WO2000038520A9 - Antimicrobial compositions - Google Patents

Abstract

Antimicrobial compositions containing 2-pyridinethiol-1-oxide zinc salt and 2-n-octyl-4-isothiazolin-3-one which have a high safety, a potent efficacy and a broad antimicrobial spectrum.

Description

 Description Antimicrobial composition Technical field

 The present invention relates to an antimicrobial composition useful for industrial use. More specifically, the combination of 2-pyridinethiol-1 zinc oxide and 2-n-octyl-4-isothiazolin-13-one provides a synergistic antimicrobial effect of these compounds. Agent composition. Background 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. However, these heavy metal compounds are highly toxic and may cause harm to human health. Furthermore, the use of heavy metal compounds as antimicrobial agents is not appropriate, as they can lead to environmental destruction.

 Many non-metallic antimicrobial agents (eg, organic iodine compounds, nitrile compounds, isothiazolone compounds, benzimidazole compounds, pyrithione compounds) developed to solve such problems of heavy metal compounds Is selective in its antimicrobial spectrum. Therefore, even if these non-metallic antimicrobial agents are applied to industrial products or industrial raw materials, especially organic materials (eg, fibers, paints, sizing agents, etc.), these antimicrobial agents have no effect. Alternatively, microorganisms that are difficult to play grow and proliferate, causing contamination of industrial products and the like, and deterioration (for example, deterioration) of industrial raw materials. Therefore, satisfactory antibacterial effects cannot be obtained with conventional antimicrobial compositions.

For this reason, attempts have been made to combine two or more antimicrobial agents to broaden the antimicrobial spectrum and increase the antimicrobial activity. However, usually only one type of antimicrobial is effective, or an arithmetic average Only effects can be obtained.

 (Problems to be solved by the invention)

 An object of the present invention is 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. Disclosure of the invention

 (Means for solving the problem)

 The present inventors have conducted intensive studies in order to solve the above-mentioned problems, and as a result, the combination of 2-pyridinethiol-1-oxoxide zinc salt and 2-n-octyl-4-isothiazoline-3-one was expected. It has been found that a synergistic effect can be obtained. In other words, they have 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 broader antibacterial spectrum can be obtained. I came to.

 According to the present invention, there is provided an antimicrobial agent composition containing 2-pyridinethiol-11-oxide zinc salt and 2-n-octyl-4-isothiazolin-3-one.

 In one embodiment, the antimicrobial composition of the present invention is a composition that inhibits the growth of, or kills, bacteria, yeast, or algae. In a preferred embodiment, the antimicrobial composition of the present invention is a composition that inhibits the growth of bacteria or algae or kills these microorganisms.

 In a particularly preferred embodiment, the antimicrobial composition of the present invention is a composition that inhibits bacterial growth or kills bacteria.

 In another particularly preferred embodiment, the antimicrobial composition of the present invention is a composition that inhibits the growth of or kills algae.

Preferably, the weight ratio of the 2-pyridinethiol-1-oxide zinc salt to the 2-n-octyl-4-isothiazolin-3-one is in the range of 20: 1 to 1:20. More preferably, the weight ratio of the 2-pyridinethiol-11-oxide salt to the 2-n-octyl-4-isothiazolin-3-one is as follows: 5: 1 to 1: 5. BEST MODE FOR CARRYING OUT THE INVENTION

 As used herein, the term "antimicrobial composition" refers to a composition that has the effect of inhibiting the growth of bacteria, yeast, or algae, or killing these microorganisms.

 A. Composition of antimicrobial composition

 A. 1. Active ingredients

 The antimicrobial composition of the present invention contains 2-pyridinethiol-11-year-old zinc oxide salt and 2-n-octyl-4-isothiazolin-3-one as active ingredients.

 2-Pyridinethiol-1-oxide zinc salt can be synthesized by the method described in US Pat. No. 3,583,999.

 2-n-octyl-4-isothiazolin-3-one can also be synthesized by the method described in J. Heterocycl. Chem. (1971), 8 (4), 571-580.

 The ratio of 2-pyridinethiol-1-oxoxide zinc salt to 2-n-octyl-4-isothiazolin-3-one in the antimicrobial agent composition depends on the type of the target microorganism and the above composition as an antimicrobial agent. It can be selected appropriately depending on the conditions used. Usually, the ratio of 2-pyridinethiol-1-oxide zinc salt to 2-n-octyl-4-isothiazolin-3-one is 20: 1 to 1:20, preferably 5: 1 to 20% by weight. 1: 5, particularly preferably 3 ::! ~ 1: The range is 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 may be simply a mixture of zinc 2-pyridinethiol-1-oxide and 2-n-octyl-4-isothiazolin-3-one, but is preferably used. May contain, in addition to 2-pyridinethiol-1-oxide zinc salt and 2-n-octyl-4-isothiazolin-3-one, suitable solvents and dispersants or carriers or other components.

