JPH11217308A - Microbicide for industrial use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a microbicide which is free from halogen atoms and shows fungicidal, antiseptic and antimicrobial effects by making the microbicide include an oxathiazine compound and a benzimidazol compound. SOLUTION: This microbicide is obtained by including (A) an oxathiazine compound e.g. 3-benzo[b]thien-2-yl-5,6-dihydro-1,4,2-oxathiazine-4-oxide or the like} of formula I (R1 and R2 are each H or a lower alkyl) and (B) a benzimidazol compound [e.g. methyl 2-benzimidazol-carbamate, 2-(4-thiazoyl) benzimidazol or the like] of formula II (R3 is H or a lower alkyl; X is a carbamate group, a thiazolyl group or the like). It is favorable that the above microbicide contains the component A and B in amounts of 95-5 pts.wt., respectively.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an industrial germicide, and more particularly, to an industrial germicide exhibiting fungicidal, antiseptic and antibacterial effects.

[0002]

2. Description of the Related Art Conventionally, various industrial waters such as a paper pulp mill and a cooling water circulation process, and metal working oils such as cutting oils,
Casein, starch paste, glue, coated paper, paper coating liquid, surface sizing agent, paint, adhesive, synthetic rubber latex, printing ink, polyvinyl alcohol film, vinyl chloride film, plastic products, cement admixture, etc. In industrial products, harmful microorganisms are easy to propagate, causing a decrease in productivity and quality, and generation of offensive odor. Therefore, many industrial germicides are used for controlling and sterilizing the propagation of these microorganisms.

[0003]

However, if these existing industrial germicides are used for a long period of time, resistant bacteria (fungi and fungi) are generated, and it is difficult to maintain their efficacy. Development of industrial germicides is desired. In many of these existing industrial germicides, compounds containing a halogen atom are used as the active ingredient. In recent years, from the viewpoints of work safety, work hygiene and environmental friendliness, these compounds contain these halogen atoms. There is a demand to reduce the use of compounds as much as possible.

Accordingly, the present invention has been made in view of such circumstances, and it is an object of the present invention to provide a novel compound which contains a compound containing no halogen atom as an active ingredient and exhibits fungicidal and antiseptic / antibacterial effects. It is to provide a safe industrial bactericide.

[0005]

In order to achieve the above object, the industrial bactericide of the present invention has the general formula (1)

[0006]

Embedded image

Wherein R 1 and R 2 each represent hydrogen or a lower alkyl group; and an oxathiazine compound represented by the general formula (2):

[0008]

Embedded image

(Wherein, R 3 represents hydrogen or a lower alkyl group, X represents a carbamate group represented by —NHCOOR ₄ (where R 4 represents an alkyl group) or a thiazolyl group). And an imidazole compound. Preferably, the oxathiazine-based compound represented by the formula (1) is
-Benzo [b] thien-2-yl-5,6-dihydro-
1,4,2-oxathiazine 4-oxide, a benzimidazole-based compound represented by the formula (2),
Methyl 2-benzimidazole carbamate and / or
Or 2- (4-thiazolyl) benzimidazole.

[0010] In the industrial fungicide of the present invention, 95 to 5 parts by weight of the benzimidazole compound represented by the formula (2) is added to 95 to 5 parts by weight of the oxathiazine compound represented by the formula (1). It is preferred to be contained in the ratio of parts.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The industrial fungicide of the present invention contains, as active ingredients, an oxathiazine compound represented by the following formula (1) and a benzimidazole compound represented by the following formula (2). . General formula (1)

[0012]

Embedded image

Wherein R 1 and R 2 each represent hydrogen or a lower alkyl group. In the formula of the oxathiazine compound represented by R 1 and R 2, the lower alkyl groups represented by R 1 and R 2 include, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, se
1 to 4 carbon atoms such as c-butyl and tert-butyl
Alkyl group. R1 and R2 are each preferably methyl.

When R1 is a lower alkyl group, one of the 5- and 6-positions of the oxathiazine ring is substituted with a lower alkyl group. In this case, preferably,
The 6-position of the oxathiazine ring is substituted with a lower alkyl group. When R1 is hydrogen, neither the 5-position nor the 6-position of the oxathiazine ring is substituted with a lower alkyl group. In this case, R1 may be deleted from the above equation (1). The most preferred embodiment of R1 is hydrogen, that is, the embodiment in which R1 is deleted in the above formula (1).

