JPH02207007A - Algicide - Google Patents

Abstract

PURPOSE:To obtain an algicide with low toxicity, containing a 3-isothiazolone compound and polyamine sulfone derivative and capable of exhibiting excellent algicidal effects by synergistic action and preventing propagation of algae in water for a long period. CONSTITUTION:An algicide containing (A) a compound expressed by formula I (R<1> is H or halogen; R<2> is H or alkyl) or a metal salt complex thereof, e.g. 4-isothiazolin-3-one and zinc chloride complex thereof, and (B) a compound (preferably with 3000-120000 molecular weight) having recurring structural units expressed by formula II (R<3> and R<4> are lower alkyl or hydroxy-lower alkyl; Y is halogen), e.g. polyamide sulfone dimethylammonium chloride, at (2:8)-(8:2) weight ratio of the ingredients (A):(B). The above-mentioned algicide is added in an amount of >=0.01mg, preferably 0.1-100mg based on 1l water.

Description

[Detailed description of the invention] (Technical field) TECHNICAL FIELD The present invention relates to an algaecide.

(Prior art and its problems) In equipment parts such as cooling towers, cooling pipes, and water storage tanks where water circulates or where water stagnates, algae adheres to the walls and grows, producing bad odors and corrosion of the equipment. This causes problems such as a decrease in cooling efficiency.

In order to eliminate the problems caused by algae, compounds of elements such as mercury, arsenic, and chromium,
Disinfectants such as trichlorophenol and sodium hypochlorite have been added to water. However, these compounds are highly toxic to the human body, and from the perspective of pollution prevention, they are
Their use is not preferred.

Low toxicity algaecides have been developed in the past, and several have been proposed.For example, poly(hexamethylene biguanides) (Japanese Patent Publication No. 57-61006), Those using 2-nitropropane-1,3-diol (Japanese Patent Publication No. 58-4682) as an algaecide or algaecide component, and 3-(3,4-diglorophenyl)-1,1 - Those consisting of dimethyl urea and citrate or ester (Japanese Patent Publication No. 12841/1984) have been proposed.

However, the low-toxicity products that have been proposed so far have had problems such as weak algae-preventing effects.

(Section of the Invention! g) An object of the present invention is to provide a new algaecide with low toxicity and excellent algaecide effect.

(Means for Solving the Problems) As a result of extensive research in order to solve the above problems, the present inventors found that two specific substances conventionally known as low toxicity substances
It was discovered that an excellent algae-proofing agent can be obtained by combining species, and the present invention was completed.

That is, the present invention provides one or more 3-isothiazolone compounds or metal salt complexes thereof represented by the general formula (wherein R1 is a hydrogen atom or a halogen atom, and R2 is a hydrogen atom or an alkyl group). .

It is an algaecide comprising a polyamine sulfone derivative having a repeating structural unit represented by the general formula (wherein R' and R' are a lower alkyl group or a hydroxy lower alkyl group, and Y is a halogen atom).

One component constituting the algaecide of the present invention has the general formula (
It is a 3-isothiazolone compound represented by 1). In general formula (II), R1 represents a hydrogen atom or a halogen atom, and examples of the halogen atom include chlorine, bromine, and iodine. Further, R2 represents a hydrogen atom or an alkyl group, and the alkyl group includes lower and higher alkyl groups, and an alkyl group having 1 to 18 carbon atoms, particularly preferably 1 to 10 carbon atoms. Such alkyl groups include methyl and ethyl.

Propyl, isopropyl, butyl, isobutyl, 5ee
-butyl, tart-butyl, pentyl, hexyl,
Examples include octyl, nonyl, decyl, etc. Among these, methyl is the most preferred.

As the metal complex of the 3-isothiazolone compound represented by the general formula ([), those represented by the following general formula are used.

In the formula, R1 and R2 have the same meanings as above, N represents a metal cation, and X represents an anion that forms a compound with the cation A which has sufficient solubility to form a complex. a is an integer of 1 or 2, and n is an integer such that the anion X satisfies the valence of the cation A.

Metals that form metal cations include barium,
cadmium, calcium, chromium, cobalt, copper, iron,
Examples include lead, lithium, magnesium, manganese, mercury, nickel, sodium disilver, strontium, tin, zinc, etc. Among these, calcium, copper, magnesium, manganese, nickel, and zinc are preferable.As the anion X, chloride ion, bromide ion, iodide ion, sulfate ion, nitrate ion, acetate ion, barchlorate ion, hydrogen sulfate ion, hydrogen carbonate ion, oxalate ion, malate ion,
Isothiazolone and its metal salt complex represented by the above general formulas (1) and (m), including p-toluenesulfonate ion, carbonate ion, phosphate ion, etc., and preferably chloride ion, bromide ion, sulfate ion, and nitrate ion. Typical examples are as follows.

4-isothiazolin-3-one and its zinc chloride complex.

2-Methyl-4-isothiazolin-3-one and its calcium chloride complex, 5-chloro-2-methyl-4-isothiazolin-3-one and its calcium chloride complex or magnesium chloride complex, 2-n-butyl-4- Isothiazolin-3-one and its zinc chloride complex, 2-n-octyl-4-isothiazolin-3-one and its iron chloride complex, 2-n-decyl-4-isothiazolin-3-one and its zinc chloride complex, etc.

The metal salt complex of isothiazolone is represented by the following formula: isothiazolone and metal salt MXn (M.

(X and n are as defined above) can be easily synthesized by reacting.