The total content of 2-pyridinethiol-1-oxide zinc salt and 2-n-octyl-4-isothiazolin-3-one in the composition of the present invention depends on the dosage form and the purpose of use. Usually, it is 0.1% to 95% by weight, preferably 0.2% to 60% by weight of the whole antimicrobial composition obtained, although it depends on the target.

 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 in general, when used in fibers, paints, adhesives, etc. A good effect can be obtained with about 1 to 100 Omg Z kg.

 A. 2. Solvents and dispersants

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

 Solvents that can be used in the antimicrobial composition of the present invention include any solvent that does not adversely affect the active ingredient, such as 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.) , Aromatic hydrocarbons (eg, benzene, toluene, xylene, solvent naphtha, methylnaphthalene, etc.), halogenated hydrocarbons (eg, chloroform, carbon tetrachloride, etc.), acid amides (eg, Etc. Mechiruhorumua bromide), esters (e.g., methyl acetate, acetic Echiruesuteru, butyl acetate ester, fatty acid glycerin ester, etc.), and nitriles such (for example, such as Asetonitoriru) and the like. These solvents can be used alone or in combination of two or more.

Examples of the dispersant that can be used in the antimicrobial composition of the present invention include any dispersant that 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-based compounds and the like can be mentioned. These dispersants can be used alone or in combination of two or more. A. 3. Carrier

 The carrier that can be used in the antimicrobial composition of the present invention includes any carrier that does not adversely affect the active ingredient, for example, clays (eg, kaolin, bentonite, acid clay, etc.), talcs (eg, talc) Powder, laurite powder, etc.), silicas (eg, diatomaceous earth, silicic anhydride, mica powder, etc.), alumina, sulfur powder, activated carbon, and the like. These carriers can be used alone or in combination of two or more.

 A. 4. Other ingredients

 The antimicrobial composition of the present invention further comprises other antimicrobial agents (for example, organochlorine fungicides, organophosphorus fungicides, organic iodine fungicides, organic sulfur fungicides, organic nitrogen fungicides, Organic nitrogen sulfur fungicides, benzimidazole fungicides, phenolic fungicides, organic acid ester fungicides, antibiotics, etc., insecticides (eg, natural insecticides, carbamate insecticides, organophosphorus insecticides) Etc.), adjuvants (eg, casein, gelatin, starch, alginic acid, agar, CMC, polyvinyl alcohol, vegetable oil, bentonite, cresol soap, etc.), deterioration inhibitors, fragrances and the like.

 B. Target bacteria

 As used herein, the term “antimicrobial composition” as defined above means a composition that has the effect of inhibiting the growth of bacteria, yeast, or algae, or killing these microorganisms. I do.

However, the antimicrobial composition of the present invention can act widely on not only the bacteria, yeast, or algae defined above, but also fungi. The antimicrobial composition of the present invention is obtained by prescribing 2-pyridinethiol-1-oxide zinc salt or 21n-year-old butyl-4-isothiazolin-3-one alone to these microorganisms in general. It has a broader antimicrobial spectrum than the resulting antimicrobial composition. It is particularly effective against bacteria, yeast, or algae, and is particularly effective against bacteria and algae. Examples of the microorganisms that can be inhibited from growing or killed by the antimicrobial agent composition of the present invention include bacteria such as Bacillus, Staphylococcus, Enterobacter, Escherichia, and Pseudomonas. , As pergi 1 lus, Au reobasidium, Chaetomium, CI adosporium, G 1 ί oc Fungi such as 1 adium genus, Penici 11ium genus, Trich odorma genus, yeasts such as Candida genus, Rhod otorula genus, Ch1 ore

Algae such as the genus 1 la, the genus Trente pohllia, the genus Nostoc, and the genus Phormidium are included.

 The antimicrobial composition of the present invention can be applied to various industrial products or industrial raw materials. Examples of such various industrial products or industrial raw materials include fibers, paints, adhesives, wood, leather, processed paper products, electronic components, wall coverings, and resin molded products.

(Example)

 The following examples further illustrate the antimicrobial efficacy of the antimicrobial composition of the present invention. The term "M I:" used in this Example refers to the minimum inhibitory concentration (P Pm) of the active ingredient in the antimicrobial composition. More specifically, in an antimicrobial composition capable of inhibiting the growth of bacteria, fungi or algae, 2-pyridinethiol-1-oxide zinc salt and 2-n-octyl-4-isothiazoline-3 — Refers to the minimum concentration of the mixture with ON.

 (Preparation of bacterial solution for inoculation)

 The bacterial solution for inoculation used in Example 1 was prepared as follows. Five separate bacteria (Bacillus subtilis IF 03134, Staphylococcus aureus I F012732, Enterobacteria aerogenes IF 01 3534, Escherichiacoli IF 03972, and Pseud) omo nasaer uginosa IF 013275) was inoculated, and cultured with shaking at 30 ° C. for 4 to 6 hours to prepare 5 kinds of bacterial solutions for inoculation.