When R2 is a lower alkyl group, the benzo [b] thiene ring may be substituted at the 4-, 5-, 6- or 7-position.
Any of the positions is substituted with a lower alkyl group. In this case, the 5-position of the benzo [b] thiene ring is preferably substituted with a lower alkyl group. Also, when R2 is hydrogen, none of the 4-position to 7-position of the benzo [b] thiene ring is substituted with a lower alkyl group. In this case, R2 may be deleted from the above formula (1). The most preferred embodiment of R2 is hydrogen, ie, in the above formula (1),
In this embodiment, R2 is deleted.

Specific examples of the oxathiazine-based compound represented by the formula (1) include, for example, 3-benzo [b] thien-2-yl-5,6-dihydro-1,4,4
2-oxathiazine 4-oxide, 3- (5-methylbenzo [b] thien-2-yl) -5,6-dihydro-
1,4,2-oxathiazine 4-oxide and 3-
Benzo [b] thien-2-yl-5-hydro-6-methyl-1,4,2-oxathiazine 4-oxide and the like.

These oxathiazine compounds represented by the formula (1) may be used alone or in combination of two or more. Of these, 3-benzo [b] thien-2 is preferred.
-Yl-5,6-dihydro-1,4,2-oxathiazine 4-oxide. The oxathiazine compounds represented by the formula (1) are described in, for example,
It can be produced by the method described in Japanese Patent No. 509986.

The general formula (2)

[0019]

Embedded image

(Wherein, R 3 represents hydrogen or a lower alkyl group, X represents a carbamate group represented by —NHCOOR ₄ (where R 4 represents an alkyl group) or a thiazolyl group). In the formula of the imidazole compound, the lower alkyl group represented by R3 includes, for example, methyl, ethyl, n-propyl, isopropyl,
n-butyl, isobutyl, sec-butyl, tert-
Examples thereof include an alkyl group having 1 to 4 carbon atoms such as butyl. Preferably, methyl is used.

When R3 is a lower alkyl group, any of the 4-, 5-, 6- and 7-positions of the benzimidazole ring is substituted with a lower alkyl group. When R3 is hydrogen, none of the 4-position to 7-position of the benzimidazole ring is substituted with a lower alkyl group. In this case, R3 may be deleted from the above equation (2). R
The most preferred embodiment of 3 is hydrogen, that is, the above formula (2)
In this, R3 is deleted.

[0022] In a carbamate group represented by -NHCOOR ₄ represented by X, the alkyl group represented by R4, for example, methyl, ethyl, n- propyl, isopropyl, n- butyl, isobutyl, sec- butyl, tert- Butyl, n-pentyl, isopentyl,
Examples thereof include an alkyl group having 1 to 8 carbon atoms such as neopentyl, n-hexyl, n-heptyl, and n-octyl. Preferably, a lower alkyl group having 1 to 4 carbon atoms,
More preferably, methyl and ethyl are used. Examples of the thiazolyl group represented by X include 2-thiazolyl, 4-thiazolyl and 5-thiazolyl. Preferably, 4-thiazolyl is used.

When X is a carbamate group, specific examples of the benzimidazole compound represented by the formula (2) include, for example, methyl 2-benzimidazole carbamate and ethyl 2-benzimidazole carbamate. No. When X is a thiazolyl group, examples thereof include 2- (4-thiazolyl) benzimidazole.

These benzimidazole compounds represented by the formula (2) may be used alone or in combination of two or more. Of these, preferably, methyl 2-benzimidazole carbamate and 2- (4-thiazolyl)
And benzimidazole. These benzimidazole compounds represented by the formula (2) can be produced by a known method.

The mixing ratio of the oxathiazine-based compound represented by the formula (1) and the benzimidazole-based compound represented by the formula (2) may be, for example, the oxathiazine-based compound 95 represented by the formula (1). 5 to 95 parts by weight of the benzimidazole compound represented by the formula (2) to 5 to 5 parts by weight, preferably 80 to 20 parts by weight of the oxathiazine compound represented by the formula (1) The benzimidazole compound represented by the formula is 20 to 80 parts by weight. When the amount of the oxathiazine-based compound represented by the formula (1) is less than 5 parts by weight, the preservative / antibacterial action may be reduced. On the other hand, when the amount of the benzimidazole-based compound represented by the formula (2) is less than 5 parts by weight, The fungicidal action may be reduced.

