JPH11116410A - Antifungal, mildew proofing and alga proofing composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an antifungal, mildew proofing and, algae proofing composition manifesting satisfactory effects for a long period at a less quantity of dosage, excellent in weatherability and chemical resistance by containing a specific triazine compound a specific isothiazoline compound and triacetylcyclodextrin. SOLUTION: This composition contains (A) a triazine compound expressed by formula I [R<1> , R<2> are each H, a (substituted)alkyl; R<3> , R<4> are each a (substituted)alkyl, a (substituted)cycloalkyl; X is a halogen, an alkylthio], (B) or isothiazoline compound expressed by formula II (R<5> is an alkyl; R<6> , R<7> are each H, a halogen) and (C) at least one kind of cyclodextrin selected from triacetyl α-, β-, and γ-cyclodextrins, in molar ratio (A): (B): (C) of 0.3 to 5:1:0.2 to 3, and preferably containing (D) a benzimidazole compound expressed in formula III [ring A is a (substituted) benzene ring; Z is -NHCOOR<8> (R<8> is an alkyl).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to at least one triazine compound and at least one isothiazoline compound.
And at least one of triacetyl α-, β- and γ-cyclodextrins (hereinafter, these three compounds may be collectively referred to as triacetylcyclodextrin) and, if necessary, at least one of benzimidazole compounds. And a fungicidal, fungicidal and anti-algae composition comprising:

[0002]

2. Description of the Related Art With the increase in demand for industrial water, the use of recirculating water systems has been actively promoted. In such use, suppression of the growth of microorganisms such as bacteria and mold is an important problem. . In addition to these industrial waters, with the diversification of industrial materials, not only disasters caused by the proliferation of microorganisms but also disasters caused by the occurrence of algae have become widespread. In particular, there is an urgent need to take measures against the occurrence of bacteria, mold, and algae in water-based emulsion paints, solvent paints, plastic products such as PVC, agricultural vinyl films, industrial cooling water, and the like.

[0003]

The industrial antibacterial, antifungal and antialgal compositions generally used at present are relatively low in toxicity. This is desirable from the viewpoint of cost reduction of antibacterial, antifungal and antialgal treatments. In addition, outdoor use such as outdoor paints and agricultural vinyl films are exposed to strong sunlight for a long time, and aqueous acrylic emulsion paints are weakly alkaline. It is required to be stable to alkali. Further, when the drug is eluted from the coating film or film, the effect is not long-lasting. Therefore, research has been conducted on antibacterial, antifungal, and antialgal compositions that exhibit an effect over a long period of time with a smaller amount of use and are excellent in weather resistance and chemical resistance.

[0004]

DISCLOSURE OF THE INVENTION In view of the above problems, the present inventors have conducted intensive studies in order to obtain a composition having a high control effect on bacteria, fungi and algae and having a long-lasting effect. It has been found that a composition containing a specific triazine compound, a specific isothiazoline compound and a triacetylcyclodextrin, and if necessary, a specific benzimidazole compound exhibits a synergistic effect, and the effect lasts for a long time. Based on the findings, the present inventors have further studied and completed the present invention. That is, the present invention relates to (1) a compound represented by the general formula (I):

Embedded image (In the formula, R ¹ and R ² represent a hydrogen atom or an alkyl group which may have a substituent, and R ³ and R ⁴ each represent an alkyl group or a substituent which may have a substituent. A cycloalkyl group, X represents a halogen atom or an alkylthio group.), A general formula (II)

Embedded image (Wherein, R ⁵ is an alkyl group, R ⁶ and R ⁷ are both hydrogen, or one is hydrogen and the other is a halogen atom), and triacetyl α-, β- and Bactericidal, fungicidal and anti-algal compositions comprising at least one γ-cyclodextrin,

