils, paper coating liquids (coating color, calcium carbonate). Slurry) and the like, which are known industrial antiseptic and fungicides, 5-chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, 4,5-dichloro- 2-n-
Isothiazolones represented by octyl-isothiazolin-3-one and 2-n-octyl-isothiazolin-3-one, 2-bromo-2-nitropropane-1,3-diol, 2,2-dibromo-2-nitro There was a problem that the antibacterial effect of the organic bromine compounds represented by -1-ethanol and 2,2-dibromo-3-nitrilopropionamide was decreased with time, and an effective antibacterial effect could not be expected for a long period of time. (Usually an antibacterial effect of 1 month or more is required).

The N-substituted N-hydroxymethylamine and its polycondensates and substituted phenol compounds used in the present invention are known as industrial antiseptic and fungicides which are stable in an alkaline pH range (Japan Antibacterial and Antifungal Agent). See "Encyclopedia of Antibacterial and Antifungal Agents" published by the Society in 1986)

[0005]

However, although N-substituted N-hydroxymethylamine and its polycondensate exhibit an effective antibacterial effect against bacteria, they are effective against fungi such as mold and yeast. In addition to the problem that its effect is weak, its antibacterial effect is remarkably reduced when used at a concentration lower than the growth inhibitory concentration of bacteria, so it was necessary to constantly measure the number of bacteria and control the amount added. .

Further, the substituted phenol compounds represented by 4-chloro-3,5-dimethylphenol (para-chloro-meta-xylenol) show resistance to bacteria, fungi and yeasts, but the resistance is The effect is weak and decreases in a relatively short period of time. In addition, there is a problem that a satisfactory antibacterial effect is not always exhibited by itself even if used in a large amount.

The object of the present invention is (1) to provide an industrial antimicrobial agent that sterilizes bacteria and fungi that spoil or deteriorate industrial products with a small amount of addition, and that prevents the development thereof over a long period of time (2) ) Providing an industrial antimicrobial agent that does not contain a diluent such as a solvent (3) Providing a method in which the growth of microorganisms is suppressed by adding a small amount to the target system (4) Water whose pH is alkaline It is intended to provide a method for suppressing the growth of microorganisms by adding a small amount to a target system containing a.

The inventors of the present invention have conducted extensive studies to achieve the above object, and as a result, by using N-substituted N-hydroxymethylamine or a polycondensate thereof and a substituted phenol compound in combination, a remarkable synergistic effect is exhibited. The fact that the effect is remarkable in the target system where the pH is alkaline, the fact that the antimicrobial effect is exerted against the microorganisms of bacteria, mold and yeast with a small amount of addition, and the effect lasts for a long period of time. And completed the present invention.

[0009]

According to the present invention, therefore, (1) the general formula (I):

[0010]

Embedded image (In the formula, R is a lower alkyl group which may be substituted with a hydroxy group, and n is an integer of 1 to 3).
Substituted N-hydroxymethylamine and its polycondensate (n
= 3, the formula:

[0011]

[Chemical 6] And (2) a) the general formula (II):

[0012]

[Chemical 7] (In the formula, m represents 1 or 2) and b) the general formula (III)

[0013]

Embedded image (In the formula, R ¹ and R ³ are the same or different and each represents a hydrogen atom or a halogen atom, R ² represents a hydrogen atom or a hydroxyl group, and X represents 1
Represents one bond, a lower alkylene group or a sulfur atom. The present invention provides an industrial antimicrobial agent, which comprises, as an active ingredient, at least one substituted phenol compound selected from compounds represented by the formula (1).

In the present invention, the "microorganism" means bacteria and fungi such as fungi and yeast. In the general formula (I), the “lower alkyl group” of the lower alkyl group which may be substituted with the hydroxy group represented by R is an alkyl group having 1 to 3 carbon atoms, for example, methyl, ethyl, n- or Examples thereof include an iso-propyl group, and an ethyl group is particularly preferable. Examples of the N-substituted N-hydroxymethylamine represented by the general formula (I) and its polycondensates include 2- (hydroxymethylamino) ethanol (hereinafter abbreviated as HMAE) and 2,4-bis (2- Hydroxyethyl)-
2,4-diaza-1-butanol, 2,4,6-tris (2-hydroxyethyl) -2,4,6-triaza-1
-Hexanol, hexahydro-1,3,5-tris (2-hydroxyethyl) -s-triazine and hexahydro-1,3,5-triethyl-s-triazine.