The industrial fungicide of the present invention containing such an oxathiazine compound represented by the formula (1) and a benzimidazole compound represented by the formula (2):
Depending on the purpose of use, for example, it can be formulated into known dosage forms such as liquids (including aqueous suspensions and oils), pastes, powders, and granules and used. Preferably, a liquid preparation and a powder preparation are used. In order to prepare a liquid formulation, the oxathiazine-based compound represented by the formula (1) and the benzimidazole-based compound represented by the formula (2) may be appropriately dissolved or dispersed in a solvent in the above-described ratio.
The solvent used at this time is not particularly limited as long as the solvent can dissolve or disperse the oxathiazine-based compound represented by the formula (1) and the benzimidazole-based compound represented by the formula (2).

Specific examples of these solvents include, for example,
Water, for example, methanol, ethanol, n-propanol, iso-propanol, n-butanol, tert
Alcohol solvents such as butanol, for example, ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, 1,4-butanediol, 1,5-pentanediol, ethylene glycol monomethyl ether Glycol solvents such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and tripropylene glycol monomethyl ether; for example, ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone;
For example, dioxane, tetrahydrofuran, ether solvents such as ethyl ether, for example, ethyl acetate, butyl acetate, ester solvents such as isobutyl acetate, for example, benzene, toluene, xylene, methyl naphthalene, aromatic solvents such as solvent naphtha, For example, halogenated hydrocarbon solvents such as carbon tetrachloride, chloroform, and methylene chloride, and polar solvents such as dimethylformamide, dimethylsulfoxide, and acetonitrile are exemplified. These solvents may be used alone or in combination of two or more.

[0028] Among the liquid preparations, it is preferable to formulate as an aqueous suspension to be suspended in water. To formulate as an aqueous suspension, for example, an oxathiazine compound represented by the formula (1) may be used. The sum with the benzimidazole compound represented by the formula (2) is 1 to the obtained preparation.
What is necessary is just to make it contain so that it may be set to 70 to 70 weight%, preferably 5 to 50 weight%, and to stir and disperse it.

Further, the industrial germicide of the present invention may be added with additives known for its purpose of use, for example, other industrial germicides, surfactants, antioxidants and the like. Other industrial germicides include, for example, 5-chloro-
2-methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, 2-n-octyl-4-isothiazolin-3-one, 4,5-dichloro-
2-n-octyl-4-isothiazolin-3-one, 2
Isothiazoline-based compounds such as -methyl-4,5-trimethylene-4-isothiazolin-3-one, 1,2-benzoisothiazolin-3-one and n-butyl-benzoisothiazolin-3-one, for example, 3-iodo- 2
-Propynyl butyl carbamate, diiodomethyl-p
Organic iodine-based compounds such as toluyl sulfone and p-chlorophenyl-3-iodopropargyl formal, for example, 4,5-dichloro-1,2-dithiol-
Dithiol compounds such as 3-one, for example, 3,3
4,4-tetrachlorotetrahydrothiophene-1,1
Thiophene compounds such as -dioxide, for example, thiocarbamate compounds such as tetramethylthiuram disulfide, for example, nitrile compounds such as 2,4,5,6-tetrachloroisophthalonitrile, for example, N-
Haloalkylthio compounds such as (fluorodichloromethylthio) -phthalimide and N- (fluorodichloromethylthio) -N, N'-dimethyl-N-phenyl-sulfamide, for example, 2,3,5,6-tetrachloro-4- Pyridine compounds such as (methylsulfonyl) pyridine, for example, pyrithione compounds such as zinc pyrithione and sodium pyrithione, for example, 2-
Benzothiazole compounds such as (4-thiocyanomethylthio) benzothiazole, for example, 2-methylthio-
4-tert-butylamino-6-cyclopropylamino-s
And triazine-based compounds such as triazine.

These other industrial fungicides may be used alone or
More than one species may be used in combination. The mixing ratio varies depending on the dosage form and the purpose of use, but for example, 0.1 to 80% by weight for a liquid preparation and 10 to 99.9 for a powder preparation.
It is preferred that the content be contained in the order of weight%. Further, as the surfactant, for example, soaps, nonionic surfactants,
Known surfactants such as anionic surfactants, cationic surfactants, amphoteric surfactants, and polymer surfactants can be used, and preferably, nonionic surfactants and anionic surfactants are used. Is mentioned.