(2) R ¹ and R 2 in the general formula (I)
R ² is a hydrogen atom or a C _1-4 alkyl group, and R ³ and R
⁴ is C which may be substituted by a C _1-4 alkoxy group
The antibacterial or antibacterial agent according to the above (1), wherein a C _3-6 cycloalkyl group optionally substituted by a _1-5 alkyl group or a C _1-4 alkoxy group, and X is a halogen atom or a C _1-4 alkylthio group. (3) R ⁵ in the general formula (II) is a C _1-18 alkyl group, and R ⁶ and R ⁷ are both hydrogen, or one is hydrogen and the other is chloro. (1) at least one selected from the group consisting of the antibacterial, antifungal and antialgal compositions according to (1) and (4) triacetyl α-, β- and γ-cyclodextrin; The antibacterial, antifungal and antialgal composition according to the above (1), which is a cyclodextrin; (5) a triazine compound represented by the general formula (I); an isothiazoline compound represented by the general formula (II); selected from α-, β- and γ-cyclodextrin The antibacterial, fungicidal, and antialgal composition according to the above (1), which contains at least one kind in a molar ratio of 0.3 to 5: 1: 0.2 to 3; The triazine compound represented by I) is 2-methylthio-4-t-butylamino-6-cyclopropylamino-
s-triazine, 2-chloro-4,6-diethylamino-s-triazine, 2-chloro-4-ethylamino-6
At least one member selected from the group consisting of -isopropylamino-s-triazine and 2-methylthio-4-ethylamino-6- (1,2-dimethylpropylamino) -s-triazine; Are 2-n-octyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one, 5-chloro-2-n-octyl-4-isothiazoline -3-one and 4-chloro-2
At least one selected from the group consisting of -n-octyl-4-isothiazolin-3-one, and at least one selected from triacetyl α-, β- and γ-cyclodextrin; Or the antibacterial, antifungal, or algal composition according to (1), which is β-cyclodextrin;

(7) Further, general formula (III)

Embedded image (Wherein the ring A is an optionally substituted benzene ring,
It is a group or a thiazolyl group represented by -NHCOOR ⁸ (wherein, R ⁸ represents an alkyl group.). The antibacterial composition according to the above (1), comprising a benzimidazole compound represented by the formula:
Fungicidal and anti-algal composition, (8) 0.2 to 3.0 mol of benzimidazole compound represented by general formula (III) to 1 mol of isothiazoline compound represented by general formula (II) (9) The ring A in the general formula (III) has no substituent or is substituted with a halogen atom or a C _1-4 alkyl group. A bactericidal, fungicidal, antialgal composition according to (7), wherein R ⁸ is a C _1-8 alkyl group or Z is a thiazolyl group; -Benzimidazole carbamate, ethyl 2
The antibacterial composition according to the above (6), comprising at least one selected from the group consisting of -benzimidazole carbamate and 2- (4-thiazolyl) benzimidazole;
Fungicidal and anti-algal compositions.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION In the triazine compound represented by the general formula (I), the alkyl group of the optionally substituted alkyl group represented by R ¹ and R ² includes:
For example, C _1-4 such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl and the like.
Alkyl groups are mentioned, and as the substituent, for example,
Methoxy, ethoxy, n- propoxy, isopropoxy, n-butoxy, isobutoxy, C _1-4 alkoxy group such as t- butoxy, for example methoxycarbonyl, C _1-4 such as ethoxycarbonyl, n- butoxycarbonyl
Alkoxycarbonyl group, hydroxyl group, amino group,
Examples thereof include a carboxyl group, a cyano group, and a halogen atom such as chlorine and bromine. Examples of the alkyl group of the alkyl group which may have a substituent represented by R ³ and R ⁴ include:
For example, C _1-5 alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-pentyl, isopentyl and the like,
Examples of the substituent include those similar to the substituents of the alkyl group represented by R ¹ and R ² . As the cycloalkyl group represented by R ³ and R ^4, for example, cyclopropyl, cyclobutyl, cyclopentyl, and C _3-6 cycloalkyl groups such as cyclohexyl. Examples of the substituent, R ¹ and R ² And the same substituents as mentioned above. X is a halogen atom such as fluorine, chlorine, bromine or iodine, or a C _1-4 alkylthio group such as methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio or isobutylthio.
Among the triazine compounds represented by the formula (I), R ¹ and R ² are preferably a hydrogen atom or a C _1-4 alkyl group, R ³ ,
A C _1-5 alkyl or cyclopropyl group wherein R ⁴ is unsubstituted or substituted by a C _1-4 alkoxy group, X
Is chlorine, methylthio, ethylthio.
The triazine compound may be a base, hydrochloric acid,
It may be in the form of a salt with an inorganic acid such as sulfuric acid, nitric acid or phosphoric acid, or a salt with an organic acid such as acetic acid, propionic acid or p-toluenesulfonic acid.