The term "polycondensate" as used herein means a polymer compound produced during the condensation reaction. These compounds can be easily prepared from monoethanolamine and paraformaldehyde (UK patent 9203).
No. 01). In addition, commercially available products (manufactured by Yoshitomi Pharmaceutical Co., Ltd., trade name "Tomicide G" or Dainippon Ink and Chemicals, Inc., trade names "Best Side 1087Y", "Best Side 1087T" manufactured by RT Vanderbilt, trade name "Vancid"
e TH ”) may be used. Mainly used as a preservative for metalworking oils.

In the general formula (III), examples of the lower alkylene group represented by X include methylene, ethylene and propylene. Examples of halogen represented by R ¹ and R ³ include chlorine and bromine. Examples of the substituted phenol compound represented by the general formula (II) or the general formula (III) include 4-chloro-3,5-dimethylphenol (hereinafter abbreviated as PCMX) and 4-chloro-3-methylphenol (hereinafter abbreviated as PCMX). , CMC), 2,2 ^, -methylenebis (4-chlorophenol) (hereinafter abbreviated as MBCP), and o-phenylphenol (hereinafter abbreviated as OPP).

Among the above-mentioned substituted phenol compounds, for example, PCMX can be produced by treating 3,5-dimethylphenol with chlorine gas or thionyl chloride. In addition, a commercial product (manufactured by Bayer AG, product name "Preventol
"CMK", "Preventol Oextra", "Preventol GD" or Mitsubishi Gas Chemical Co., Inc., trade name "PCMX") may be used. Mainly used as a disinfectant and a raw material for cosmetics.

The industrial antimicrobial agent of the present invention comprises 2-hydroxymethylaminoethanol represented by the general formula (I) or a polycondensate thereof and the general formula (II) or the general formula (II).
20: 1 to the substituted phenol compound represented by I)
A weight ratio of 9: 1, more preferably a weight ratio of 9: 1 to 1: 9 is preferable because a remarkable synergistic effect is exhibited.

The synergistic effect of the present invention means that the minimum inhibitory concentration against bacteria is 1/3 as compared with the case where they are used alone.
It means an effect of reducing the amount to ˜1 / 10, an effect that the bacterium spreads to all bacteria, fungi and yeasts, and an effect of inhibiting the growth of bacteria, fungi and yeasts and extending the period for 2 to 4 weeks. The active ingredient of the present invention is usually preferably used in the form of a liquid formulation. However, the present invention is not limited to this, and may be used in the form of powder or the like depending on the object of use.

In the case of a one-pack formulation, a hydrophilic organic solvent is usually used. If the target system contains water,
In consideration of dissolution and dispersibility of the active ingredient, it is preferable to use water or a hydrophilic organic solvent and, if necessary, a liquid agent containing a dispersant. Examples of the hydrophilic organic solvent include amides such as dimethylformamide, glycols such as ethylene glycol, propylene glycol, diethylene glycol and dipropylene glycol, methyl cellosolve, phenyl cellosolve, diethylene glycol monomethyl ether, dipropylene glycol monomethyl ether and tripropylene glycol. Examples thereof include glycol ethers such as monomethyl ether, alcohols having up to 8 carbon atoms or esters such as methyl acetate, ethyl acetate, 3-methoxybutyl acetate, 2-ethoxymethyl acetate, 2-ethoxyethyl acetate and propylene carbonate.