Examples of the nonionic surfactant include, for example,
Examples thereof include polyoxyalkylene aryl phenyl ether, polyoxyethylene nonyl phenyl ether, and a block copolymer of ethylene oxide and propylene oxide. Examples of the anionic surfactant include a metal salt of an alkyl benzene sulfonic acid, a metal salt of an alkyl naphthalene sulfonic acid, a polycarboxylic acid type surfactant, a metal salt of a dialkyl sulfosuccinate, a ammonium salt of polyoxyethylene distyrenated phenyl ether sulfate, Lignin sulfonic acid metal salts and the like, such as sodium salts, potassium salts, magnesium salts and the like.

Examples of the antioxidant include, for example, 2,
6-di-t-butyl-4-methylphenol, 2,2 ′
Phenolic antioxidants such as -methylenebis [4-methyl-6-t-butylphenol]; and amine antioxidants such as alkyldiphenylamine and N, N'-di-s-butyl-p-phenylenediamine. .

These surfactants and antioxidants include:
For example, in the case of a liquid, 0.1 to 20 parts by weight is added to 100 parts by weight of the liquid. The industrial bactericide of the present invention thus obtained is formulated with a new active ingredient, exhibits its effect on fungicide, antiseptic and antibacterial, and can be used as a fungicide, antiseptic and antibacterial. for that reason,
For example, various industrial waters such as paper pulp mills and cooling water circulation processes, metal working oils such as cutting oils, casein, starch paste, glue, coated paper, paper coating liquids, surface sizing agents, paints, ship bottom paints It can be effectively applied to various industrial products such as adhesives, synthetic rubber latex, printing ink, polyvinyl alcohol film, vinyl chloride film, plastic products, cement admixture, especially for coated paper and paper. It can be suitably used for applications such as coating liquids, paints, adhesives, and plastic products.
In particular, the industrial disinfectant of the present invention does not discolor even when subjected to heat treatment, so it is kneaded when melt-molding a thermoplastic product, and is suitably used, for example, when producing an antibacterial plastic product. be able to.

While many of the existing industrial germicides contain a compound containing a halogen atom as an active ingredient, the industrial germicide of the present invention uses only a compound containing no halogen atom as an active ingredient. Since it is contained, it is excellent in work safety, work hygiene and environment. The amount of the industrial bactericide of the present invention may be appropriately determined depending on the application target, and acts as an active ingredient concentration of about 0.005 to 20%, preferably about 0.01 to 5%. Preferably.

[0035]

As described above, the industrial bactericide of the present invention contains a new active ingredient and is effective in preventing fungicides and preservatives.
It has an antibacterial effect and can exert its effect even when resistant bacteria (fungi, mold, and algae) are generated against existing industrial germicides. In addition, the industrial germicide of the present invention contains only a compound containing no halogen atom as an active ingredient, and thus is excellent in work safety, work hygiene and environment.

[0036]

The present invention will be described more specifically with reference to the following examples. 1) Preparation of sample 3-benzo [b] thien-2-yl-5,6-dihydro-1,4,2-oxathiazine 4-oxide
BTO) and methyl 2-benzimidazole carbamate (hereinafter referred to as MBC) are shown in Table 1 respectively.
The active ingredient concentration in acetone dissolved in acetone at the ratio shown in (a total concentration of BTO and MBC)
Was adjusted to 1000 ppm.

In Table 1, the sample No. 2-No. Sample No. 4 is an example belonging to the category of the present invention. 1 and No. 5 is a comparative example not belonging to the category of the present invention.

[0038]

[Table 1]

2) Mold-proof test (inhibition circle method) As a test mold, Cladosporium and Cladosporioides cultured on potato dextrose liquid agar medium were used.
dosporium cladosporioides kurokawa mold, Aspergillus niger (black mold), Penicillium citrinum (blue mold)
And a mixture of these with Alternaria sp. And a Sabouraud medium solution was used as a test mold liquid.

A filter paper of 30 × 30 mm was immersed in the acetone solution of the sample prepared in the above 1), then pulled up, and dried at 40 ° C. for 1 day, so that each sample permeated each filter paper. Was prepared. Each filter paper impregnated with each sample was affixed to the center of an agar plate that had been solidified by pouring a Sabouraud medium sterilized by an autoclave into a petri dish having a diameter of 9 cm.