Preferred specific examples of the triazine compound represented by the formula (I) include, for example, 2-methylthio-4
-T-butylamino-6-cyclopropylamino-s-
Triazine, 2-chloro-4,6-diethylamino-s-
Triazine, 2-chloro-4-ethylamino-6-isopropylamino-s-triazine, 2-methylthio-4-ethylamino-6- (1,2-dimethylpropylamino) -s-triazine and the like. General formula (I
In the isothiazoline compound represented by I), examples of the alkyl group represented by R ⁵ include a C _1-18 linear or branched alkyl group, preferably a C _1-3 or C _6-12 alkyl group. Groups, more preferably methyl, ethyl and n-octyl. Examples of the halogen represented by R ⁶ or R ⁷ include halogens such as fluoro, chloro and bromo, and among them, preferred is chloro. Specific examples of the isothiazoline compound represented by the general formula (II) include 2-methyl-4-isothiazolin-3-one, 2-n-octyl-4-isothiazolin-3-one, 5-chloro-2-methyl- 4-isothiazolin-3-one, 5-chloro-2-n-octyl-4-
Isothiazolin-3-one, 4-chloro-2-n-octyl-4-isothiazolin-3-one, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one and the like.

The triacetyl α-, β used in the present invention
-And γ-cyclodextrin are compounds represented by the following general formula (IV). When n is 6, α-isomer, when n is 7, β-isomer, and when n is 8, γ-isomer. is there.

Embedded image (In the formula, R ⁹ is an acetyl group, and n is 6, 7 or 8.) In the present invention, at least one of triacetyl α-, β- and γ-cyclodextrin may be used, and two The above may be used in combination. Among the α-, β- and γ-forms, the α- and β-forms, particularly the β-form, are advantageous for exhibiting the effects of the present invention.

In the benzimidazole compound represented by the general formula (III), the ring A represents an optionally substituted benzene ring. Examples of the substituent of the benzene ring represented by ring A include a hydroxyl group, a halogen atom (eg, chlorine, fluorine, bromine and iodine), a cyano group,
Examples include an amino group, a carboxyl group, an alkyl group (eg, a C _1-4 alkyl group such as methyl, ethyl, propyl, etc.) and an alkoxy group (eg, a C _1-4 alkoxy group such as methoxy, ethoxy, propoxy, etc.). Preferred are, for example, halogen atoms, C _1-4 alkyl groups and the like, and particularly preferred are C _1-3 alkyl groups such as methyl, ethyl and propyl. These substituents may be the same or different and may be substituted with 1 to 4, preferably 1 or 2. Z is a group represented by NHCOOR ⁸ (R ⁸ represents an alkyl group) or a thiazolyl group.
Examples of the alkyl group represented by R ⁸ include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl and n-octyl include alkyl groups C _1-8, such as, preferred are methyl, ethyl, alkyl groups C _1-3, such as n- propyl. Examples of the thiazolyl group include 4-thiazolyl and 5-thiazolyl.

