JPH10158102A - Growth retarding agent for algae and moss - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a growth retarding agent for algae and moss that contain a specific ionene type polymer and a specific antimicrobial agent, has growth retarding effects on terrestrial algae and moss without contaminating environment, and can be produced easily at a low cost. SOLUTION: This growth retarding agent for algae and moss contains an ionene type polymer of formula I [(x) is an integer of 2-6; (y) is an integer of 3-11] or formula II [(z) is an integer of 2-6] which has a molecular weight of 1,000-10,000 and is easily produced by a reaction of a tertiary diamine with a dihalide or epihalohydrin, and an organic anionic antimicrobial agent, for example, a sorbinate or benzoate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a growth inhibitor useful for algae and moss, especially terrestrial algae and moss.

[0002]

2. Description of the Related Art Algae and moss reproduce together with ornamental plants and agricultural plants, and impair the appearance and cause odor. Also,
Even on golf courses, it occurs on the green, hurt the aesthetics,
In order to hinder the growth of turf, suppression is required.

[0003] Copper sulfate, slaked lime, certain pesticides, and quaternary ammonium compounds are said to be effective in suppressing the growth of algae. However, copper sulfate can be harmful to plants,
Slaked lime harms plants when used too much. Pesticides are subject to strict restrictions to pollute the environment and must be used with extreme caution. Certain quaternary ammonium compounds are effective as algicides, but have a surfactant effect and, when added to water in small amounts, have problems in foaming workability as well as irritation to the skin.

[0004] The suppression of moss growth involves the use of pesticides but does not provide a sufficient growth suppression effect, and also has problems in terms of environment and safety.

Japanese Patent Publication No. 50-25728 proposes a method for suppressing the growth of algae by bringing poly [oxyethylene (dimethylimino) ethylene (dimethylimino) ethylene dichloride] into contact with algae. For example, there are some types that cannot provide a sufficient effect.

Accordingly, the present inventors have developed an anti-algal agent comprising an ionene-type polymer (Japanese Patent Application No. 7-201289), and have conducted extensive studies on a wide range of effective agents such as algae and moss. The present invention has been completed.

[0007]

SUMMARY OF THE INVENTION The present invention provides an inexpensive growth inhibitor which has an effect of inhibiting the growth of terrestrial algae and moss in particular, is free from environmental pollution and is easy to produce.

[0008]

Means for Solving the Problems That is, the present invention provides

Embedded image (Where x = 2 to 6, y = 3 to 10 in the formula, and x and y are integers) or

Embedded image (However, z is 2 to 6 in the formula, and z is an integer.)
The present invention relates to a growth inhibitor comprising an ionene-type polymer of No. 00 and an organic anionic antibacterial agent such as sorbate or benzoate, and particularly useful for land algae and moss.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION First, the ionene-type polymer of the present invention will be described. The polymer can be easily produced by reacting a tertiary diamine with a dihalide or epihalohydrin.

The ionene-type polymer is a water-soluble polymer electrolyte having a quaternary ammonium ion in the main chain of the polymer. Examples of the tertiary diamine include tetramethylethylenediamine, tetraethylethylenediamine, tetramethylpropanediamine, tetraethylpropanediamine, tetramethylbutanediamine, tetraethylbutanediamine, tetramethylhexanediamine, tetraethylhexanediamine, and the like. Diamines having groups are preferred. Examples of the dihalide include dichloropropane, dichlorobutane, dichlorohexane, dichlorodecane and the like. As the epihalohydrin, those in which the halogen is chlorine, fluorine, bromine, or iodine are targeted, but epichlorohydrin is preferable for economic reasons.

As a method for producing the above-mentioned ionene-type polymer, a tertiary diamine is mixed with a dihalide or epihalohydrin.
In the latter case, the reaction may be carried out with stirring at 70 to 95 ° C. for 6 to 30 hours. If the temperature is lower than 70 ° C., the yield of the ionene-type polymer is poor.

