JPH115707A - Antialgal agent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition capable of exhibiting effect over a long period in a small amount and excellent in weather resistance and chemical resistance by compounding a specific triazine compound with a specific isothiazolin compound and as necessary, a specific benzimidazole compound at a specific ratio. SOLUTION: This antialgal agent composition comprises (A) a triazine compound represented by formula I [R<1> and R<2> are each H, a (substituted)alkyl, etc.; R<3> and R<4> are each a (substituted)alkyl, a (substituted)cycloalkyl, etc.; X is a halogen, etc.], (B) an isothiazolin compound represented by formula II (R<5> is an alkyl; R<6> and R<7> are simultaneously H or either one thereof is H and the other is a halogen) and as necessary, (C) a benzimidazole compound represented by formula III [A ring is a (substituted)benzene ring; Z is thiazolyl, etc.]. In the above composition, the component A is compounded with the component B at a weight ratio of (1:(0.2 to 3) and the component C is compounded at a weight ratio of 0.2-3.0 based on the component B.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an antialgal composition comprising at least one triazine compound, at least one isothiazoline compound and, if necessary, at least one benzimidazole compound in a specific ratio.

[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 algae emergencies in water-based emulsion-type paints, solvent-type paints, plastic products such as PVC, vinyl films for agricultural use, and industrial cooling water.

[0003]

Although the generally used anti-algal composition is relatively low in toxicity, it is important to minimize the amount of the anti-algae composition from the viewpoints of pollution, the environment and reduction of the algal treatment cost. Is desirable. Also, those used outdoors, such as outdoor paints and agricultural vinyl films, are exposed to strong sunlight for a long time, and water-based acrylic emulsion paints are weakly alkaline. Is required to be stable to ultraviolet rays and alkalis. Accordingly, research has been conducted on an alga-proofing composition which exhibits an effect over a longer period with a smaller amount of use and is excellent in weather resistance and chemical resistance.

[0004]

In view of the above problems, the present inventors have conducted intensive studies to obtain substances and compositions having a high control effect on algae. As a result, a specific triazine compound and a specific isothiazoline compound, and Have found that a specific benzimidazole compound is blended at a specific ratio to achieve a synergistic anti-algal effect, and based on the knowledge, further studies have been carried out to complete the present invention. That is, the present invention relates to (1) 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) and a general formula (I
I)

Embedded image (In the formula, R ⁵ is an alkyl group, R ⁶ and R ⁷ are both hydrogen, or one represents hydrogen and the other represents halogen.)
The isothiazoline compound represented by
(2) R ¹ and R ² in the general formula (I) are a hydrogen atom or C _1-4
An alkyl group, R ³ and R ⁴ may be substituted by C _1-4 alkoxy C _1-5 alkyl group or a C
(3) The algagic composition according to the above (1), wherein the C _3-6 cycloalkyl group optionally substituted by a _1-4 alkoxy group, X is a halogen atom or a C _1-4 alkylthio group.
The algicidal agent according to the above (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. The composition (4) comprising the triazine compound represented by the general formula (I) and the isothiazoline compound represented by the general formula (II) in a weight ratio of 1: 0.5 to 2 (1). A) an antialgal composition according to

(5) When the triazine compound represented by the general formula (I) is 2-methylthio-4-tert-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-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one, 5-chloro-2-n-octyl-4-isothiazolin-3-one and 4-chloro-2- at least one member selected from the group consisting of n-octyl-4-isothiazolin-3-one
Algae-protecting composition according to the above (1), which is a seed;

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.). (1) The benzimidazole compound represented by formula (II) is contained in a weight ratio of 0.2 to 3.0 with respect to the isothiazoline compound 1 represented by formula (II). (7) ring A in formula (III) has no substituent,
Or a benzene ring substituted with a halogen atom or a C _1-4 alkyl group, wherein R ⁸ is a C _1-8 alkyl group,
Or the group consisting of (5) the anti-algal agent composition according to the above (5), wherein Z is a thiazolyl group, and (8) methyl 2-benzimidazole carbamate, ethyl 2-benzimidazole carbamate and 2- (4-thiazolyl) benzimidazole. The anti-algal composition according to the above (5), comprising at least one member selected from the group consisting of:

[0006]

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 formula (I), R ¹ and R ² are preferably hydrogen atoms or C _1-4 alkyl groups, and R ³ and R ⁴ are not substituted or C _1-4 A compound wherein a C _1-5 alkyl group or a cyclopropyl group substituted with an alkoxy group, and X is chlorine, methylthio, or ethylthio. The triazine compound may be a base or a salt with an inorganic acid such as hydrochloric acid, 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 and 2-methylthio-4-ethylamino-6
(1,2-dimethylpropylamino) -s-triazine and the like. In the isothiazoline compound represented by the general formula (II), examples of the alkyl group represented by R ⁵ include a C _1-18 linear or branched alkyl group, preferably C _1-3 or C _{6. A -12} alkyl group, 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.
Preferred among them is chloro.