The benzimidazole compound represented by the general formula (III) may be a salt thereof, for example, an inorganic acid salt such as hydrochloride, nitrate or phosphate, or an organic acid such as paratoluenesulfonate or methylsulfonate. It may be used in the form of a salt. Specific examples of the benzimidazole compound represented by the general formula (III) and a salt thereof include, for example, methyl 2-benzimidazole carbamate, ethyl 2
-Benzimidazole carbamate, 2- (4-thiazolyl) benzimidazole, methyl nitrate of 2-benzimidazole carbamate, ethyl nitrate of 2-benzimidazole carbamate, hydrochloride of 2- (4-thiazolyl) benzimidazole, methyl 2-benz P-Toluenesulfonate of imidazole carbamate, p of ethyl 2-benzimidazole carbamate
-Toluenesulfonic acid salt, p-toluenesulfonic acid salt of 2- (4-thiazolyl) benzimidazole and the like. In the antibacterial, fungicidal and antialgal compositions of the present invention, among the combinations of compound (I) and compound (II),
Combination of -methylthio-4-tert-butylamino-6-cyclopropylamino-s-triazine and 2-n-octylisothiazolin-3-one and further methyl
Combination with 2-benzimidazole carbamate exerts an excellent synergistic effect on antibacterial, antifungal and algal effects. In addition, in the composition of the present invention, the dissolution of the active ingredient from the coating film or film is suppressed by the addition of triacetylcyclodextrin, and the effect is considered to be long-lasting.

The composition of the present invention containing the triazine compound (I), the isothiazoline compound (II) and the triacetylcyclodextrin and, if necessary, the benzimidazole compound (III) can be prepared in the form of a liquid (water suspension, oil) or solid (Granules, fine granules, powders) and pastes. For use as a liquid or paste, a diluent of water or an organic solvent may be used.
Examples of the organic solvent include alcohol solvents such as methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, and butyl alcohol; ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; for example, dichloroethane, chloroform, Halogenated hydrocarbon solvents such as carbon chloride, for example, dioxane, ether solvents such as tetrahydrofuran, for example, aprotic polar solvents such as dimethylformamide, dimethyl sulfoxide, acetonitrile, for example, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene Glycol, propylene glycol, dipropylene glycol,
Tripropylene glycol, polypropylene glycol, 1,4-butanediol, 1,5-pentanediol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, tripropylene glycol monomethyl Glycol solvents such as ethers are exemplified. Preferred are glycol solvents, particularly preferred are ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and the like.

The compounding ratio of the triazine compound (I), the isothiazoline compound (II) and the triacetylcyclodextrin in the composition of the present invention is from 0.3 to 0.3 in molar ratio.
5: 1: 0.2-3, preferably 0.5-3: 1: 0.5
２2. When the benzimidazole compound (III) is further compounded, it is used in a molar ratio of 0.2 to 3.0, preferably 0.5 to 2, with respect to the compound (II). The composition of the present invention is an aqueous emulsion paint,
Solvent-type paint, aqueous latex, adhesive, water used in the paper pulp process, mixed with industrial cooling water, etc.
Exhibits an anti-algal effect. The composition of the present invention can further contain other fungicide fungicides. In that case, the ratio of a diluent used, for example, water or an organic solvent, can be changed depending on the type of compounding agent. Further, in the present invention, additives known for the purpose and use thereof, for example, a surfactant, an antioxidant, and the like may be added. As a fungicide, for example, 3-
Organic iodine-based compounds such as iodo-2-propynyl-butyl-carbamate, diiodomethyl-p-toluylsulfone, p-chlorophenyl-3-iodopropargylformal, for example, 4,5-dichloro-1,2-
Thiol compounds such as dithiol-3-one, for example, thiophene compounds such as 3,3,4,4-tetrachlorotetrahydrothiophen-1,1-dioxide;
For example, thiocarbamate compounds such as tetramethylthiuram disulfide, for example, 2,4,5,6-
A nitrile compound such as tetrachloroisophthalonitrile, for example, N- (fluorodichloromethylthio)-
Phthalimide, N- (fluorodichloromethylthio)-
Haloalkylthio compounds such as N, N'-dimethyl-N-phenyl-sulfamide, for example, 2,3,5
Pyridine-based compounds such as 6-tetrachloro-4- (methylsulfonyl) pyridine, for example, pyrithione-based compounds such as zinc pyrithione and sodium pyrithione are exemplified.