The above-mentioned ionene-type polymer is obtained, for example, by preparing tetramethylhexanediamine and dichloropropane in order to obtain a polymer having x = 6 and y = 3 in Chemical formula 1.
For example, the reaction may be performed at a molar ratio of 1: 1.
In order to obtain a polymer with y = 3, tetramethylpropanediamine and dichloropropane may be reacted at a molar ratio of 1: 1. Further, in the chemical formula 2, in order to obtain a polymer of z = 4, tetramethylbutanediamine and epichlorohydrin may be reacted at a molar ratio of, for example, 1: 1.

The important point of the present invention is to add an organic anionic antibacterial agent to the above-mentioned ionene-type polymer in order to express the growth inhibiting effect on algae and moss widely.

Examples of the organic anionic antibacterial agent include sorbate and benzoate.

It should be noted that in the state of an acid such as sorbic acid or benzoic acid, the solubility in water is low, so that it is difficult to use it and no synergistic effect is obtained when used in combination with the polymer. Therefore, it must be in the form of a salt such as potassium sorbate and sodium benzoate. .

When the organic anionic antibacterial agent is added to the ionene-type polymer, the molar ratio of the N ⁺ cation in the ionene-type polymer to the anion (COO ⁻ ) of the organic anionic antibacterial agent in the aion is 1: 1. 0.5-2
It is added in such a ratio that In particular, 1: 1 is preferred. When used for moss, the use ratio of the two is preferably 1: 0.5 to 1.5, especially 1: 1.

Furthermore, in the present invention, it was also found that the use of a polyacrylate together with an organic anionic antibacterial agent makes it possible to suppress plant damage to plants. As a use ratio of sodium polyacrylate, a molar ratio of ions (a molar ratio of N ⁺ : COO ⁻ ions) to the ionene type polymer is 1: 0.04 to 0.2. 0.0
If the amount is less than 4, the effect of preventing plant phytotoxicity is weak,
If the addition amount is more than 0.2, the effect of inhibiting the growth of algae and moss is weakened.

The molecular weight of the polyacrylate is preferably about 1,000 to 10,000 in terms of viscosity average molecular weight.

Japanese Patent Application Laid-Open No. 63-256192 describes a combination of a water-soluble sorbate and a water-soluble alkali metal salt as a bulking inhibitor, but bulking is caused by a filamentous fungus. ,
This is different from the present invention for algae and moss. Also, JP-A-6
JP-A-71286 describes a bactericide (antibacterial agent) effective against filamentous fungi, which is a reaction product of a dialkylamine and epihalohydrin or a sorbate, but is used as a bulking inhibitor.

The production and use method of the growth inhibitor of the present invention is as follows.
It is dissolved in water so as to have a concentration of 5.0% by weight, and an organic anionic antibacterial agent and, if necessary, a polyacrylate are added thereto and dissolved by heating. Alternatively, after an aqueous solution of an ionene-type polymer and an aqueous solution of a polyacrylate are mixed well, an organic anionic antibacterial agent may be added thereto, followed by heating and dissolving. The thus-produced growth inhibitor of the present invention is applied at a rate of 1 to ¹⁰ L per 1 m ² where terrestrial algae or moss is growing.

The growth inhibitor of the present invention exhibits the best effect because the ionene type polymer in the growth inhibitor is
At x = 6 and y = 3.

As the ionene type polymer, one having a viscosity average molecular weight in the range of 1,000 to 10,000 is used. If it is less than 1,000, no effect can be expected.
If it exceeds 000, handling becomes difficult and the effect is reduced.

Examples of the present invention will be described below, and the present invention will be described in more detail. However,% is weight% unless otherwise specified.
Is shown.

(Examples) 1) Growth inhibitor A N, N, N ', N'-tetramethylethylenediamine (98%, Tokyo Chemical Industry Co., Ltd.)
49.3 g) and dichloromethane (manufactured by Tokyo Chemical Industry Co., Ltd.).
7 g and 90 g of distilled water are mixed and stirred (800 rpm)
Under a temperature of 95 ° C. for 16 hours.
A 00 ionene-type polymer was produced. The ionene-type polymer was diluted with ion-exchanged water to make a 46% strength aqueous solution, and 100 g was placed in a 500 ml beaker and potassium sorbate (98%, manufactured by Yoneyama Chemical Co., Ltd.) 6
0.5 g and 150 g of ion-exchanged water are added and mixed and stirred.
After heating and dissolving at 0 ° C. for 2 hours, the mixture was allowed to cool to room temperature to obtain the growth inhibitor of the present invention (the molar ratio of N ⁺ in the ionene-type polymer to COO ⁻ ion in potassium sorbate = 1: 1).

