JPH0676288B2 - Agricultural and horticultural germicides and plant disease control agents - Google Patents

Description

The present invention relates to an agricultural / horticultural germicide and a plant disease control agent.

Recently, since soil pollution and residual toxicity of crops due to the use of pesticides have become social problems as so-called pesticide pollution, the development of pesticides with particularly high safety has been desired. As for bactericides, resistant bacteria against various drugs result in their effects being impaired, and countermeasures against them are eagerly awaited.

Conventionally, it has been known that certain metal compounds have a bactericidal effect against plant diseases such as crops. However,
Although these compounds show a relatively high bactericidal effect in an in vitro test, they cannot show a sufficient effect in an actual field test. Therefore, it is necessary to increase the concentration or amount of the compound used, and as a result, phytotoxicity becomes a problem.

In view of the above-mentioned purpose, the present inventors have clarified the mechanism of disease generation in plants and clarified the mechanism of action of various test compounds against pathogenic bacteria in order to carry out the creation and development of more effective pesticides. The inventors have found that the agent of the present invention has a bactericidal effect greater than or equal to a synergistic effect and is an excellent agent with no chemical damage, and completed the present invention.

The present invention comprises at least one selected from Group A shown below.
Containing, as an active ingredient, one kind of ingredient (active ingredient A), at least one kind of ingredient selected from group B (active ingredient B), and at least one kind of ingredient selected from group C (active ingredient C). The present invention provides an agricultural and horticultural germicidal agent and a plant disease controlling agent.

A: LiCl, NaHCO ₃ , Na ₂ CO ₃ , KHCO ₃ , K ₂ CO ₃ , CuSO ₄ , CuC
l ₂ , 8-oxyquinoline copper, CuSO ₃ , AgNO ₃ , AgCl, AuC
_{l 3, HAuCl 4, MgSO 4} , MgCO 3, 3MgCO 3 · Mg (OH) 2 · 3H
₂ O, CaCl ₂ , ZnCl ₂ , FeCl ₂ , FeCl ₃ , CoCl ₂ , NiCl ₂ , AlCl
₃ , MnCl ₂ , TiCl ₄ , P ₂ O ₅ , Ammonium molybdate, Ag ₂ CO
₃ , MgCl ₂ , MgSO ₃ , CaSO ₄ , ZnSO ₄ , FeSO ₄ , MnO ₂ , TiO ₂ and MoO ₃ B: 8-oxyquinolinol, crown ether, oxalic acid, citric acid, fumaric acid, polyphosphoric acid, tannic acid,
Alginic acid, phytic acid, or salts thereof, phytin,
Vegetable gums, wax and pullulan C: fatty acids, fatty acid esters of aliphatic polyhydric alcohols, sucrose fatty acid esters, and purified lecithin powder.

The present inventors have conducted various experiments in order to investigate the reason why a certain metal compound has a relatively high bactericidal effect in an in vitro test, but in an actual field test, it cannot give a sufficient effect. It was As a result, one of the causes is that amino acids, proteins, ATP (plant component), etc., which are often present in or on the plant surface, form a complex with the metal ion (called M ⁺ ) of the active ingredient metal compound. It was clarified that it was because of it. This point will be described in more detail below.

Various metal compounds, which are the active ingredients A of the present invention, show relatively high bactericidal effect by directly acting on pathogens in a model experiment in a room, but they are 1000 on field plants.
The effect cannot be sufficiently enhanced even at high concentrations around ppm. In order to elucidate the reason for this and to create more effective pesticides, we first clarified the mechanism of action of these test compounds against pathogenic bacteria. As a result, all of these test compounds showed NAD → NADH ₂ and
It was found to inhibit the process of NADP → NADPH ₂ . This is because NAD or NADP must complex with H _{2 in} order to form a complex with ions (M ⁺ ) such as Cu ⁺⁺ , Ag ⁺ , and Au ⁺ , in the body. NAD in pathogenic bacteria
→ When NADH ₂ and NADP → NADPH ₂ reactions are inhibited, ATP
It is impossible to biosynthesize and decompose various compounds, including the production of Therefore, the pathogenic bacteria die.

Next, an experiment was conducted to clarify the reason why the bactericidal effect of these test compounds is lost on the plant body. That is, various compounds were added to the test compound solution, and the effects on the bactericidal effect were observed. As a result, amino acids, proteins,
It has been found that the bactericidal activity of the test compound decreases when biological components such as ATP are added. Since these biological components form complexes with metal ions, amino acids, M ⁺ , proteins,
M ⁺ , ATP · M ⁺ is formed, and the treated M ⁺ is adsorbed and NAD or
NADP loses the opportunity to form a complex with M ⁺ and thus the bactericidal effect of the test compound. Moreover, the above-mentioned biological components are attached not only in the plant body but also in large quantities on the plant surface (components generated from wounds, dead branches, etc.).