As the dispersant, a cationic surfactant,
Anionic surfactants, nonionic surfactants or amphoteric surfactants are suitable, and nonionic surfactants are preferred from the viewpoint of stability as a preparation. Examples of the nonionic surfactant include higher alcohol ethylene oxide adducts (ethylene oxide is abbreviated as EO hereinafter), alkylphenol (EO) adducts, fatty acid (EO) adducts, and polyhydric alcohol fatty acid esters. (EO) adduct,
Higher alkylamine (EO) adducts, fatty acid amide (EO) adducts, oil and fat (EO) adducts, propylene oxide [P. Abbreviated as O.) (EO) copolymer, alkylamine (PO) (EO) copolymer adduct, fatty acid ester of glycerin, fatty acid ester of pentaerythritol, fatty acid ester of sorbitol and sorbitan, Examples thereof include fatty acid ester of sugar, alkyl ether of polyhydric alcohol, and alkylolamide.

When the active ingredient of the present invention, especially the compound of the general formula (II) or the general formula (III) is poorly soluble in water, it is preferable to add a calculated amount of alkali to form an aqueous solution. As the alkali, alkali hydroxide such as sodium hydroxide and potassium hydroxide or alkali carbonate such as sodium carbonate and potassium carbonate is used. The compounding ratio of these preparations is such that the total amount of the active ingredients is 1 to 50 parts by weight, preferably 30.
˜50 parts by weight, the dispersant is at least 0.01 parts by weight, preferably 0.01 to 0.1 parts by weight, per 1 part by weight of the total of the active ingredients.
It is preferably parts by weight, and the balance is preferably water or a hydrophilic organic solvent.

Further, for the system to be sterilized in which the active ingredient of the present invention can be directly dissolved or dispersed, it can be diluted directly or with a solid diluent (for example, kaolin, clay, bentonite, CMC, etc.), and if necessary, The surfactant may be used to form a powder. In the above one-pack formulation, a formulation that does not contain a diluent such as the above solvent or a dispersant such as a surfactant is preferable from the viewpoint of economy in transportation and formulation stability.

From this point of view, a liquid industrial antioxidant comprising at least one compound of the general formula (I) and its polycondensate and at least one compound of the general formula (II) and the general formula (III). A microbial agent is provided. In the industrial antimicrobial agent, the compound of general formula (I) or a polycondensate thereof is used as a solvent for the compound of general formula (II) or general formula (III).

From the viewpoint of the solubility of the solute in a solvent and its stability, the industrial antimicrobial agent is 60 to 99 parts by weight, preferably 8 to 80 parts by weight, of the compound of the general formula (I) and its polycondensate.
40 to 1 part by weight, preferably 20 to 5 parts by weight of the compound of the general formula (II) or the general formula (III), relative to 0 to 95 parts by weight.
It is preferable to dissolve it in a proportion of parts by weight. The addition amount of the industrial antimicrobial agent of the present invention varies depending on the target system, but it is usually 50 to 2000 mg / total amount of active ingredients.
Addition of 1, preferably 100 to 1000 mg / l exerts an effective antimicrobial effect. The industrial antimicrobial agent of the present invention is preferably used as a one-part formulation as described above, but each active ingredient may be separately added to the target system in combination. The antimicrobial agent of the present invention is applied to a water-based composition that is damaged by microorganisms. For example, the water-based composition includes: 1) Paper coating liquids used in paper and pulp mills (coating color, calcium carbonate slurry). ), Synthetic resin emulsion (SBR latex, etc.), starch paste, etc. 2) Other metal processing oils (cutting oil, rolling oil, etc.), fiber oils, emulsion paints, adhesives, sizing agents, latex compounds, cement dispersants, etc. Industrial products are mentioned. Among the above industrial products, the antimicrobial agent of the present invention is an industrial product containing alkaline water, particularly water having a pH of 9 or more, such as metalworking oil (cutting oil, rolling oil, etc.) showing alkaline pH, fiber oil agent, It is preferably applied to a coating liquid for paper (coating color, calcium carbonate slurry) and the like.

According to the present invention, the target system is represented by the general formula (I)
50 to 200 of at least one compound and a polycondensate of
0 mg / l, preferably 100-1000 mg / l, and at least one compound of general formula (II) and general formula (III) 0.5-800 mg / l, preferably 1-400 mg / l A method for suppressing the growth of microorganisms is provided. Here, the target system means an aqueous composition that causes damage by the microorganisms described above.