 (Preparation of spore suspension for inoculation)

 The spore suspension for inoculation used in Example 2 was prepared as follows. Each fungus

Four species (As pergillusni ger I F06341, G liocladi um virens IF 06355, Penici 1 1 i um funicu 1 os um IF 06345, and Trichoder ma viride IF 05720) were added to four drug-free potato dextrose agar plates. Cultured on the ground to form spores. Next, the fungal spores were dispersed in sterile water to which 0.005% of a lubricant was added to prepare four kinds of spore suspensions for inoculation.

 (Preparation of algae suspension for inoculation)

 The algal suspension for inoculation used in Example 3 was prepared as follows. BB liquid medium (50 ml) was inoculated with ChlorellapyrenoidosaNiES226, and cultured with shaking at 25 for 14 days to prepare an algal suspension for inoculation.

 (Example 1)

 Add 2-pyridinethiol-1-oxide zinc salt and 2-n-octyl-4-isothiazolin-3-one to dimethylsulfoxide in the respective weight ratios shown in Table 1 below to obtain 5 antimicrobial agents. An agent composition was prepared. Next, a serially diluted aqueous solution (0.2 ml) of the antimicrobial agent composition was added to the ordinary broth liquid medium (10 ml) to prepare each test medium. Each test medium is inoculated with the above inoculum (0.1 ml), cultured at 30 for 24 hours, and the presence or absence of bacterial growth is determined by visual inspection of the turbidity of the medium. did. The minimum concentration of a mixture of 2-pyridinethiol-11-oxide zinc salt and 2-n-octyl-4-isothiazolin-3-one that could inhibit bacterial growth in the medium was defined as MIC. Table 1 shows the MIC for each bacterium of the antimicrobial composition at each weight ratio.

 1) Drug A: 2-pyridinethiol 1-oxide zinc salt

2) Drug B: 2-n-octyl 4-isothiazoline-3-one (Example 2)

 2-Pyridinethiol-1-oxide zinc salt and 2-n-octyl-4-isothiazolin-3-one were added to dimethyl sulfoxide at the respective weight ratios shown in Table 2 below to give 5 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 test medium was inoculated with the spore suspension (1 ml) for inoculation described above, cultured at 28 ° C for 7 days, and then visually inspected for the growth of the fungus on the medium to determine whether the fungus had grown. Each was decided. The minimum concentration of a mixture of 2-pyridinethiol-11-oxide zinc salt and 2_n-octyl-4-isothiazolin-3-one that could inhibit fungal growth on the medium was defined as MIC. Table 2 shows the MIC for each fungus of the antimicrobial composition at each weight ratio. Table 2

 1) Drug A: 2-pyridinethiol-1-oxoxide zinc salt

 2) Drug B: 2—n—tactyl 4-isothiazoline—3—one

(Example 3)

Zinc 2-pyridinethiol-1-oxide and 2-n-octyl-4-isothiazolin-3-one were added to dimethyl sulfoxide at the weight ratios shown in Table 3 below to give 5 A microbial agent composition was prepared. Next, this antimicrobial group A serially diluted aqueous solution (0.1 ml) of the product was added to BB agar medium (15 ml) to prepare each test medium. Each test medium is inoculated with the above algal suspension for inoculation (lml), cultured at 25 ° C, 15001 ux for 14 days, and then visually examined for algal growth on the medium. Was determined respectively. The minimum concentration of a mixture of 2-pyridinethiol-1-oxide zinc salt and 2-n-octyl-4-isothiazolin-3-one that could inhibit the growth of algae on the medium was defined as MIC. Table 3 shows the MIC for the algae of the antimicrobial composition at each weight ratio. Table 3

 1) Drug A: 2 Pyridinethiol-1 year old zinc oxide salt

 2) Drug B: 2n-octyl-4-isothiazoline-3-one From Tables 1, 2 and 3, the antimicrobial composition of the present invention is different from the conventional antimicrobial composition by the synergistic effect of the active ingredient. It is shown to have higher efficacy and a broader antibacterial spectrum. 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 kept very low compared to when the active ingredient is used alone. Industrial applicability

ADVANTAGE OF THE INVENTION According to this invention, the antimicrobial agent composition which contains 2-pyridinethiol-1-oxide zinc salt and 2-n-octyl- 4-isothiazolin-3-one as an active ingredient is obtained. By combining these two active ingredients, An antimicrobial composition having a synergistic effect of components, 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 and has little effect on the environment. INDUSTRIAL APPLICABILITY The antimicrobial composition of the present invention is effective for the preservative and fungal control of various industrial products and industrial raw materials.

Claims

The scope of the claims An antimicrobial composition comprising 1.2-pyridinethiol 1-oxide zinc salt and 2-n-octyl-4-isothiazolin-3-one. 2. The weight ratio of the 2-pyridinethiol-11-year-old zinc oxide salt to the 2-n-octyl-4-isothiazolin-3-one is in the range of 20: 1 to 1:20. The antimicrobial composition according to claim 1. 3. The weight ratio of the 2-pyridinethiol-1-oxide zinc salt to the 2-n-octyl-4-isothiazolin-3-one is in the range of 5: 1 to 1: 5. 2. The antimicrobial composition according to 1.