JP2586105B2 - Algicides and fungicides - Google Patents

Description

The present invention relates to an algicidal / bactericide. The algicidal / bactericide of the present invention is used for, but not limited to, the suppression of the growth and proliferation of algae and general bacteria generated in industrial water, cooling tower treated water, and the like.

[PRIOR ART] Algae-related obstacles include obstacles to industrial water supply systems;
Failure of the heat exchanger in the circulating cooling system of the cooling tower of the building; failure due to stains on products in paper and dyeing plants.

Green algae such as Ulothrix, Spirogyra, Chlorella, etc .; Oscillaria (Oscilla)
and diatoms such as Nitzschia are known.

As an agent for suppressing the growth and proliferation of these algae, polyamine sulfone obtained by copolymerizing dimethyldiallylammonium chloride and sulfur dioxide is disclosed in JP-A-61-194002.
This polyamine sulfone not only has a strong algicidal activity against algae, particularly green algae, but also has the advantage that it is non-effervescent and non-irritating to humans, livestock and other warm-blooded animals. .

[Problems to be Solved by the Invention] In addition to algae, obstacles in industrial water and cooling tower treated water are caused not only by algae but also by microorganisms (bacteria and molds). Clogging occurs. Especially in recent years,
When water is saved in the open-circulation cooling water system and high concentration operation is performed, nutrients are concentrated for the microorganisms in the water, and as a result, the microorganisms that have propagated are distributed to the sprinklers, fillers, and heat exchangers of the cooling tower. It adheres and forms ooze, causing various disorders such as accelerated corrosion and clogging, and general bacteria that are one of the causes of these disorders are mainly Zoogloea and Sphaerotilus.

However, although polyamine sulfone and polyamine are effective against algae (especially green algae), no effect is observed on general bacteria, and as an agent for industrial water and cooling tower treatment water, algicidal / algae effective against algae and general bacteria is effective. There was a need for a fungicide.

Accordingly, an object of the present invention is to provide a novel algicide / bactericide which is effective against algae and general bacteria.

[Means for Solving the Problems] The present inventor has found that as a result of long-term research, homopolymerization of polyamine sulfone and / or dialkyl diallyl ammonium chloride obtained by copolymerizing dialkyl diallyl ammonium chloride and sulfur dioxide is carried out. When N- (2-hydroxyalkyl) -aminomethanol is mixed and used with the polyamine obtained by the above, the growth of general bacteria is suppressed, and the growth of algae is also suppressed at the same time.
Furthermore, the range of algicidal effect is expanded as a synergistic effect,
That is, it has been found that the types of alga that can be algicidally increased and the amount of drug required for algicidal reduction was reduced.

Therefore, the present invention relates to a polyamine sulfone obtained by copolymerizing a dialkyldiallylammonium chloride and sulfur dioxide and / or a polyamine obtained by homopolymerizing a dialkyldiallylammonium chloride, and N- (2-hydroxyalkyl)
-An algicidal / fungicidal agent characterized by containing amino methanol as an essential component.

 Hereinafter, the present invention will be described in detail.

The polyamine sulfone used as an essential component in the algicidal and fungicide of the present invention is obtained by copolymerizing a dialkyldiallylammonium chloride and sulfur dioxide, and has the formula (Wherein, R is a lower alkyl group). The molecular weight of the polyamine sulfone is usually from 2,000 to 350,000. The molecular weight of the polyamine sulfone is determined not only from the algicidal property but also from the foaming aspect.In order to suppress the generation of foam when the polyamine sulfone is added to the liquid to be treated, the higher the molecular weight, the better, In the context of algicidal properties, the molecular weight is optimally between 90,000 and 120,000.

In the above formula (I), R is a lower alkyl group such as methyl, ethyl or propyl group, but it is most preferable to use a polyamine sulfone in which R is a methyl group in view of the availability of raw materials and the price.

In the algicide / bactericide of the present invention, a polyamine obtained by homopolymerizing a dialkyldiallylammonium chloride can be used instead of or together with the polyamine sulfone.

This polyamine has the formula (Wherein, R is a lower alkyl group). The molecular weight of this polyamine ranges from 50,000 to 70, taking into account algicidal and other properties.
It is preferably 0,000, most preferably 120,000-170,000.

In the above formula (II), R is a lower alkyl group such as a methyl, ethyl or propyl group, but it is most preferable to use a polyamine in which R is a methyl group in view of the availability of raw materials and the price.

The algicidal / bactericide of the present invention contains N- (2-hydroxyalkyl) -aminomethanol as another essential component together with the polyamine sulfone and / or polyamine. The alkyl group in N- (2-hydroxyalkyl) -aminomethanol is preferably a lower alkyl group such as a methyl, ethyl, propyl and butyl group. N- in which the alkyl group is a propyl group
It is particularly preferred to use (2-hydroxypropyl) -aminomethanol.