After spraying a certain amount of the test mold liquid,
Culture was performed under culture conditions for 4 weeks. After observing the growth state of the mold 3 weeks and 4 weeks after the culture,
Transparent zone (halo) around the filter paper that prevents the growth of microorganisms
The width of the zone of inhibition was calculated from the extent to which the bacterium was formed, and the antibacterial activity against mold was evaluated. Table 2 shows the results. In Table 2, the degree of growth is based on the following criteria.

-: No mold growth is observed on the filter paper. ±: Very slight mold growth is observed on the filter paper. +: Mold growth is observed in an area of 1/3 or less on the filter paper. In Table 2, the width of the stop band was calculated as follows. (Because the inhibition zone in the antifungal test does not form a clean ring-shaped inhibition zone like the inhibition zone in the antiseptic / antibacterial test described below, it becomes a partially spotted inhibition zone. The width of the middle inhibition zone is described as an average value measured at 5 to 6 points.)

[0043]

(Equation 1)

[0044]

[Table 2]

As is clear from Table 2, the results after 4 weeks show that Samples 2 to 4 containing both MBC and BTO were Samples 1 and 5 each containing MBC or BTO alone. It turns out that it is excellent compared with. In addition, it can be seen that the antibacterial activity against mold is the most excellent in the sample 2, that is, the composition blended with 75 parts by weight of MBC and 25 parts by weight of BTO.

3) Antiseptic / antibacterial test (inhibition circle method) Escherichia coli (Escheriachia)
coli, Escherichia coli, Gram-negative bacteria (hereinafter referred to as E. coli), and Staphylococcus aureus (Staph
ylococcus aureus, Staphylococcus aureus, Gram-positive bacteria)
(Hereinafter referred to as S. aureus), and the test bacteria solution was prepared without mixing them, and except that the culture conditions were set at 33 ° C. for 18 hours. A similar test was performed. The width of the inhibition zone was calculated from the extent to which a transparent zone (halo) for inhibiting the growth of microorganisms was formed around the filter paper, and the antibacterial activity against bacteria was evaluated. Table 3 shows the results.

[0047]

[Table 3]

As is apparent from Table 3, MBC and B
It can be seen that Samples 2 to 4 in which both TOs are blended are superior to Samples 1 and 5 in which MBC or BTO is used alone. In addition, it can be seen that the antibacterial activity against bacteria is the most excellent when the sample 4 is mixed, that is, when the ratio of MBC is 25 parts by weight and BTO is 75 parts by weight.

4) Heat Resistance Coloring Test As an example, 90 parts by weight of 6,6-nylon in the form of white powder was added with 10 parts by weight of a mixed powder blended at a ratio of 25 parts by weight of MBC / 75 parts by weight of BTO, and the powder was kept as it was. After mixing, the mixture was melted and heated at 250 ° C. for 3 minutes. After cooling to room temperature, the coloration of 6,6-nylon was visually observed.

As a comparative example, N- (fluorodichloromethylthio) -phthalimide (10 parts by weight), which is an existing industrial germicide, was used. Was visually observed. As a result, the color was light yellow in the example, but was dark brown in the comparative example.

Claims (4)

[Claims] 1. A compound of the general formula (1) (Wherein, R1 and R2 each represent hydrogen or a lower alkyl group) and an oxathiazine-based compound represented by the following general formula (2): (Wherein, R3 is hydrogen or a lower alkyl group, and X is -N
A carbamate group represented by HCOOR ₄ (wherein R 4 represents an alkyl group) or a thiazolyl group; An industrial fungicide comprising a benzimidazole compound represented by the formula (1): 2. The oxathiazine-based compound represented by the formula (1) is 3-benzo [b] thien-2-yl-
5,6-dihydro-1,4,2-oxathiazine 4-
The industrial fungicide according to claim 1, which is an oxide. 3. The industrial use according to claim 1, wherein the benzimidazole compound represented by the formula (2) is methyl 2-benzimidazole carbamate and / or 2- (4-thiazolyl) benzimidazole. Fungicide. 4. The composition according to claim 1, wherein the benzimidazole compound represented by the formula (2) is contained in a proportion of 5 to 95 parts by weight based on 95 to 5 parts by weight of the oxathiazine compound represented by the formula (1). The industrial disinfectant according to any one of claims 1 to 3.