JP2002284606A - Antimicrobial composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide antimicrobial composition being highly safe, highly effec tive, and having a broad antibacterial spectrum. SOLUTION: This antimicrobial composition contains 2-bromo-2- nitro-1,3-propanediol and poly[oxyethlene(dimethyliminio)ethylene(dimethyliminio) ethylenedichloride].

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an antimicrobial composition useful for industrial applications. More specifically, 2-bromo-
An antimicrobial composition having a synergistic effect of these compounds by combining 2-nitro-1,3-propanediol and poly [oxyethylene (dimethyliminio) ethylene (dimethyliminio) ethylenedichloride]. .

[0002]

2. Description of the Related Art Conventionally, inorganic or organic compounds containing heavy metals such as mercury, tin and copper (hereinafter referred to as "heavy metal compounds") have been widely used as antimicrobial agents for industrial products or industrial raw materials. ing. But,
Since these heavy metal compounds are highly toxic, there is a risk of adversely affecting the human body. Furthermore, it is not appropriate to use heavy metal compounds as antimicrobial agents, because they can lead to environmental destruction.

Many nonmetallic antimicrobial agents (eg, organic iodine compounds, nitrile compounds, isothiazolone compounds, benzimidazole compounds, pyrithione compounds) developed to solve the problems of such heavy metal compounds. Compound) has selectivity in its antimicrobial spectrum. For this reason, these non-metallic antimicrobial agents
Industrial products or raw materials, especially organic materials (for example,
Even when applied to emulsions, paints, pastes, etc.), these antimicrobial agents do not work, or microorganisms that do not work well grow and proliferate, contaminating industrial products and the like, or altering the quality of industrial raw materials (for example, Deterioration). Therefore, satisfactory antimicrobial effects cannot be obtained with conventional antimicrobial compositions.

[0004] Therefore, attempts have been made to broaden the antibacterial spectrum and increase the antimicrobial activity by combining two or more antimicrobial agents. However, usually, only one type of antimicrobial agent exerts its effect, or only an arithmetic average effect is obtained.

[0005]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and an object of the present invention is to provide an antimicrobial composition having high safety, high efficacy, and a broad antibacterial spectrum. It is to be.

[0006]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that
It has been found that an unexpected synergistic effect can be obtained by a combination of nitro-1,3-propanediol and poly [oxyethylene (dimethyliminio) ethylene (dimethyliminio) ethylenedichloride]. That is, it has been found that the combination of the above two compounds enhances the potency as compared with the case where each compound is used alone, and that an antimicrobial composition having a wider antibacterial spectrum can be obtained, leading to the completion of the present invention. Was.

According to the present invention, an antimicrobial agent containing 2-bromo-2-nitro-1,3-propanediol and poly [oxyethylene (dimethyliminio) ethylene (dimethyliminio) ethylenedichloride] A composition is provided.

Preferably, the weight ratio of the 2-bromo-2-nitro-1,3-propanediol to the poly [oxyethylene (dimethyliminio) ethylene (dimethyliminio) ethylenedichloride] is 20: 1 to
The range is 1:20. More preferably, the weight ratio of the 2-bromo-2-nitro-1,3-propanediol to the poly [oxyethylene (dimethyliminio) ethylene (dimethyliminio) ethylene dichloride] is 5: 1. The range is 1: 5.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION As used herein, the term "antimicrobial composition" refers to a composition having an effect of inhibiting the growth of bacteria, fungi, yeasts, algae, etc., or killing these microorganisms. Means things.

A. Composition of antimicrobial composition A. 1. Active Ingredient The antimicrobial composition of the present invention comprises 2-bromo-2-nitro-1,3-propanediol and poly [oxyethylene (dimethyliminio) ethylene (dimethyliminio) ethylenedichloride] as active ingredients. contains.

2-bromo-2-nitro-1,3-propanediol can be synthesized, for example, by the method described in JP-B-49-20761.

Poly [oxyethylene (dimethyliminio) ethylene (dimethyliminio) ethylene dichloride] is available, for example, as WSCP (60% aqueous solution) sold by Bachman Laboratories.

