KR900006520B1 - Process for enhancing the activity of plant protecting agents by using cyclodextrin - Google Patents

Abstract

A fungicidal plant protecting compsn. comprises 3-90 wt.% of a fungicide and 1-90 wt.% of cyclodextrin (alpha, beta or gamma) opt. with usual auxillary agents. - Specifically the ratio of fungicidal active ingredient and cyclodextrin is 90:1-1:5, pref. 2-5:1. The fungicidal active ingredient is pref. benomyl, BCM, metomeclan or phenarimol.

Description

Bactericidal plant protection composition and sterilization method using the same

The present invention relates to a novel plant protection agent, and more particularly, to a bactericidal plant protection composition and a sterilization method using the same.

Recently, articles and patents on the use of cyclodextrins as plant protection agents have been published [Novenyvedelem. 19, 364 (1983): J Szejtle Cyclodextrin and Containing Complexes thereof, Akademiaikiado, Budapest, 1982], for example molinat (S-ethyl-N, N-hexmethylene-thiocarbamate), benthiocarb (S By forming a complex of -4-chlorobenzyl-diethylthiocarbamate) and dichloropus (2,2-dicholovinyl-dimethyl-phosphate), the volatility of the active ingredient is satisfactorily reduced and the activity of the pesticide residues is reduced. Mikasa Chemical Industrial Corporation Japan Publication No. 881806, DOS

No. 2,422,316 (1974), Acta chem. Aced. Sci Hung. 107,195 (1981)], ethyl-parathion (O, O-dimethyl-O-4-nitrophenyl-phosphothioate) and natural pyredrin and pyredrin agents to remarkably significant changes Increased stability to light and oxygen [Pestic. Sci. 11,134 (1980): US Pat. No. 3,846,551 (1974): Nippon Noyaku Kagaishi 1,41 (1976), 2,41 (1977)] Diclobenyl (2,6-dichloro-

The benzonitrile) active ingredient was easily sublimed and the particle product stuck together, preventing it by forming a complex with cyclolotextrin [5th Int. Cong. Pesticide Chem (IUPAC) Kyoto (1983)].

In addition, the complex form of 2-chloromethane-phosphonic acid with cycloxdextrin releases ethylene permanently when it comes into contact with plant tissues, thereby activating the active ingredient very quickly, thereby releasing ethylene more effectively. [Acta chem . Acad. Sci. Hung. 107,231 (1981).

Thus, conventionally, cyclodextrin could not be useful as a fungicide.

It is therefore an object of the present invention to provide a bactericidal composition consisting of cyclodextrins having a satisfactory activity such as a known bactericidal component. Such bactericidal active ingredient preparations can achieve the same bactericidal effect even if they have higher activity or have a lower daily dose of the active ingredient, and are economically effective and do not contaminate the surrounding environment. It is.

The present invention provides a bactericidal plant protection composition containing 3-90% of bactericidal active ingredient by weight in a mixture of 1-90% of cyclodextrin by weight and, if necessary, a known adjuvant. The bactericidal composition according to the invention contains the bactericidal active ingredient and cyclodextrin in a ratio of 90: 1-1: 5, preferably 2-5.1.

The composition according to the present invention may preferably consist of the following bactericidal active ingredients: benomil = 1-butylcarbamoyl-benzimidazole-2-methyl-carbamate; BCM = 2-Carbomethoxyamino-benzimidazole, Metomelan = l- (3,5-dichlorophenyl) -3-methoxymethyl-pinolidine-2,5-dione: phenarimol = 2 , 4'-dichloro-α '-(pyrimidin-5-yl) -diphenyl-methanol

As cyclodextrins, α-, β- and γ-cyclomyxtrins and mixtures thereof may be used. According to another embodiment of the present invention, the ratio of the active ingredient to cyclodextrin may be as follows.