Specific examples of the isothiazoline compound represented by the general formula (II) include 2-n-octyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one, -Chloro-2-n-octyl-4-isothiazolin-3-one, 4-chloro-2-
and n-octyl-4-isothiazolin-3-one. 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 and a halogen atom (for example,
Chlorine, fluorine, bromine and iodine), cyano group, amino group, carboxyl group, alkyl group (for example, methyl,
A C _1-4 alkyl group such as ethyl, propyl, etc.) and an alkoxy group (eg, C _1-4 alkoxy group such as methoxy, ethoxy, propoxy, etc.).
For example, a halogen atom, a C _1-4 alkyl group and the like can be mentioned, and particularly preferred are C, such as methyl, ethyl and propyl.
_1-3 alkyl groups are exemplified. These substituents may be the same or different and have 1 to 4, preferably 1 or 2
It may be replaced. Z is a group represented by NHCOOR ⁸ (R ⁸ represents an alkyl group) or a thiazolyl group. R ⁸
Examples of the alkyl group represented by are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl and n-octyl A C _1-8 alkyl group is preferred, and a preferred one is a C _1-3 alkyl group such as methyl, ethyl and n-propyl.

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. The compound (I) in the antialgal composition of the present invention
And the compound (II), particularly, 2-methylthio-4-tert-butylamino-6-cyclopropylamino-s-triazine and 2-n-octylisothiazoline-
Specific ratio combinations of 3-one and also methyl
The combination of the specific ratio with 2-benzimidazole carbamate exerts an excellent synergistic effect on the alga repellent effect.

The composition of the present invention containing the triazine compound (I), the isothiazoline compound (II) and, if necessary, the benzimidazole compound (III) can be used as a liquid (water suspension, oil), a solid (granules, It can be used as dosage forms such as fine granules and 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,
Glycol solvents such as tripropylene glycol monomethyl ether 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 mixing ratio of the triazine compound (I) and the isothiazoline compound (II) in the present invention is in the range of 1: 0.2 to 3, preferably 1: 0.5 to 2, by weight. When the benzimidazole compound (III) is further compounded, the weight ratio of the compound to the compound (II) is 0.2 to 0.3.
0, preferably used in the range of 0.5 to 2. Algae to be controlled by the algae preventive composition of the present invention is a plant that grows in water and has an assimilating pigment and independently lives in vegetative life, among which cyanobacteria, green algae, brown algae, and red algae , Yellow algae, yellow-brown algae and the like. The algicidal composition of the present invention is particularly effective in controlling green algae and cyanobacteria. It is also possible to mix 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, its purpose,
Known additives such as a surfactant and an antioxidant may be added depending on the use. As a disinfectant, 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-tetrachlorotetrahydrothiophene-1,1-dioxide, for example, thiocarbamate compounds such as tetramethylthiuram disulfide For example, 2,4,5
Nitrile compounds such as 6-tetrachloroisophthalonitrile, for example, haloalkylthio compounds such as N- (fluorodichloromethylthio) -phthalimide, N- (fluorodichloromethylthio) -N, N'-dimethyl-N-phenyl-sulfamide Compound, for example, 2,
3,5,6-tetrachloro-4- (methylsulfonyl)
Pyridine-based compounds such as pyridine, for example, pyrithione-based compounds such as zinc pyrithione and sodium pyrithione, and the like can be mentioned.

The mixing ratio of these fungicides varies depending on the dosage form and the purpose of use, but is generally 0.1 with respect to the whole preparation.
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. In addition, by adjusting the amount of addition to the applicable substance according to the purpose of use, about 0.00
It is preferable to act as an active ingredient concentration of 5 to 20% by weight, preferably about 0.01 to 1% by weight. 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. As the anionic surfactant,
Alkyl benzene sulfonic acid metal salt, alkyl naphthalene sulfonic acid metal salt, polycarboxylic acid type surfactant, dialkyl sulfosuccinate metal salt, polyoxyethylene distyrenated phenyl ether sulfate ammonium salt, lignin sulfonic acid metal salt and the like,
Examples of the metal salt include a sodium salt, a potassium salt, and a magnesium salt.

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. The anti-algal composition of the present invention is prepared by adding the triazine compound (I) and the isothiazoline compound (II), and further, if necessary, the benzimidazole compound (III), depending on the type of the object to be blended. The total concentration is usually 0.1 to 50,000
ppm, preferably 1 to 30,000 ppm, more preferably 50 to 20,000 ppm, particularly preferably about 1,000 to 10,000 ppm.