The amount of raw materials used in this reaction preferably corresponds to the stoichiometric amount of product, although an excess of isothiazolone or metal salt MXn may be used. Although complexing of both raw materials can be carried out at any temperature in the range of 0 to 100°C, it generally proceeds easily at room temperature. The reaction can be carried out in a solution or in a slurry. When the reaction is carried out in a solution, any solvent that can sufficiently dissolve both reactants can be used, including water, methanol, ethanol, etc. It is recommended to use alcohol.

The isothiazolone metal salt complex that forms precipitates or remains in solution. When the product is an insoluble solid, it can be separated by filtration, and when it is not a solid, it can be separated by removing the solvent.0 When using the isothiazolone metal salt complex in the algaecide of the present invention, it can be separated as a solid. The complex may be used as a separated complex, or it may be used as a solution. Therefore, when producing the algaecide of the present invention, a method may be adopted in which the inthiazolone and metal salt MXn calculated in advance are mixed together with other carriers.

The other component constituting the algaecide of the present invention is a polyamine or sulfone derivative having a repeating structural unit represented by the general formula (■). In general formula (n), R
3. The lower alkyl group represented by R4 includes methyl,
Examples of the hydroxy lower alkyl group include ethyl, propyl, isopropyl, butyl, and isobutyl groups. Examples of the hydroxy lower alkyl group include groups in which part or all of the hydrogen atoms of the above-mentioned alkyl group are substituted with a hydroxy group. Also, Y
Examples include chlorine, bromine, and iodine-fluorine.

Specific examples of polyamine sulfone derivatives include, for example:
The following can be mentioned.

Polyaminesulfone dimethyl ammonium chloride.

Polyamine sulfone dimethyl ammonium bromide.

Polyaminesulfone dimethylammonium iodide.

Polyaminesulfonemethylhydroxyethylammonium chloride, Polyaminesulfonediethylammonium chloride, Polyaminesulfoneethylhydroxyethylammonium chloride, Polyaminesulfonepropylhydroxyethylammonium chloride, Polyaminesulfonedipropylammonium chloride.

Polyaminesulfone methyl hydroxypropylammonium chloride.

Polyaminesulfone methylhydroxybutylammonium chloride, etc.

The polyamine sulfone derivative used in the present invention has a molecular weight of 1000 to 700,000, preferably 300.
It is preferred to use a range of 0-120,000.

In order to obtain a good algae-proofing effect in the algae-proofing agent of the present invention,
It is necessary to use the above two components in combination, and the weight ratio of both is preferably set in the range of 1710 to 1O/1, preferably 278 to 8/2.

(Effects of the Invention) Although the algaecide of the present invention is composed of low-toxic substances, it exhibits an excellent algaecide effect due to the synergistic effect of both components, and when added to target water, Prevents algae growth in water for a long period of time. In this case, the amount of algaecide added (total amount of the above two components) is water IQ
0.01 mg or more, preferably 0.1 to 100
It is a percentage of mg.

The algaecide of the present invention can also be used in combination with other components such as scale control agents and rust preventives.

(Example) Next, the present invention will be explained in more detail with reference to Examples. Note that all parts shown below are based on weight.

Example Various algaecides having the following component compositions were prepared.

Inventive product (1) Polyamine sulfone dimethyl ammo: 10 (parts) Nium chloride (molecular weight: 100,000) Water Inventive product (n): 80 Water Inventive product (m) = 80 Water Inventive product (iv) 2 80 2-octyl-3-isothiazolone: 10 Water comparative product (1): 80 (parts) Comparative product (■) Comparative product (III) Comparative example (1v) Comparative example (V) 2-octyl-3-isothiazolone: 20 (department)
Test Example 1 Chlorella vulgaris (
C, v) and 1Jlothrix 5p (U, s
and two types of green algae (abbreviated as p).

Phormidia + foveolarum (P,
abbreviated as f) and 0scillataria agard
Using two types of blue-green algae, ii (abbreviated as 0 and a), an anti-algae test was conducted as follows.

After adding 00 parts of the test algae solution that has been cultured in advance to tap water containing 10 weights of each algae culture medium, dispense 200cc each into a colben. Add a certain amount. During the test period, these kolbens were kept at a constant temperature (20
℃) Placed in an aquarium, placed near a window, and cultured with intermittent aeration for 5 times during the day for 2 hours each (total 6 hours), and after oral administration (20 days)
The degree of algal growth was observed with the naked eye and with a microscope, and the effectiveness was determined. The results are shown in Table 1.

The numerical values shown in the table indicate the minimum concentration (ppll) of the algae preventive agent (aqueous solution) that completely inhibits growth.

Furthermore, the code shown in the table indicates complete growth of the test bacteria.

Table-1 3...Good growth 2...Poor growth 1...Very poor growth 0...No growth Table-2 Test Example 2 As an anti-algae agent in a 50-ton cooling tower Inventive products (1) to (IV) and comparative products (1) to (V) were added to cooling water at a concentration of 20 ppm, and after 10 days, the growth state of algae was examined. Its growth condition is 5
Evaluation was performed using a stepwise method, and the results are shown in Table 2.

(Evaluation criteria) 4...Dominant growth

Claims (1)

[Claims] (1) General formula ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (I) (In the formula, R^1 is a hydrogen atom or a halogen atom, R^2 is a hydrogen atom or an alkyl group) 3-isothiazolone One or more compounds or metal salt complexes thereof, and general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (II) (In the formula, R^3 and R^4 are lower alkyl groups or hydroxy lower alkyl groups. , Y represents a halogen atom).