Benomil Cyclotextin = 2-5: 1

BCM: cyclotextrin = 2-5: 1

Ethmelan: Cyclomictrin = 2-20: 1

Penarimol: cyclodextrin = l-100: 1

The present invention also provides a method for sterilizing the composition according to the invention by treating the surface of the plant or other surface, preferably at a rate of 0.5-6 Kg / ha, in particular 1.2-1.6 Kg / ha.

The present invention provides a known bactericidal active ingredient and a cyclodextrin exhibiting a synergistic effect from any one or two of the following factors: the unique bactericidal activity of the cyclodextrin and the solubility enhancing the effect of the cyclodextrin. The bactericidal activity of such cyclodextrins has never been published in the past, and its bactericidal activity can be demonstrated by the following experiment.

That is, agar culture medium consisting of 0.1-0.2-0.5-1.0-2.0-5.0-10.0-20.0-l00.0-200.0-400.0--800.0-1200.0-1500.0-2000.0-3000.0μg β-cyclodextrin per milliliter Prepare each of the petri dishes in a Petri dish, and then cut the mycelium discs with the surface cultures of the three test bacteria and place them in the agar nutrient medium in the Petri dish, and then incubate them under temperature control to increase the diameter of the selected colonies. Prepare a control like this. Diffusion of colony form and staining material was achieved from the bacteria in the culture medium and the results are well calculated and the results are shown in Table 1 below.

Table 1

Bactericidal Effect of β-Cyclodextrin

Β-cyclodextrin has a qualitative effect in the range of 0.1-20 μg / ml of the working dose. The bactericidal effect of cyclodextrin is due to the change in the microorganism and colony tissue and color, and the amount of dye penetrated into the culture medium. It appeared on its own. However, at higher doses, cyclodextrins were already quantitative in nature, where the diameter reduction of colonies could be measured and the biomass of the formation was markedly reduced (Table 1). It shows that it suppresses the form of the breeding organism.

On the other hand, the greatest feature that increases the solubility of the cyclodextrin in the form of complexes is the active ingredient molecularly dispersed (ie, substantially degraded) and slightly or slightly more fine molecules (fine crystals, fines). The fact is that complexes containing cyclodextrin actives, which are also present in molecularly dispersed form, also appear in aqueous solutions, except for mycelium, which is composed of droplets. Such a system is characterized by an unusually dynamic equilibrium (at 10 ^-8 sec ^-1) . The active ingredient mixed in the containing complex acts in the same way from the point of view of being absorbed like the freely decomposed active ingredient, since the composition of the molecularly decomposed micromolecules becomes suitable for direct absorption. Cyclodextrins can be satisfactorily supplemented, thereby accelerating the rate of absorption. In other words, we also are able to use less active ingredient to achieve the same efficiency

The positive effect of cyclodextrin resulting from the solubility of the active ingredient is shown in the examples using benomil, wherein the active ingredient (1-butylcarbamoyl-benzimidazole-2-betayl-carbamate) is a systematic disinfectant, When not dissolved in water and decomposed in water, it is rapidly decomposed into ethyl-benzimidazole carbaate which has a bactericidal effect until it is less soluble in water, i.e., benomil and benomil + cyclodextrin, respectively, in water at a temperature of 25 ° C. After stirring, the solubility data as shown in the following Table 2 are obtained. (Benomil and Benomil-β-cyclodextrin were respectively stirred at a temperature of 25 ° C. in water, and the samples were filtered and the decomposed benomil component was filtered. Minutes were analyzed by an ultraviolet spectrophotometer)

[Table 2]

Increased solubility of benomil under β-cyclodextrin effect

Benomil was purchased from the market under the trade name Fundazo1 50WP with a 50% active ingredient of benomil. Table 3 below shows the solubility and solubility data of the mixture of benomil, benomil and cyclomixtrin, Fundazo1 50WP and Fundazo1 50WP and cyclodextrin, and the solubility data for the mixture of cyclotextrin. It is 3000μ9 / ml by weight and stirred at 25 ° C. Benomil is a 100% active ingredient, and the benomil concentration of the benomil and cyclodextrin mixture is 17.3%, and the benomil concentration of the Fundazo1 50WP and cyclodextrin mixture is 8.65%. The solubility of benomil increased over 4 hours is shown in Table 3.