2) Growth inhibitor B N, N, N ', N'-tetramethyl 1,6-hexanediamine (98%) 24.1 g
And 29.1 g of distilled water were mixed, and 28.5 g of hydrochloric acid (36%) was added dropwise in an ice water bath under stirring (800 rpm). 30
After stirring for 2 minutes, the liquid temperature was kept at 25 ° C., and
g was added dropwise. After stirring for 1 hour, a mixture of 24.1 g of N, N, N ', N'-tetramethylhexanediamine and 29.1 g of distilled water was added dropwise, and the mixture was heated to 70 ° C. and reacted for 30 minutes. 9,000 ionene-type polymers were produced. 100 g of this ionene-type polymer is placed in a 500 ml beaker, and sodium benzoate (special grade, manufactured by Wako Pure Chemical Industries, Ltd.) 5
0.1 g and 100 g of ion-exchanged water are added and mixed and stirred.
After heating and dissolving at 0 ° C. for 2 hours, the mixture was allowed to cool to room temperature to obtain the growth inhibitor of the present invention (the molar ratio of N ⁺ in the ionene-type polymer to COO ⁻ ion in sodium benzoate = 1: 1).

3) Growth inhibitor C 9.15 g of N, N, N ', N'-tetramethyl-1,3-fluorobenzeneamine and 53.5 g of distilled water are mixed, and the mixture is stirred in an ice water bath under stirring (800 rpm). (36%) 14.2 g was added dropwise. The mixture was stirred for 30 minutes, the liquid temperature was kept at 25 ° C., and 13.1 g of dichloromethane was dropped. After stirring for 1 hour, a mixture of 9.15 g of N, N, N ', N'-tetramethylfluoroamine and 53.5 g of distilled water was added dropwise.
The temperature was raised to 0 ° C. and reacted for 30 minutes.
500 inventive polymers were prepared. 100 g of this ionene-type polymer was placed in a 500 ml beaker, and 39.5 g of potassium sorbate (98%, manufactured by Yoneyama Pharmaceutical Co., Ltd.)
2.77 g of sodium polyacrylate (manufactured by Toagosei Co., Ltd., 50% aqueous solution) and 150 g of ion-exchanged water were heated and dissolved at 80 ° C. for 2 hours with mixing and stirring, then allowed to cool to room temperature, and then allowed to cool to room temperature. The molar ratio of N ⁺ in the ionene-type polymer: COO ^{− in} potassium sorbate: COO ⁻ ion in sodium polyacrylate = 1: 1.4: 0.08) was obtained.

4) Growth inhibitor D N, N, N ', N'-tetramethyl 1,6-hexadiamine (98%, manufactured by Wako Pure Chemical Industries, Ltd.)
24.2 g, 1,6-dichlorohexane (98%,
21.5 g of distilled water and 104.3 g of distilled water were mixed and reacted at 100 ° C. for 20 hours under stirring (800 rpm) to produce an ionene-type polymer having a viscosity average molecular weight of 5,700. 100 g of this ionene-type polymer was added to 5
In a 00 ml beaker, add 100 g of ion-exchanged water, and add sodium benzoate (special grade, manufactured by Wako Pure Chemical Industries, Ltd.) 1
8.5 g, sodium polyacrylate (Toagosei Co., Ltd.)
, 50% aqueous solution), mixing and stirring 80
℃ in cooling to heating for 2 hours after dissolution at room temperature, growth regulators of the present invention (in the ionene polymer N ^+: COO in sodium benzoate ^-: CO in the sodium polyacrylate
O ^- molar ratio of the ion = 1: 0.7: 0.1) was obtained.