2-Bromo-2-nitro-1,3-propanediol and poly [oxyethylene (dimethyliminio) ethylene (dimethyliminio) in the antimicrobial composition
Ethylene dichloride] can be appropriately selected depending on the kind of the target microorganism and the conditions under which the composition is used as an antimicrobial agent. Usually, the ratio between 2-bromo-2-nitro-1,3-propanediol and poly [oxyethylene (dimethyliminio) ethylene (dimethyliminio) ethylene dichloride] is 20: 1 to 1:20 by weight. , Preferably 5: 1 to 1:
5, particularly preferably in the range of 3: 1 to 1: 3.

The antimicrobial composition of the present invention can be used in a form depending on the purpose of use. For example, the antimicrobial composition of the present invention is simply a mixture of 2-bromo-2-nitro-1,3-propanediol and poly [oxyethylene (dimethyliminio) ethylene (dimethyliminio) ethylenedichloride]. May be present, but preferably 2-
In addition to bromo-2-nitro-1,3-propanediol and poly [oxyethylene (dimethyliminio) ethylene (dimethyliminio) ethylenedichloride] may contain suitable solvents and dispersants or carriers or other components. .

The total content of 2-bromo-2-nitro-1,3-propanediol and poly [oxyethylene (dimethyliminio) ethylene (dimethyliminio) ethylene dichloride] in the composition of the present invention is as follows: Although it depends on the dosage form and the purpose of use, it is usually 0.1% by weight to 95% by weight of the whole obtained antimicrobial agent composition,
Preferably it is 0.2% by weight to 60% by weight.

The amount of the antimicrobial agent composition of the present invention varies depending on the composition and the type and concentration of the target microorganism, but is generally used in emulsions, paints, pastes and the like. Has a good effect at about 1 to 10,000 mg / kg.

A. 2. Solvent and dispersant When the target system is various industrial aqueous systems, it is preferable to prepare a liquid containing a solvent and a dispersant, as described later, in consideration of the dissolution and dispersibility of the active ingredient. .

The solvent which can be used in the antimicrobial composition of the present invention includes any solvent which does not adversely affect the active ingredient, for example, water, alcohols (eg, methyl alcohol, ethyl alcohol, ethylene glycol, propylene glycol) , Diethylene glycol, glycerin, etc.), ketones (eg, acetone, methyl ethyl ketone, etc.), ethers (eg, dioxane, tetrahydrofuran, cellosolve, diethylene glycol dimethyl ether, etc.), aliphatic hydrocarbons (eg, hexane, kerosene, etc.), aromatics Hydrocarbons (eg, benzene, toluene, xylene, solvent naphtha, methylnaphthalene, etc.), halogenated hydrocarbons (eg, chloroform, carbon tetrachloride, etc.), acid amides (eg, dimethylformamide) ) Esters (e.g., methyl acetate, ethyl acetate, acetic butyl ester, fatty acid glycerin ester, etc.), and nitriles (e.g., acetonitrile), and the like.
These solvents can be used alone or in combination of two or more.

The dispersant which can be used in the antimicrobial composition of the present invention includes any dispersant which does not adversely affect the active ingredient, for example, a surfactant. Examples of such surfactants include soaps, sulfates of higher alcohols, alkylsulfonic acids, alkylarylsulfonic acids, quaternary ammonium salts, oxyalkylamines,
Fatty acid esters, polyalkylene oxide compounds,
Anhydrosorbitol compounds and the like can be mentioned. These dispersants can be used alone or in combination of two or more.

A. 3. Carrier As the carrier that can be used in the antimicrobial composition of the present invention, any carrier that does not adversely affect the active ingredient, for example,
Clays (e.g., kaolin, bentonite, acid clay, etc.), talcs (e.g., talc powder, laurite powder, etc.),
Silicas (for example, diatomaceous earth, silicic acid anhydride, mica powder, etc.), alumina, sulfur powder, activated carbon and the like can be mentioned.
These carriers can be used alone or in combination of two or more.

A. 4. Other Ingredients The antimicrobial composition of the present invention may further contain other antimicrobial agents (for example, organochlorine germicides, organophosphorus germicides, organic iodine germicides, organic sulfur germicides, organic nitrogen germicides). Agents, organic nitrogen-sulfur fungicides, benzimidazole fungicides, phenolic fungicides, organic acid ester fungicides, antibiotics, etc.), insecticides (eg, natural insecticides, carbamate insecticides, organophosphorus insecticides) Agents, etc.), adjuvants (eg, casein, gelatin, starch, alginic acid, agar, C
MC, polyvinyl alcohol, vegetable oil, bentonite,
Cresol soap), a deterioration inhibitor, a fragrance and the like.