Cyclodextrins by themselves add 1.5-2 folds to increase the solubility of both the original benomil and the formulated Fundazo 150WP, with a remarkable amount of the active ingredient of benomil in the mixture of cyclodextrins. The biological effect arises from the fact that the concentration of benomil in the aqueous solution, which can have a substantial biological effect in the same time period, is quite high.

Table 3

Increased solubility of benomyl from Fundazo1 under the effect of β-cyclodextrin

The solubility of benomil in various materials consisting of benomil was measured by stirring in water at a temperature of 25 ° C., so that the solid material 2000 μg / m1 had a weight corresponding to the following amount of benomil.

2000 μg / m1 for benomil

For Benomil + β-Cyclodextrin: Benomil 350μg / m1 + β-Cyclodextrin 1650μg / m

For Fundazol 50 WP: 1000 μg / m1

For Fundazo1 50WP + β-cyclodextrin Fundazo1 50WP 175 μg / m1 + cyclodextrin 1650 μg The following test demonstrates a surprising synergy between known fungicides and β-cyclodextrins, resulting in stable and highly dispersed test substances. The aqueous suspension of was added to the agar culture medium at the required concentration (0.1-200 μg / ml) and then the culture medium was poured into a petri dish. Mycelial discs are cut from the surface culture of the test bacteria and placed in a Petri dish containing the test substance. The discs are then incubated with temperature control to increase the colony diameter and prepare such controls. This test is repeated three times.

Table 4 below shows the effects of the fungicide Fundazo1 50WP (benomil concentration 50%) and Fundazo1 50WP + 10% β-cyclodextrin, demonstrating the synergistic activity of β-cyclodextrin, in particular the sclerobacterial gray matter (Botrytis). satisfactory to cinerna) and monilia furutigena

Table 4

Bactericidal Activity of Fundazo1 and Re-reacted β-cyclodextrin

Metometholane is a contact disinfectant that is insoluble in water, so that the activity of [l- (3,5-dicholophenyl) -3-methoxymethyl-pinolidine-2,5-dione and metomelan is cyclized. It was satisfactorily increased by the addition of dextrin, and Table 5 shows the bactericidal effect of metmelan and metmelan + 10% β-cyclodextrin.

Table 5

Increasing the activity of metmeclan by adding 10% β-cyclodextrin

In vivo testing was performed in flour-shaped fungi (host parasites) using a compound of phenarimol [2.4'-dichloro-α (pyrimidin-5-yl) -diphenyl-ethanol] and β-cyclodextrin. This experiment was repeated three times on phytotrons under the same ambient conditions (20 ° C, 90.0% humidity, roughness-9000 lux).

In a culture dish (diameter 11 cm), an average of 160 plants (5-6 cm test bench) were treated with a stable aqueous suspension of 8 m1 consisting of test substances, and the results are shown in Table 6. Inhibitory activity was calculated by the Hinfner-Papp formula using the infectious index.

Table 6

In Vivo Testing of Penarimol + β-Cycolodextrin against Wheat Flour Fungal Host Parasites

As a continuation of the experiments, testing whether known linear xtrins obtained by heat 'enzymes or acid degradation of starch have the same effect as cyclocodextrins clearly shows that the cyclodextrins have such bactericidal synergistic activity. .

Industrial applicability

As a result, the synergistic effect of cyclodextrin can realize the same or rather increased sterilization effect of known commonly used bactericidal active ingredients, thereby reducing the cost according to the active ingredients. The risk of environmental pollution is also reduced.

Embodiment of the present invention

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited to the following Examples.