As a result, by using the composition containing the active ingredients A, B and C of the present invention, the ions of the metal salt compound which is the active ingredient A can be formed on the plant without forming a complex with the plant component. It has been found that a high bactericidal effect can be exhibited.

The characteristics of the composition of the present invention include, in particular, citrus black spot fungus, showing an extremely excellent effect on rain-borne pathogens, suppressing abnormal metabolic reaction induced in plants by invasion of plant pathogens. Preventing the formation of lesions, imparting disease resistance to plants, increasing disease resistance, and having a large medicinal effect, it is possible to reduce the amount used and the concentration used. Despite the presence of the above, the phytotoxicity due to this is not only extremely small, but rather, these metals prevent the metal deficiency caused when it is deficient in the plant body, and as a trace element element of the plant, It can be mentioned that it is effective in promoting growth.

Next, as the fatty acid of the active ingredient C of the present invention, a saturated fatty acid of C _{8 to} C ₂₂ is used, and as the fatty acid ester of an aliphatic polyhydric alcohol or sucrose, the polyhydric alcohol component is glycerin, propylene glycol, sorbitol or sorbitan. a C ₃ -C saturated or unsaturated ₆ aliphatic polyhydric alcohol and the like, fatty acid component is a saturated fatty acid C ₈ -C _22, such as caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, Stearic acid, arachidic acid, behenic acid or unsaturated fatty acids such as oleic acid, linoleic acid,
In addition to single fatty acids such as linolenic acid and ricinolenic acid, mixed fatty acids such as beef tallow, cottonseed oil, rapeseed oil, hydrogenated oil and other natural animal and vegetable oil-derived fatty acids are mentioned. Specific examples include glycerin monostearate, sorbitan monolaurate, sorbitan monostearate, glycerin monooleate, glycerin monosoybean oil fatty acid ester, and glycerin monocotton oil fatty acid ester.

As the crown ether of the active ingredient B of the present invention, 14-
Crown-4 (14-Cr-4), 15-Crown-5 (15
-Cr-5), 18-crown-6 (18-Cr-6) and the like. These may be appropriately selected according to the ionic diameter of the metal salt of Group A. For example, for Cu salt, 15
-For crown-5 (15-Cr-5), Ag or Au salt, 18-crown-6 (18-Cr-6) may be selected.

As the polyphosphoric acid or its salt, pyrophosphoric acid, triphosphoric acid, trimetaphosphoric acid, tetrametaphosphoric acid and their sodium or potassium salts are preferable.

As the vegetable rubber substance, gum arabic, gum tattoo gum, guar gum, locust bean gum, karaya gum,
Tragacanth gum, arabinogalactan, etc. are suitable,
Suitable wax substances are carnauba wax, rice bran, paraffin wax, and the like.

It is considered that the controlling agent of the present invention has a high bactericidal effect because of the following reasons [I] and / or [II]. That is, [I] the metal ion of the metal salt compound which is the active ingredient A is chelated by the other active ingredients B and C (in this case, it is weakly bound in the process of formulation).
By being chelated in this way, the metal ion of the active ingredient is protected from the biological components on the plant, and the complex formation with the biological components can be prevented. Therefore, the metal ions can easily reach the plant pathogen, and the bactericidal effect of the metal ions can be efficiently exhibited. In this case, it is better to adjust the pH appropriately. this is,
This is because pH plays an important role in ionization of metal compounds and activation of chelates.

[II] When a metal salt coated with an insoluble film (fatty acid ester of aliphatic polyhydric alcohol, sucrose fatty acid ester, wax component, etc.) is put into water, the insoluble film hydrates and becomes a monolayer or bilayer molecule. Forming spheres, the metal salt dissolves in it, producing metal ions. The metal ions are protected from biological components by this coating. The surface of the pathogen, etc. is covered with wax components, and the metal ion droplets covered with the lipophilic film easily attach to and integrate with the pathogen, allowing the metal ions to enter the pathogen and have a bactericidal effect. It can be used efficiently.

The control agent of the present invention is, for example, black spot of citrus, scab, scab, anthracnose, cucumber anthracnose, cucumber leaf spot, rice blast, rice leaf blight, pear wilt, grape as in the test examples described below. Exhibits excellent efficacy against various plant diseases such as vine cracking disease.