The mixing ratio of these fungicides varies depending on the dosage form and the purpose of use.
９９99.9% by weight.
For example, 0.1 to 30% by weight for a solution, 10 to 80% by weight for a wettable powder, and 10 to 99.
It is preferably about 9% by weight, and in the case of a suspension, about 0.1 to 90% by weight. It is preferable that the active ingredient concentration is adjusted to about 0.005 to 20% by weight, preferably about 0.01 to 1% by weight by adjusting the amount added to the applicable substance according to the purpose of use. As the surfactant, known surfactants such as soaps, nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, and polymer surfactants can be used. it can. Among them, a nonionic surfactant and an anionic surfactant are preferably used. Examples of the nonionic surfactant include polyoxyalkylene aryl phenyl ether, polyoxyethylene nonyl phenyl ether, ethylene oxide and propylene oxide block copolymer, and the like. 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 polyoxyethylene distyrenated phenyl ether sulfate ammonium salt,
Lignin sulfonic acid metal salts and the like, and examples of the metal salts include sodium salts, potassium salts, and magnesium salts.

As the antioxidant, 2,6-di-t-
Phenolic antioxidants such as butyl-4-methylphenol and 2,2'-methylenebis [4-methyl-6-t-butylphenol]; alkyldiphenylamine;
Examples include amine antioxidants such as N'-di-s-butyl-p-phenylenediamine. For example, in the case of a liquid, these surfactants and antioxidants are added in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the liquid. In the composition of the present invention, the total concentration of the triazine compound (I), the isothiazoline compound (II) and the triacetylcyclodextrin, and if necessary, the total concentration of the benzimidazole compound (III) is usually 0.1 depending on the type of the object to be blended. It can be blended so as to be about 90 to 90% by weight, preferably about 1 to 80% by weight.

[0016]

Next, the present invention will be further described with reference to Examples, Comparative Examples and Test Examples of the present invention, but the present invention is not limited to these. In the following description, compound names are abbreviated as follows. 2-methylthio-4-t-butylamino-6-cyclopropylamino-s-triazine: triazine (I) 2-n-octyl-4-isothiazolin-3-one: O
IT Triacetyl β-cyclodextrin: Triacetyl β
CD methyl 2-benzimidazole carbamate: MBC Also,% and parts are% by weight and parts by weight, respectively. Example 1 50 g of OIT and 300 g of triacetyl βCD were dissolved in 500 ml of ethyl acetate and stirred for 4 hours. The obtained liquid was concentrated to dryness by an evaporator, and to the residue were added 50 g of triazine (I), 550 g of water, and 50 g of Emulgen A-90 (nonionic surfactant, manufactured by Kao Corporation), followed by stirring for 2 hours. The suspension particles were pulverized using a bead mill (bead diameter: 2 mm) to further reduce the particles of the obtained suspension to prepare a stable suspension.

Example 2 50 g of OIT, 400 g of triacetyl βCD, 50 g of Emulgen A-90 and 450 g of water were mixed and stirred for 24 hours. Then, 50 g of triazine (I) was added, and the mixture was further stirred for 2 hours. The suspension particles were pulverized using a bead mill (bead diameter: 2 mm) to further reduce the particles of the obtained suspension to prepare a stable suspension. Example 3 50 g of OIT, 200 g of triacetyl βCD, 50 g of triazine (I), 650 g of water and Emulgen A-90
Using 50 g of, a stable suspension was prepared in the same manner as in Example 1. Example 4 50 g of OIT, 50 g of MBC, triacetyl βCD30
Using 0 g, 50 g of triazine (I), 500 g of water and 50 g of emulgen A-90, a stable suspension was prepared in the same manner as in Example 1.

Comparative Example 1 50 g of OIT, 50 g of triazine (I), Emulgen A
A stable suspension was prepared in the same manner as in Example 2 using 50 g of -90 and 850 g of water. Comparative Example 2 OIT 50 g, Triazine (I) 50 g, MBC 50
g, 50 g of Emulgen A-90 and 800 g of water to prepare a stable suspension in the same manner as in Example 2.