5) Growth inhibitor E N, N, N ', N'-tetramethyl 1,3-fluoro-diamine (manufactured by Wako Pure Chemical Industries, Ltd.
98%, reagent grade 24.2 g and 1,6-dichlorohexane (98%)
%, Manufactured by Merck & Co., Ltd.) and 104.3 g of distilled water were mixed and reacted at 100 ° C. for 20 hours under stirring (800 rpm) to produce an ionene polymer having a viscosity average molecular weight of 5,700. 100 g of this ionene-type polymer is placed in a 500 ml beaker, 63.5 g of sodium benzoate (special grade, manufactured by Wako Pure Chemical Industries, Ltd.), 4.35 g of sodium polyacrylate (50% aqueous solution, manufactured by Toagosei Co., Ltd.), ion exchange It was allowed to cool water 200g at mixing and stirring 80 ° C. until 2 hours heating and dissolving at room temperature after growth inhibitor of the present invention (in the ionene polymer N ^+: COO in sodium benzoate ^-: during polyacrylic acid COO ^- Ion molar ratio = 1: 1.
9: 0.1).

6) Growth inhibitor F N, N, N ', N'-tetramethyl 1,6-hexadiamine 20.6 g and 1,10-dichlorotechan (96%, manufactured by Merck) 25.3 g and distillation Water 104.
1 g and mixed at 95 ° C. under stirring (800 rpm) for 25 minutes.
The reaction was carried out for a time to produce an ionene-type polymer having a molecular weight of 1,500. 100 g of this ionene-type polymer is 500
22.3 g of potassium sorbate, 1.47 g of sodium polyacrylate (manufactured by Toagosei Co., Ltd., 50% aqueous solution) and 100 g of ion-exchanged water were mixed and heated at 80 ° C. for 2 hours with stirring and dissolved to room temperature. After cooling, the growth inhibitor of the present invention (the molar ratio of N ⁺ in the ionene-type polymer: COO ^{− in} potassium sorbate: COO ⁻ ion in polyacrylic acid = 1: 0.95: 0.05) was obtained. Was.

7) Growth inhibitor G An ionene-type polymer was produced in the same manner as the growth inhibitor A. 100 g of this ionene type polymer is 500 ml
In a beaker, 30.5 g of potassium sorbate and 150 g of ion-exchanged water were added, and the mixture was heated and melted at 80 ° C. for 2 hours with mixing and stirring, and then allowed to cool to room temperature. The growth inhibitor of the present invention (N ^{+ in} ionicene-type polymer: sorbin COO in the acid potassium ^-
(Ion molar ratio = 1: 0.5).

8) Growth Inhibitor H An ionene-type polymer was produced in the same manner as the growth inhibitor C. 100 g of this ionene type polymer is 500 ml
In a beaker, add potassium sorbate (Yoneyama Pharmaceutical Co., Ltd.)
, 98%), 1.73 g of sodium polyacrylate (manufactured by Toagosei Co., Ltd., 50% aqueous solution), and 100 g of ion-exchanged water. Growth inhibitor of the present invention (N ⁺ in the ionene type polymer: COO ^{− of} potassium sorbate: molar ratio of COO ⁻ ion in polyacrylic acid = 1: 0.75:
0.05).

Comparative Examples 1 to 3 Comparative Example 1 Potassium sorbate (Yoneyama Pharmaceutical Co., Ltd., 9
(8%) 32.5 g was put into a 500 ml beaker and dissolved in 300 ml with ion exchanged water. (Comparative Example 2) An ionene-type polymer was produced by the same operation as that of the growth inhibitor A. (Comparative Example 3) An ionene-type polymer was produced by the same operation as that of the growth inhibitor B.

[0033] <Evaluation Test 1> growth inhibitor A of the present invention to Koryo grass cyanobacteria Nostoc commune are growing (160cm ^2/1 compartment), B, C, D, E, F the ionene polymer in terms of solid content Was diluted with ion-exchanged water to give a 0.3% aqueous solution and sprayed 50 ml. Similarly, Comparative Examples 1 to 3
Was diluted with ion-exchanged water so as to be a 0.3% aqueous solution and sprayed with 50 ml of the solution, and the time-dependent change in the growth state of the jellyfish was observed. An appropriate amount of water was sprayed every day. * The growth inhibitor was re-sprayed 2 weeks later.

[0034]

[Table 1] Growth status of blue-green algae Ichryusa (0: no change 1: slight discoloration 2: 1/2 discoloration and partial growth 3: discoloration more than 1/2 4: discoloration more than 4/5 5: discoloration overall) As described above, the growth inhibitor of the present invention has a very excellent growth inhibitory effect on algae and has no phytotoxicity to turf.