When the control agent of the present invention is applied, the above-mentioned active ingredients A, B and C are directly applied, or a suitable solid carrier, liquid carrier or emulsifying dispersant similar to the agrochemical formulations generally known in the art. Can be used for formulation into any dosage form such as granules, powders, emulsions, wettable powders, tablets, oils, sprays, and smoke sprays. Examples of these carriers include clay, kaolin, bentonite, acid clay, diatomaceous earth, calcium carbonate, solid carriers such as nitrocellulose, starch and lactose, and as liquid carriers,
Water, methanol, ethanol, acetone, dimethylformamide, ethylene glycol and the like can be mentioned. In addition, auxiliary agents generally used in the preparation, such as sulfates of higher alcohols, polyoxyethylene alkyl
Allyl ether, alkyl allyl polyethylene glycol ether, alkyl allyl sorbitan monolaurate, alkyl allyl sulfonate, alkyl sulfonate, alkyl aryl sulfonate, 4th
A graded ammonium salt, polyalkylene oxide, sodium lignin sulfonate, sodium dinaphthylmethane sulfonate, polypropylene glycol fatty acid ester and the like can be appropriately added.

The active ingredient of the composition of the present invention, that is, the mixing weight ratio of the compound selected from the group A and the compound selected from the group B and the group C is not particularly limited, but is 99: 1 to 5:95, It is preferably 95: 5 to 60:40. The mixing weight ratio of the compound selected from the group B and the compound selected from the group C is not particularly limited, but about 6: 1 to 1: 4 is suitable.

The mixing ratio of the active ingredient is 10 to 10 for emulsion, wettable powder, etc.
About 90% by weight is suitable, and as powders, oils, etc., 0.
About 1 to 10% by weight is suitable, but these temperatures may be appropriately increased or decreased depending on the purpose of use.

Furthermore, the control agent of the present invention can be used by appropriately mixing it with other fungicides, herbicides, insecticides, fertilizer substances, soil conditioners and the like.

Next, examples of the control agent of the present invention will be shown.
What is indicated by "part" is "part by weight".

Example 1 to 34 CuSO ₄ 50 parts (component A) and 10 parts of soluble starch are dissolved in water. 20 parts of caprylic acid (component C) and 20 parts of 8-oxyquinolinol (component B) are dissolved in ethanol or acetone. Mix both mixed solutions with stirring. Then, it is dried and powdered to obtain a wettable powder.

The powder is obtained by adding a suitable carrier, such as talc, to the wettable powder and mixing them well.

The composition of the type obtained by the above operation is shown in Table A.

Examples 35-67 CuSO ₄ 40 parts (component A) and citric acid 40 parts (component B) about 3 parts.
Use 00 mesh powder. Glycerin monostearate
10 parts (component C) are dissolved in acetone or methanol.
The powder was added to the solution, and the solution was heated under reduced pressure or atmospheric pressure to about 50 ° C.
To dry powder. Lactose (10 parts) is added to this product to homogenize it to obtain a wettable powder.

The powder can be obtained by adding a suitable carrier such as talc to the above dry powder and thoroughly mixing them.

The composition of the type obtained by the above operation is shown in Table B.

Example 68~77 Na ₂ CO ₃ 50 parts (component A) and powder of about 300 mesh.
Dissolve and suspend 30 parts of sodium polyphosphate (component B) in ethanol or acetone. The above powder is added to this and stirred for a while. The solvent is distilled off and dried to give a powder.

Meanwhile, 9 parts of glycerin monooleate (component C) and 1 part of lauric acid (component C) are suspended in acetone or ether. The dry powder is added to this, stirred, and dried under reduced pressure or normal pressure (50 ° C.) to obtain a powder. To this, 10 parts of soluble starch is added and mixed uniformly to obtain a wettable powder.

The powder is obtained by adding a carrier such as talc to the above dry powder and thoroughly mixing and homogenizing it.

The composition of the type obtained by the above operation is shown in Table C.

Next, test examples of various plant disease control effects of the composition of the present invention are shown, and the outline thereof is as follows.

Test Example 1 (citrus black spot disease) After thoroughly washing the shoots of pot-planted Wenzhou mandarin oranges cultivated in a greenhouse in running water, the test compound solution diluted to a predetermined concentration was used to grind the leaves of Wenzhou mandarin oranges (0.01% w / v). ) Was sprayed (this condition is based on the assumption of actual spraying in the field). As a control, a group to which the ground material was not added and a water spraying group were provided.