B. Bacteria of Interest The antimicrobial compositions of the present invention generally act broadly on bacteria, fungi, yeasts, algae, and the like, and
It has a broader antimicrobial spectrum than the antimicrobial composition obtained by formulating 2-nitro-1,3-propanediol or poly [oxyethylene (dimethyliminio) ethylene (dimethyliminio) ethylenedichloride] alone. . Microorganisms whose growth can be inhibited or killed by the antimicrobial composition of the present invention include Bacillus genus and Staphylococcus.
ccus), Enterobacter, Escherichia, Pseudodom
onas) Bacteria such as genus, Aspergillus
Genus, Aureobasidium, Chaetomium, Cladospori
um), Gliocladium, Penicillium, Trichoderm
a) Fungi such as genus, yeasts such as Candida and Rhodotorula, Chlorella
Genus, Sumiremo (Trentepohlia), Nostoc (Nosto)
c) genus, algae such as genus Phormidium and the like.

The antimicrobial composition of the present invention can be applied to various industrial products or industrial raw materials. Such various industrial products or industrial raw materials include emulsions, paints, sizing agents, metal working oils, and the like.

[0024]

The following examples further illustrate the antimicrobial efficacy of the antimicrobial composition of the present invention. The term "MIC" used in this example refers to the minimum inhibitory concentration (ppm) of an active ingredient in an antimicrobial composition. More specifically, 2-bromo-2-nitro- in an antimicrobial composition capable of inhibiting the growth of bacteria or algae.
Refers to the minimum concentration of a mixture of 1,3-propanediol and poly [oxyethylene (dimethyliminio) ethylene (dimethyliminio) ethylene dichloride].

(Preparation of bacterial solution for inoculation) The bacterial solution for inoculation used in Example 1 was prepared as follows. In five separate normal broth broths (10 ml), five bacteria, Bacillus subtilis IFO 3134,
Staphylococcus aureus
us) IFO 12732, Enterobacter erogenes (Enter
bacterium aerogenes IFO 13534, Escherichia coli IFO 3972, and Pseudomonas aeruginosa IFO 13275
, And cultured with shaking at 30 ° C. for 4 to 6 hours.
A seed inoculum was prepared.

(Preparation of Spore Suspension for Inoculation) The spore suspension for inoculation used in Example 2 was prepared as follows. Four fungi, Aspergillus niger
s niger) IFO 6341, Gliocladium virens (Gli)
ocladium virens) IFO 6355, Penicillium funiculosum IFO 6345, and Trichoderma viride IFO 5720
Was cultured on four drug-free potato dextrose agar plates to form spores. Next, the fungal spores were dispersed in sterilized water containing 0.005% of a lubricant,
Four spore suspensions for inoculation were prepared.

(Preparation of Algal Suspension for Inoculation) The algal suspension for inoculation used in Example 3 was prepared as follows. B
Chlorella pyrenoidosa NIES 226 in old's Basal liquid medium (50 ml)
Was inoculated and cultured with shaking at 25 ° C. for 14 days to prepare an algal suspension for inoculation.

Example 1 2-bromo-2-nitro-
1,3-propanediol and poly [oxyethylene (dimethyliminio) ethylene (dimethyliminio) ethylene dichloride] were added to ion-exchanged water at the respective weight ratios shown in Table 1 below, and 5 A microbial agent composition was prepared. Then, normal broth liquid medium (10ml)
Then, a serially diluted aqueous solution (0.2 ml) of the antimicrobial agent composition was added to each to prepare each test medium. Each test medium was inoculated with the above inoculum (0.1 ml), and 30
After culturing at 24 ° C. for 24 hours, the presence or absence of bacterial growth was determined by visual inspection of the turbidity of the medium. A minimum of a mixture of 2-bromo-2-nitro-1,3-propanediol and poly [oxyethylene (dimethyliminio) ethylene (dimethyliminio) ethylenedichloride] which can inhibit the growth of bacteria in the medium. The concentration was taken as MIC. Table 1 shows the MIC for each bacterium of the antimicrobial composition at each weight ratio.