Preservatives containing benomil as active ingredient

Benomil purchases a spray powder in the form of a wet powder with a trade name Fundaz of 50 WP with a concentration of 50% of the active ingredient, and produces a product having the same activity and having a smaller amount of the active ingredient as follows.

In other words, 35 Kg of benomil made of very small powder in the air mill and 15 Kg (humidity l3%) of crystalline cyclodextrin made of very small powder in the air mill, 40 Kg of condensed potassium sulfide and 5 Kg of sulfide wet powder and water 5 Kg of a 50% nonionic surfactant (preferably preheated Genacol PGM at 50 ° C.) is mixed in a homogenizer, and then the mixture is dried, ground into very small powders and separated into particles for storage. Finally pack

Example 2

The steps of making the components into very small powder, homogenizing, drying and re-homogenizing are carried out in the same manner as in Example 1 except that the composition is as follows.

Benomyl (active ingredient l00%) 40 Kg

Condensed Calcium Carbonate 40 Kg

Tensiopix BC2 2.5Kg

Totamine 5Kg

β-Cyclomixtrin 12.5Kg

Example 3

Seed Treatment Composition Containing Benomil as Active Ingredient

It is carried out in the same manner as in Example 1, but the composition is as follows.

Benomil 35 Kg

Diothilan l Kg

Evidel l Kg

Tyros N20 l Kg

Aerosil "300" 0.5Kg

Safranin P Extra 2 Kg

38 Kg of Spray Dried Raw Material Changed to Cyclodextrin Mixture

(about 48% of β-cycloxtrin, α- and-21.5Kg

α-cyclodextrin content 2%, partially

Separated starch content about 50%)

Example 4

Seed Treatment Composition (2-Carbomethoxy Aminobenzimidazole) Containing Abem as Active Ingredient

The Aben active ingredient was dissolved in hydrochloric acid under heating and neutralized with an emulsion consisting of a mixture of bovine ammonium hydroxide, paraffin oil and β-cyclodextrin. The suspension was then stabilized with surfactants in a known manner to give To prepare a seed treatment having the same composition.

Ash 15%

Paraffin oil 19.8%

β-cyclodic 1 screen 5%

Ethylene glycol 5. 6%

Ammonium chloride (neutralized with hydrochloric acid solution) about 10%

Various surfactants,

Emuljogen M 0.24%

Atrox 4868 B 1 6%

Triton X45 1 9%

Tensiopix L051 0.2%

Tensiopix 821 0 2%

Charge to 100% water.

Claims (9)

A bactericidal plant protection composition comprising 3-90% bactericidal active ingredient by weight in a mixture consisting of 1-90% cyclodextrin by weight and, if necessary, a known adjuvant. The composition of claim 1, wherein the bactericidal active ingredient and the cyclodextrin are contained in a ratio of 90: 1-1: 5, preferably 2-5: 1. The composition according to claim 1, wherein the bactericidal active ingredient is benomil, BCM, metomelan or phenarimol The composition of claim 1, wherein the cyclodextrin consists of α-, β1 or γ-cyclodextrin. The composition of any one of claims 1, 2, 3 or 4, wherein benomil and cycldextrin are contained in a ratio of 2-5: 1, preferably 3.5: 1.5. The composition ratio according to any one of claims 1, 2, 3 or 4, wherein the BCM cycldextrin is contained in a ratio of 2-5: 1, preferably 3: 1. 5. The composition of claim 1, 2, 3, or 4, wherein the metmeclan and cycloextrin are contained in a ratio of 2-20: 1, preferably 10: 1. 5. A composition according to any one of claims 1, 2, 3 or 4 wherein phenarimol and cyclodextrin are contained in a ratio of 1-100: 10, preferably 1: 5. A plant protection agent composition comprising, on a plant or other surface thereof, a composition comprising 1 to 90% of the cyclomictrin by weight and, optionally, a known adjuvant, containing 3-90% of the bactericidal active ingredient by weight. Sterilization method to treat at a rate of -1.6Kg / ha.