<Evaluation Test 2> The growth inhibitors A, B, C, D, E, and F of the present invention were reduced to 0% in terms of the solid content of an ionene-type polymer in the seagrass turf (160 cm ² / compartment) where the green alga Hibimidoro was growing. The solution was diluted with ion-exchanged water to a concentration of 0.3% and sprayed with 50 ml. Similarly, the drugs of Comparative Examples 1 to 3 were diluted to a 0.3% aqueous solution and sprayed with 50 ml, and the time course of the growth state of the green algae was observed. An appropriate amount of water was sprayed every day. * The growth inhibitor was re-sprayed 2 weeks later.

[0036]

[Table 2] Growth status of green alga Hibimidoro (0: no change 1: slight discoloration 2: 1/2 discoloration and partial growth 3: discoloration more than 1/2 4: discoloration more than 4/5 5: discoloration as a whole) In addition, the growth inhibitor of the present invention has an excellent growth inhibitory effect on green algae and has no phytotoxicity to turf.

<Evaluation Test 3> The growth inhibitor A of the present invention was applied to soil (160 cm ² / compartment) where yagake was growing.
G and H were sprayed in a volume of 50% so as to be a 0.3% aqueous solution in terms of an ionene-type polymer solid content. Similarly, the drugs of Comparative Examples 1 to 3 were diluted with ion-exchanged water to 0.3%. And moss growth was observed over time. * It was sprayed again two weeks later.

[0038]

[Table 3] Growing state of turbidity (0: no change 1: slight discoloration 2: 1/2 discoloration and partial growth 3: discoloration of 1/2 or more 4: discoloration of 4/4 or more 5: discoloration of the whole) Thus, among the growth inhibitors of the present invention, those in which the molar ratio of N ⁺ in the ionene type polymer to COO ⁻ ion in the anionic antibacterial agent is 1: 1 have an excellent growth inhibiting effect on moss. And it turned out to be safe.

<Evaluation Test 4> Korai turf (160 cm ²
/ 1 section) in the growth inhibitors A, B, C, D, E,
F and G were diluted with ion-exchanged water so as to be a 0.9% aqueous solution in terms of ionene-type polymer solid content and sprayed with 50 ml, and the state of the phytotoxicity of the growth inhibitor of the present invention on turf was observed. * It was sprayed again two weeks later.

[0040]

[Table 4] Grass condition (1: yellowing 2: fairly yellowing 3: slightly yellowing 4: almost green 5: green) As shown in Table 4, about 3 which usually uses the growth inhibitor of the present invention is used.
Even when used at twice the concentration, addition of sodium polyacrylate showed almost no harm to turf.

[0041]

The growth inhibitor of the present invention comprises:

Embedded image (Where x = 2 to 6 and y = 3 to 10 in the formula, and x and y are integers) or

Embedded image (Where z is 2 to 6, and z is an integer) represented by an ionene-type polymer having a viscosity average molecular weight of 1,000 to 10,000 and an organic anionic antibacterial agent such as sorbate and benzoate. And an excellent growth-inhibiting agent that exhibits an excellent growth-inhibiting effect on algae or moss and that is easy to produce and extremely safe. The growth inhibitor of the present invention further comprises sodium polyacrylate containing N 2 in an ionene-type polymer.
⁺ : By adding COO ⁻ ions in the sodium polyacrylate in a molar ratio of 1: 0.04 to 0.2, chemical damage to plants can be prevented.

Claims (3)

[Claims] [Claim 1] (Where x = 2 to 6, y = 3 to 10 in the formula, and x and y are integers) or (However, z is 2 to 6 in the formula, and z is an integer.)
A growth inhibitor for algae or moss comprising an ionene type polymer of No. 00 and an organic anionic antibacterial agent. (2) (Where x = 2 to 6, y = 3 to 10 in the formula, and x and y are integers) or (However, z is 2 to 6 in the formula, and z is an integer.)
A growth inhibitor for algae or moss comprising an ionene-type polymer of No. 00, an organic anionic antibacterial agent and a polyacrylate. 3. The growth inhibitor for algae or moss according to claim 1, wherein the organic anionic antibacterial agent is sorbate or benzoate.