[0014]

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 methyl 2-benzimidazole carbamate: MBC Also,% and parts are% by weight and parts by weight, respectively. Example 1 In a stirrer equipped with a stirring blade, 10 g of triazine (I) was added.
5 g of OIT and 85.0 g of methyl carbitol were added and stirred at 300 RPM for 3 minutes to obtain 100 g of the preparation.

Examples 2 to 4 In the same manner as in Example 1, a predetermined amount of the ingredients fried in Table 1 was mixed and dissolved to obtain 100 g of each preparation. Comparative Examples 1 to 3 In the same manner as in Example 1, a predetermined amount of the ingredients fried in Table 1 was mixed and dissolved to obtain 100 g of each preparation.

[Table 1]

Test Example 1 Anti-algae test Examples 1-4 containing active ingredients as shown in Table 1
And about the comparative examples 1-3, the algicidal effect with respect to a paint was compared. The results are shown in [Table 2]. However, as the test algal solution, Chlamy cultured in Allen liquid medium was used.
domonasreinhardtii (Chlamydomonas reinhardti), Euglena gracilis (Euglena gracilis), Chlorella sp. (Chlorella sp.), Phormid
iumramosum, Ulothrix
variabilis (Uroslicks variabilis), Osc
A mixed solution of illatoria 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 2]. After coating and drying, the alga-proofing effect was evaluated by the following test method. The test method and criteria are as follows.

1) 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 25 ° C. for 24 hours, pulled up, and irradiated with ultraviolet light of (b) for 3 days. I did it. (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 species, the cells were cultured at 25 ° C under light irradiation (light for 16 hours and dark for 8 hours). (4) Four weeks after the culture, the degree of algal growth on the test piece was determined. 2) Judgment criteria-: No growth of algae 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.

3) Judgment result

[Table 2]

Test Example 2 Stability test The amount of triazine (1) and / or OIT shown in Table 3 was added to 1,000 g of a carbonate buffer solution (pH 9.1), mixed well, and mixed with test solutions 1 to 7. Was prepared. Each test solution was sealed in a glass container and placed in a thermostat at 50 ° C. for 3 days while irradiating with ultraviolet light having a strength of 2.7. Then, triazine (1) and O
The residual ratio (% by weight) of each IT was measured.

[Table 3] As is clear from Table 3, triazine (1) and OI
Test No. T in which the compounding ratio of T is within the range of the present invention.
In Trials 1 to 3, both triazine (1) and OIT show a high residual ratio, but in Test Nos. 4 to 7 in which the use alone or the mixing ratio is out of the range of the present invention, the residual ratio of the active ingredient is low. Therefore triazine (1)
And OIT also have a synergistic effect on weather resistance and chemical resistance.

[0020]

The anti-algae composition of the present invention comprising the triazine compound, the isothiazoline compound and, if necessary, the benzimidazole compound in a specific ratio is effective for controlling a wide range of algae, and has weather resistance and chemical resistance. It is an industrial alga-proofing agent composition which is excellent in water resistance and can be suitably used as a liquid preparation. In particular, it is useful as an industrial disinfectant added to aqueous emulsion paints, solvent-type paints, plastic products such as vinyl chloride, industrial cooling water, and the like.

Claims (8)

[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. A cycloalkyl group, X represents a halogen atom or an alkylthio group) and a general formula (I
I) (In the formula, R ⁵ is an alkyl group, R ⁶ and R ⁷ are both hydrogen, or one represents hydrogen and the other represents halogen.)
The isothiazoline compound represented by
An algicidal composition containing in the range of 2-3. 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 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. Anti-algal composition. 4. The method according to claim 1, wherein the triazine compound represented by the general formula (I) and the isothiazoline compound represented by the general formula (II) are contained in a weight ratio of 1: 0.5-2. Anti-algal composition. 5. 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 The antialgal composition according to claim 1, which is at least one member selected from the group consisting of: 6. 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.). The algicidal composition according to claim 1, wherein the benzimidazole compound represented by the formula (1) is contained in a weight ratio of 0.2 to 3.0 with respect to the isothiazoline compound 1 represented by the general formula (II). . 7. The ring A in the formula (III) is a benzene ring having no substituent or substituted with a halogen atom or a C _1-4 alkyl group, and R ⁸ is a C _1-8 alkyl group. Or Z is a thiazolyl group.
The anti-algal composition according to the above. 8. The method according to claim 5, further comprising at least one member selected from the group consisting of methyl 2-benzimidazole carbamate, ethyl 2-benzimidazole carbamate and 2- (4-thiazolyl) benzimidazole. Algae composition.