[0029]

[Table 1]

Example 2 2-Bromo-2-nitro-
1,3-propanediol and poly [oxyethylene (dimethyliminio) ethylene (dimethyliminio) ethylene dichloride] were added to ion-exchanged water at the respective weight ratios shown in Table 2 below, and 5 antioxidants were added. A microbial agent composition was prepared. Next, a serially diluted aqueous solution (0.3 ml) of the antimicrobial composition was added to a potato dextrose agar medium (15 ml) to prepare each test medium. Each of the test media is inoculated with the spore suspension (1 ml) for inoculation described above,
After culturing at 28 ° C. for 7 days, the presence or absence of fungal growth was determined by visual inspection of the fungal growth on the medium. 2-bromo-, which can inhibit the growth of fungi on the medium.
The minimum concentration of a mixture of 2-nitro-1,3-propanediol and poly [oxyethylene (dimethyliminio) ethylene (dimethyliminio) ethylenedichloride] was defined as MIC. Table 2 shows the MIC for each fungus of the antimicrobial composition at each weight ratio.

[0031]

[Table 2]

Example 3 2-Bromo-2-nitro-
1,3-Propanediol and poly [oxyethylene (dimethyliminio) ethylene (dimethyliminio) ethylene dichloride] were added to ion-exchanged water at the respective weight ratios shown in Table 3 below, and 5 A microbial agent composition was prepared. Next, a serially diluted aqueous solution (0.1 ml) of the antimicrobial composition was added to Bold's Basal agar medium (15 ml) to prepare each test medium. Each test medium was inoculated with the above inoculated algal suspension (1 ml), cultured at 25 ° C. and 1500 lux for 14 days, and then visually examined for the growth of algae on the medium to determine whether or not the algae had grown. Each was decided. A minimum of a mixture of 2-bromo-2-nitro-1,3-propanediol and poly [oxyethylene (dimethyliminio) ethylene (dimethyliminio) ethylenedichloride] that can inhibit the growth of algae on the medium. The concentration was taken as MIC. Table 3 shows the MICs of the antimicrobial composition at each weight ratio with respect to algae.

[0033]

[Table 3]

From Tables 1, 2 and 3, it can be seen that the antimicrobial composition of the present invention has higher efficacy and a broader antibacterial spectrum than conventional antimicrobial compositions due to the synergistic effect of the active ingredients. Is shown. Furthermore, it is shown that the concentration of the antimicrobial composition used to inhibit the growth of the same amount of bacteria, fungi or algae can be extremely low as compared to the case where the active ingredient is used alone.

[0035]

According to the present invention, 2-bromo-2-nitro-1,3-propanediol and poly [oxyethylene (dimethyliminio) ethylene (dimethyliminio) ethylenedichloride] are contained as active ingredients. An antimicrobial composition is obtained. By combining these two active ingredients, a synergistic action of these ingredients is obtained, and an antimicrobial composition having high safety, high efficacy, and a broad antibacterial spectrum is provided. Furthermore, since the concentration of the active ingredient contained in the antimicrobial composition of the present invention can be kept low, it can be prepared at extremely low cost,
The impact on the environment is small. INDUSTRIAL APPLICABILITY The antimicrobial composition of the present invention is effective in preserving and preventing fungi of various industrial products and industrial raw materials.

Claims (3)

[Claims] 1. An antimicrobial composition comprising 2-bromo-2-nitro-1,3-propanediol and poly [oxyethylene (dimethyliminio) ethylene (dimethyliminio) ethylenedichloride]. 2. The 2-bromo-2-nitro-1,3-
The antimicrobial agent according to claim 1, wherein the weight ratio of propanediol to the poly [oxyethylene (dimethyliminio) ethylene (dimethyliminio) ethylene dichloride] is in the range of 20: 1 to 1:20. Composition. 3. The 2-bromo-2-nitro-1,3-
The antimicrobial agent according to claim 1, wherein the weight ratio of propanediol to the poly [oxyethylene (dimethyliminio) ethylene (dimethyliminio) ethylene dichloride] is in the range of 5: 1 to 1: 5. Composition.