In the method of the present invention, if each active ingredient is less than the above-mentioned minimum concentration, a sufficient antimicrobial effect cannot be obtained, which is not preferable, and even if it is added in excess of the above-mentioned maximum concentration, further antimicrobial effect can be obtained. It is economically unfavorable because it does not exist. In the method of the present invention, at least one compound of the general formula (I) and its polycondensate, and the general formula (II)
And the compound of the general formula (III) is used in combination with at least one compound in a weight ratio of 20: 1 to 1: 9, preferably 9: 1 to 1: 9. It is more preferable because a synergistic effect is exhibited.

[0028]

【Example】

Examples (formulation examples) Two types of active ingredients of the present invention were dissolved in a solvent to prepare formulation examples 1 to 3.
Was prepared, and alkali was added to the two active ingredients of the present invention and dissolved in water to prepare Preparation Examples 4 and 5. Formulation Examples 6 to 8 were prepared by adding a large amount because one of the active ingredients, HMAE, also serves as a solvent. Formulation Example 1 HMAE 50 parts by weight OPP 10 parts by weight Diethylene glycol 40 parts by weight Formulation Example 2 HMAE 50 parts by weight MBCP 10 parts by weight Diethylene glycol 40 parts by weight Formulation Example 3 HMAE 50 parts by weight PCMX 10 parts by weight Diethylene glycol 40 parts by weight Formulation Example 4 HMAE 50 Parts by weight PCMX 10 parts by weight Sodium hydroxide 2 parts by weight Water 38 parts by weight Formulation example 5 HMAE 50 parts by weight MBCP 10 parts by weight Sodium hydroxide 2 parts by weight Water 38 parts by weight Formulation example 6 HMAE 90 parts by weight PCMX 10 parts by weight Formulation example 7 HMAE 90 parts by weight MBCP 10 parts by weight Formulation Example 8 HMAE 90 parts by weight CMC 10 parts by weight The relationship between compounds and abbreviations is as follows.

HMAE: 2- (hydroxymethylamino) ethanol OPP: o-phenylphenol MBCP: 2,2′-methylenebis (4-chlorophenol) PCMX: p-chloro-m-xylenol CMC: p-chloro-m- Cresol Example 1 1% of a rotten starch slurry was added to a calcium carbonate slurry for papermaking (pH 9.9) to prepare a test sample. The drug was prepared by mixing HMAX and PCMX in various ratios. Each drug was added to the sample sample, and the viable cell count of bacteria, mold and yeast after incubation at 30 ° C for 48 hours was measured.
The concentration was determined to be 0 ³ cells / ml or less. The result is shown in FIG.
2, 3 and Table 1.

[0030]

[Table 1]

From FIGS. 1, 2, and 3 and Table 1, the drug (HMAE
And PCMX) for HMA against bacteria, mold and yeast.
The best effect is shown at a ratio of E: PCMX = 9: 1. Therefore, the other experiments (HMAE and M
Only BCP, HMAE to OPP, HMAE to CMC) at a ratio of 9: 1 were examined. Example 2 A standard sample Escherichia coli was inoculated into a buffer solution having a pH of 9.0, which was used as a test sample, and each drug shown in Table 2 was added. The viable cell count of this sample was measured when the L-shaped tube was shaken at 30 ° C. for 3 hours.

[0032]

[Table 2]

Example 3 Mineral oil: 70 parts by weight, oleic acid: 4.5 parts by weight, triethanolamine: 3 parts by weight, Ionet MO-600
(Sanyo Chemical Co., Ltd. sf): 7.5 parts by weight, Ionette S-80 (Sanyo Chemical Co., Ltd. s.f): 15 parts by weight of a composition was prepared and diluted 20 times with industrial water. (PH 8.9) and used as a sample.

The following chemicals were added to this sample sample at 30 ° C.
The appearance and the viable cell count when the sample was left to stand in a constant temperature bath were measured daily. (Bacterial species: Pseudomonas sp., Micrococcus sp.)