Test Example 1 1) Algae prevention test The preparations obtained in Examples 1 to 4 and Comparative Examples 1 and 2 were tested for their antialgal effect on paint. The results are shown in [Table 1]. The test algae solution was prepared from Ch
lamydomonas reinhardtii (Chlamydomonas reinhardti), Euglena gracilis (Euglena gracilis), Chlorella sp. (Chlorella sp.), Phormidi
um ramosum, Ulothrix
variabilis (Uroslicks variabilis), Osci
A mixed solution of llatoria neglecta (Ossilatoria neglecta) was used. As the test paint, an acrylic-styrene emulsion paint was used, and the formulation was added to the paint so as to have the concentration shown in [Table 1], and a paint having the same weight as the filter paper was uniformly applied on No. 5 qualitative filter paper. After applying and drying, the anti-algal effect was evaluated by the following test method. The test method and criteria are as follows.

Test method (1) A paint sample was cut into a size of 30 × 30 mm, (a) immersed in 200 ml of water at a temperature of 40 ° C. for 24 hours, then lifted up and subjected to (b) ultraviolet irradiation for one day. This operation 5
Repeated times. (2) An Allen's agar medium sterilized in an autoclave was poured into a Petri dish having a diameter of 9 cm, and a test piece was stuck to the center of an agar plate that had been solidified. (3) After spraying the mixed algal solution of 6 types, the cells were cultured in an environment of 25 ° C., irradiated with light for 16 hours, not irradiated for 8 hours. (4) Four weeks after the culture, the degree of algal growth on the test piece was determined. Judgment criteria-: No algal growth was observed on the test surface. ±: Very little algae growth is observed on the test surface. +: The growth of algae is observed on 1/3 or less of the test surface. ++: Algae growth is observed on 2/3 or less of the test surface. +++: Algae growth is observed on 2/3 or more of the test surface.

2) Antifungal test The preparations obtained in Examples 1 to 4 and Comparative Examples 1 and 2 were tested for their antifungal effect on paint. The results are shown in [Table 1]. The test solution was Cladosporium and Cladosporioides (Cl. Cultivated on potato dextrose liquid agar).
adosporium cladosporioides, Mucor spinesens, Rhodotorla rubra (Rhodo)
torula rubra), Saccharomyces cerevisiae (Sa)
A mixture of Ccharomyces cerevisiae) and Alternaria spices (Alternaria sp.) in a Sabouraud medium was used. As the test paint, an acrylic-styrene emulsion paint was used, and the formulation was added to the paint so as to have the concentration shown in [Table 1], and a paint having the same weight as the filter paper was uniformly applied on No. 5 qualitative filter paper. After coating and drying, the antifungal effect was evaluated by the following test method. The test method and criteria are as follows.

Test Method (1) A paint sample was cut into a size of 30 × 30 mm, (a) immersed in 200 ml of water at a temperature of 40 ° C. for 24 hours, then pulled up, and subjected to ultraviolet irradiation (b) for one day. This operation 5
Repeated times. (2) Sabouraud medium sterilized in an autoclave is
The specimen was affixed to the center of an agar plate that had been poured into a 1 cm Petri dish and allowed to solidify. (3) After spraying the five kinds of mixed mold liquid, the cells were cultured in an environment of 28 ° C. (4) The degree of growth of the mold 4 weeks after the culture was determined. Judgment criteria-: No mold growth was observed on the test surface. ±: Very little mold growth is observed on the test surface. +: The growth of mold was observed on 1/3 or less of the test surface. ++: Mold growth is observed on 2/3 or less of the test surface. +++: Mold growth is observed on 2/3 or more of the test surface.

3) Judgment results of anti-algal test and anti-mold test

[Table 1] As is clear from the above [Table 1], the preparations of Examples 1 to 4 containing triacetylcyclodextrin were 4 weeks later than the preparations of Comparative Examples 1 and 2 not containing it. And it was clearly superior in antifungal effect.