In the algicidal / fungicide of the present invention, polyamine sulfone and / or polyamine and N- (2-hydroxyalkyl)-
Aminomethanol is preferably used in such a ratio that the former is 95 to 50 parts and the latter is 5 to 50 parts by weight. The reason is that if the amount of N- (2-hydroxyalkyl) -aminomethanol is less than 5 parts, the synergistic effect is poorly expressed, and if it exceeds 50 parts, the effect is not only saturated but also disadvantageous in cost. Because.

The algicidal / bactericide of the present invention comprises polyamine sulfone and / or
Or a polyamine and N- (2-hydroxyalkyl)-
It is obtained by dissolving amino methanol in water in the above-mentioned ratio. This aqueous solution can be used as it is as an algicidal / bactericide aqueous solution.

In addition to the essential components, other components commonly used in algicidal and fungicidal agents, such as stabilizers and preservatives, may be added.

In using the algicidal / bactericide of the present invention, polyamine sulfone and / or polyamine and N- (2-hydroxyalkyl) -aminomethanol are used at a concentration such that the total amount thereof is 20 to 100 ppm. It is preferably added to a liquid to be treated such as industrial water or cooling tower treatment water. The reason is that if the amount is less than 20 ppm, the effect is not sufficient, and if it exceeds 100 ppm, the effect is saturated.

[Action] The algicidal / bactericide of the present invention comprises polyamine sulfone and / or
Or a polyamine and N- (2-hydroxyalkyl)-
When used in combination with aminomethanol, it exhibits algicidal and bactericidal effects. Further, by using both drugs together, an effect is exhibited also on cyanobacteria which is ineffective by using polyamine sulfone or polyamine alone. Also, the amount of drug required for algicidal treatment can be reduced. Although the details of the cause of this synergistic effect are unknown, it is considered that the mechanism of action of the two drugs is different. That is, the action of polyamine sulfone or polyamine is that polyamine sulfone or polyamine is adsorbed on the cell surface and damages the cell surface, but N- (2-hydroxyalkyl)
The action of aminomethanol is that it penetrates the cell membrane,
It is thought to cause intracellular damage, and through these different mechanisms of action, the combined use of both drugs is thought to accelerate the cell damage effect.

[Examples] In order to further explain the present invention, examples are shown below.
However, these examples show preferred specific examples of the present invention, and the present invention is not limited to these examples.

Example 1 As the polyamine sulfone, a polymer (molecular weight 100,000) obtained by copolymerization of dimethyldiallylammonium chloride and sulfur dioxide, in which R is a methyl group in the repeating unit of the above formula (I) was used (hereinafter, referred to as “polyamine sulfone”). In this example, this polymer is abbreviated as polyamine sulfone (R = CH ₃ ).

As N- (2-hydroxyalkyl) -aminomethanol, N- (2-hydroxypropyl) -aminomethanol (molecular weight: 105, water-soluble, alkali-soluble, appearance: liquid, specific gravity: 1.08, 1% solution pH: 10.6, non-ionic)
Was used.

Polyamine sulfone (R = CH ₃ ) and N- (2-hydroxypropyl) -aminomethanol are mixed at a ratio of 90/10, and the mixture is dissolved in water at room temperature to prepare polyamine sulfone (R = CH ₃ ) and N An algicidal / bactericide aqueous solution having a total concentration of-(2-hydroxypropyl) -aminomethanol of 10% was obtained.

For comparison, a polyamine sulfone (R = CH ₃ ) alone was dissolved in water at room temperature to obtain an aqueous solution having a polyamine sulfone (R = CH ₃ ) concentration of 10%. Also for comparison,
N- (2-Hydroxypropyl) -aminomethanol alone was dissolved in water at room temperature to obtain an aqueous solution in which the concentration of N- (2-hydroxypropyl) -aminomethanol was 10%.

The following tests were performed using these aqueous solutions.

The sample used for the test was obtained from cooling tower cooling water of a building in Chuo-ku, Tokyo. This cooling water was water obtained by concentrating approximately 10 times the tap water (drinking water) in Tokyo, and had general water quality as urban cooling water.

Sterilization test: The above three kinds of aqueous solutions were added to 100 ml of the above sample so that various concentrations of the drug were obtained, and the solution was allowed to stand in a thermostat at 20 ° C. After 96 hours, the number of surviving general bacteria was determined by a general bacteria test. The general bacteria test used a method using a simple detection paper for general bacteria (paper method).

The results are shown in Table 1. The number of living general bacteria in the table is the number of bacteria in 1 ml.