[0035]

[Table 3]

Example 4 A test sample was prepared by inoculating the standard bacterium Escherichia coli in a buffer solution of pH 4.0, and each drug was added. The MIC ^* was obtained when this sample was shaken in an L-shaped tube at 30 ° C. for 3 hours.

[0037]

[Table 4]

Examples 1 and 4: Example 1 was conducted at pH 9.9.
It was a Lucari sample, and Example 4 was weakly acidic at pH 4.0.
It is a sample. To these, the industrial antimicrobial agent of the present invention is added.
When added, drugs common to both (HMAE and PCMX =
Compared with 9: 1), MIC ^*However, Example 1 is 80, actual
Example 4 is 100. Therefore, the industrial antimicrobial of the present invention
Agents have a particularly good effect on alkaline target systems
Demonstrate.

[0039]

INDUSTRIAL APPLICABILITY The industrial antimicrobial agent of the present invention is particularly effective when the target system is alkaline and requires a small amount of the drug, and is effective against any of bacteria, fungi and yeasts and has long-term efficacy. Persists.

[Brief description of drawings]

FIG. 1 shows the synergistic effect of HMAE and PCMX on bacteria.

FIG. 2 shows the synergistic effect of HMAE and PCMX on fungi.

FIG. 3 shows the synergistic effect of HMAE and PCMX on yeast.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display location (A01N 33/08 31:14)

Claims (11)

[Claims] 1. A general formula (I): (In the formula, R is a lower alkyl group which may be substituted with a hydroxy group, and n is an integer of 1 to 3).
Substituted N-hydroxymethylamine and its polycondensate (n
= 3, the formula: And (2) a) the general formula (II): (In the formula, m represents 1 or 2) and b) the general formula (III): (In the formula, R ¹ and R ³ are the same or different and each represents a hydrogen atom or a halogen atom; R ² represents a hydrogen atom or a hydroxyl group;
Represents one bond, a lower alkylene group or a sulfur atom. ) At least one substituted phenol compound selected from the compounds represented by the formula (1) is contained as an active ingredient. 2. The industry according to claim 1, wherein a compound of the general formula (I) in which R is an ethyl or hydroxyethyl group or a polycondensate thereof and a compound of the general formula (II) in which m is 2 are used as active ingredients. Antimicrobial agent. 3. A compound of general formula (I) wherein R is a hydroxyethyl group, n is 1, and R ¹ and R ³ are both chlorine atoms, R
The industrial antimicrobial agent according to claim 1, wherein ² is a compound of the general formula (III) having a hydroxy group as an active ingredient. 4. A compound of general formula (I) or a polycondensate thereof and a compound of general formula (II) or general formula (III) are contained in a polymerization ratio of 20: 1 to 1: 9. Item 1. The industrial antimicrobial agent according to Item 1. 5. The compound of the general formula (I) or a polycondensate thereof and the compound of the general formula (II) or the general formula (III) are contained in a polymerization ratio of 9: 1 to 1: 9. Item 1. The industrial antimicrobial agent according to Item 1. 6. An industrial antioxidant comprising at least one compound of the general formula (I) or a polycondensate thereof according to claim 1 and at least one compound of the general formula (II) and the general formula (III). Microbial agent. 7. A compound of the general formula (I) or a polycondensate thereof in an amount of 60 to 99 parts by weight, and a compound of the general formula (II) or the general formula (II
The industrial antimicrobial agent according to claim 6, which comprises 40 to 1 part by weight of the compound of I). 8. The general formula (I) according to claim 1 as a target system.
50 to 1000 mg / l of the compound of claim 1 or its polycondensate and 5 to 400 mg / l of the compound of general formula (II) or general formula (III) according to claim 1 are added in combination to inhibit the growth of microorganisms. Method. 9. A combination ratio of the compound of the general formula (I) or the polycondensate thereof and the compound of the general formula (II) or the general formula (III) in a weight ratio of 20: 1 to 1: 9. Item 9. A method for suppressing proliferation according to item 8. 10. The method for inhibiting growth according to claim 8 or 9, wherein the target system contains water and its pH is alkaline. 11. The pH of the target system is 9 or higher.
10. The method for suppressing growth according to any one of 10 to 10.