[0024]

EFFECT OF THE INVENTION The antibacterial, antifungal and antialgal compositions containing the triazine compound, isothiazoline compound and triacetylcyclodextrin according to the present invention and, if necessary, a benzimidazole compound can be used for controlling a wide range of fungi, molds and algae. This is an industrial alga-proofing composition which is effective and has a long-lasting effect, has excellent weather resistance and chemical resistance, and can be suitably used as a liquid agent. Especially as an industrial antibacterial, fungicidal and anti-algal agent added to water-based emulsion paints, solvent-based paints, adhesives, leather, plastic products such as vinyl chloride, water used in the paper pulp process, industrial cooling water, etc. Useful.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C09D 5/14 C09D 5/14

Claims (10)

[Claims] 1. A compound of the general formula (I) (In the formula, R ¹ and R ² represent a hydrogen atom or an alkyl group which may have a substituent, and R ³ and R ⁴ each represent an alkyl group or a substituent which may have a substituent. Or a cycloalkyl group, X represents a halogen atom or an alkylthio group), and a triazine compound represented by the general formula (II): (Wherein, R ⁵ is an alkyl group, R ⁶ and R ⁷ are both hydrogen, or one is hydrogen and the other is a halogen atom), and triacetyl α-, β- and A bactericidal, fungicidal and anti-algal composition comprising at least one γ-cyclodextrin. 2. In the general formula (I), R ¹ and R ² are a hydrogen atom or a C _1-4 alkyl group, and R ³ and R ⁴ are
_A C _1-5 alkyl group optionally substituted by a _1-4 alkoxy group or a C _3-6 cycloalkyl group optionally substituted by a C _1-4 alkoxy group, wherein X is a halogen atom or C _1-4 alkylthio The antibacterial, antifungal and antialgal composition according to claim 1, which is a base. 3. The compound of claim 1, wherein R ⁵ in the general formula (II) is a C _1-18 alkyl group, and R ⁶ and R ⁷ are both hydrogen, or one is hydrogen and the other is chloro. Bactericidal, fungicidal and anti-algal compositions. 4. The antibacterial, antifungal and antibacterial composition according to claim 1, wherein at least one selected from triacetyl α-, β- and γ-cyclodextrin is triacetyl α- or β-cyclodextrin. Algae composition. 5. A compound comprising at least one compound selected from the group consisting of a triazine compound represented by the general formula (I), an isothiazoline compound represented by the general formula (II), and triacetyl α-, β- and γ-cyclodextrin. 0.3-5 in ratio:
The antibacterial, antifungal and antialgal composition according to claim 1, which is contained in the range of 1: 0.2 to 0.3. 6. The triazine compound represented by the general formula (I) is 2-methylthio-4-t-butylamino-6-cyclopropylamino-s-triazine, 2-chloro-4,
6-diethylamino-s-triazine, 2-chloro-4
-Ethylamino-6-isopropylamino-s-triazine and 2-methylthio-4-ethylamino-6
At least one selected from the group consisting of (1,2-dimethylpropylamino) -s-triazine, wherein the isothiazoline compound represented by the general formula (II) is 2-n-octyl-4-isothiazoline-3- ON, 5-chloro-
Group consisting of 2-methyl-4-isothiazolin-3-one, 5-chloro-2-n-octyl-4-isothiazolin-3-one and 4-chloro-2-n-octyl-4-isothiazolin-3-one At least one selected from triacetyl α-, β- and γ-cyclodextrin;
The antibacterial, antifungal and algal compositions according to claim 1, which are-or -cyclodextrin. 7. A compound of the general formula (III) (Wherein the ring A is an optionally substituted benzene ring,
It is a group or a thiazolyl group represented by -NHCOOR ⁸ (wherein, R ⁸ represents an alkyl group.). 2. The antibacterial, antifungal and antialgal composition according to claim 1, which contains a benzimidazole compound represented by the formula: 8. The method according to claim 7, wherein the benzimidazole compound represented by the general formula (III) is contained in the range of 0.2 to 3.0 mol based on 1 mol of the isothiazoline compound represented by the general formula (II). Antibacterial, antifungal and antialgal compositions. 9. The ring A in the formula (III) is a benzene ring having no substituent or substituted by a halogen atom or a C _1-4 alkyl group, and R ⁸ is a C _1-8 alkyl group. The antibacterial, antifungal and antialgal composition according to claim 7, wherein Z is a thiazolyl group. 10. The method according to claim 6, further comprising at least one selected from the group consisting of methyl 2-benzimidazole carbamate, ethyl 2-benzimidazole carbamate and 2- (4-thiazolyl) benzimidazole. Bacteria, fungicidal and anti-algal compositions.