As apparent from Table 1, the polyamine sulfone (R
= CH ₃ ) and N- (2-hydroxypropyl) -aminomethanol have a bactericidal effect of N- (2-hydroxypropyl) -aminomethanol alone (concentration of 30 ppm at 0 ppm / ml). It falls short of the polyamine sulfone _{(R = CH 3) / N-} (2- hydroxypropyl)
The amino-methanol ratio is 90/10 and N- (2
Despite the composition having a very low ratio of -hydroxypropyl) -aminomethanol, the number of living general bacteria was 0 / ml at a concentration of 100 ppm, and polyamine sulfone (R = C
H ₃ ) was far superior to the bactericidal effect of the single product (the number of surviving general bacteria at the same concentration of 100 ppm: 8 bacteria / ml).

Algae killing test: Blue algae (Oscillat) grown in the above cooling tower
Oria limosa) was taken in an appropriate amount (about 1 g), placed in a beaker, and made up to 100 cc with tap water after residual chlorine removal. Three kinds of aqueous solutions containing various concentrations of the drug were added to this solution, and immediately mixed well to homogenize the algae. Then, the solution was allowed to stand in a sunny place and stirred well once a day.

At the same time, a 20W fluorescent lamp was placed 30 cm above and continued to emit light. Water temperature was 15-25 ° C. Green algae (Cladop)
hora sp.), algae that grew on the surface of the irrigation canal in Suginami-ku, Tokyo were sampled and subjected to the same tests as cyanobacteria. After 96 hours, the algae were cut off with tweezers and examined under a microscope (JIS K0101 64.4.2 method). The death of the algae was visually observed by the presence or absence of respiratory action and decolorization of the algae. Lethal dose of algae by drugs represented by the lethal concentration (LC), showed concentration corresponding to 50% mortality in a semi-lethal concentration LC _50.

 Table 2 shows the results.

As apparent from Table 2, the polyamine sulfone (R
= CH ₃ ) and N- (2-hydroxypropyl) -aminomethanol are the same as polyamine sulfone (R = CH ₃ ) alone for green algae, but polyamine for cyanobacteria sulfone (R = CH ₃₎ and N-
(2-Hydroxypropyl) -aminomethanol is significantly more effective than a single product, showing a synergistic effect.

As can be seen from Tables 1 and 2, the mixture of polyamine sulfone (R = CH ₃ ) and N- (2-hydroxypropyl) -aminomethanol suppresses the growth and proliferation of general bacteria, and also inhibits cyanobacteria and green algae. Inhibits the growth and proliferation of, and has a remarkable synergistic effect, especially on cyanobacteria.

Example 2 polyaminesulfon (R = CH ₃₎ and N-(2-hydroxypropyl) - except that the ratio between the amino methanol was 60/40 was performed in the same manner as in Example 1. The results are shown in Tables 3 and 4.

As is clear from Tables 3 and 4, the polyamine sulfone (R = CH ₃ ) and N- (2
-Hydroxypropyl) -aminomethanol mixture,
It suppresses the growth and proliferation of general bacteria and suppresses the growth and proliferation of blue-green algae and green algae.

Example 3 Instead of the polyamine sulfones (R = CH ₃ ) of Examples 1 and 2, a polyamine having a molecular weight of 150,000 (R = C), which is a homopolymer of a dialkyldiallylammonium chloride.
Tables 5 and 6 show the results of similar algicidal and bactericidal tests using H ₃ ). The ratio of polyamine (R = CH ₃ ) and N- (2-hydroxypropyl) -aminomethanol was 70/30 and used in the test.

As is clear from Tables 5 and 6, the mixture of polyamine (R = CH ₃ ) and N- (2-hydroxypropyl) -aminomethanol suppresses the growth of general bacteria and is remarkable against cyanobacteria. Shows a synergistic effect.

[Effects of the Invention] According to the present invention, polyamine sulfone, which is a copolymer of dialkyldiallylammonium chloride and sulfur dioxide, and / or polyamine, which is a homopolymer of dialkyldiallylammonium chloride, have N- (2-
The combined use of (hydroxyalkyl) -aminomethanol suppresses the growth and proliferation of general bacteria, suppresses the growth and proliferation of algae such as green algae, and shows a particularly remarkable effect on cyanobacteria.

Therefore, polyamine sulfone and / or polyamine and N
The algicidal / disinfectant of the present invention containing-(2-hydroxyalkyl) -aminomethanol as an essential component is extremely effective in preventing troubles in a water supply system for industrial water and a cooling tower heat exchanger in a building.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification number Agency reference number FI Technical display location A01N 33:08)

Claims (1)

(57) [Claims] 1. A polyamine sulfone and / or a polyamine obtained by homopolymerizing a dialkyldiallylammonium chloride obtained by copolymerizing a dialkyldiallylammonium chloride and sulfur dioxide, and N- (2-hydroxyalkyl)- An algicidal / bactericide comprising amino methanol as an essential component.