After air-drying, inoculate citrus black spot fungus (4 x 10 ⁵ cells / ml),
After keeping it in a humid chamber at 25 ° C. for 2 days, it was cultivated in a glass greenhouse.
After 3 weeks, the number of each lesion was counted and the control value was obtained.
The results are shown in Table 1. The control value was calculated according to the following formula.

1-50 lesions (1), 51-150 lesions (2), 151 or more lesions (3), and disease-free (0) are investigated separately, and the severity and control value (%) are calculated by the following formula. did.

(However, n ₁ , n ₂ , and n ₃ indicate the disease levels ₁ , ₂ , and ₃ , respectively, and N indicates the total number of leaves.) From this result, it was found that the bactericidal effect of the test compound is reduced depending on the plant components.

The number of lesions on the untreated plot is 638 / leaf, which is a test under moderate to frequent conditions.

Test Example 2 (citrus black spot disease) According to Test Example 1, a solution of the test compound at a predetermined concentration [with addition of a ground product of Satsuma mandarin orange (0.01% w / v) was added] was sprayed to examine the control effect. The results are shown in Table 2.

Test Example 3 (citrus black spot disease) According to Test Example 1, a solution of a test compound having a predetermined concentration was sprayed to examine the control effect. In addition, in this test example, a ground product (0.01 w / v) of Satsuma mandarin orange leaf was added. The results are shown in Table 3.

Test Example 4 (Kankantsui Tsutsui Disease) In Test Example 1, a control value was determined by inoculating a suspension of fungal disease fungus in place of the black spot disease fungus. The control value calculation method is
According to Test Example 1. The results are shown in Table 4. However,
The number of lesions was 1 to 5 (1), 6 to 10 (2), 11 or more (3), and no disease (0).

In addition, in this test example, ground tangerine leaves (0.01% w /
v) was added.

The number of lesions in the untreated plot was 50 / leaf (multi-occurrence).

Test Example 5 (cucumber anthracnose) Cucumber (variety: Sagamihanjiro) seedlings (2/3 pots 2 to 3 plants) grown for 2 weeks were given a certain concentration of drug (ground cucumber leaf grind (0.01% w / v)). 300 ml per 25 pots was uniformly sprayed and dried. 28 cucumber carbon pathogens on slants
Cucumber seedlings of 5 blocks in which 50 spores were formed by culturing at 1 ° C for 1 week to form spores and suspending the spores in pure water (spore concentration: 3 x 10 ⁶ cells / ml) in 25 pots 1 block. Was spray-inoculated with a spray gun. Disease was caused in the wet room for 2 days after inoculation, and the number of lesions was investigated 5 days later. The control value was calculated according to the following formula.

The results are shown in Table 5.

The number of lesions in the untreated plot was 235 / leaf (rapid condition).

Test Example 6 (Bacterial Bacterial Spot of Cucumber) Krehasoil was packed in a perforated cup having a diameter of 6.5 cm, and 10 sprouting cucumber seeds were sown in each cup and cultivated in an air-conditioned greenhouse for about 2 weeks. Then, a predetermined concentration solution of the reagent to be added (cucumber leaf ground product 0.01% w / v added) was spray-dispersed on this. After air-drying, inoculate with cucumber spot bacterial pathogens (2 × 10 ⁸ cells / ml) that were shake-cultured in PDA medium, and then inoculate the cucumber seedlings in a wet room (RH 100%, 25 ° C) for 3-5 days. The number of spots was investigated. The control value is calculated in Test Example 11
According to.

The number of lesions in the untreated plot was 103 / leaf (multi-occurrence).

The results are shown in Table 6.

Test Example 7 (rice blast) Rice (cultivar: 10 stones) was grown in a greenhouse in a synthetic resin pot with a diameter of 6 cm for 10 plants per pot. The crushed product (0.01% w / v added) was sprayed on the rice plants. Spores of rice blast fungus separately cultivated in rice husk medium (including powdered yeast, extract, soluble starch, sucrose, and chaff) were suspended in water (spore concentration, 4 × 10 ⁵ /
ml), spray this on rice plant and inoculate it at a temperature of 27 ° C and humidity.
It was put in a constant temperature and humidity box of 95% or more to cause illness. On the 5th day of inoculation, the number of lesions per leaf was calculated and the control value was calculated. The control value was calculated according to Test Example 5. The results are shown in Table 7.

Test Example 8 (white leaf blight of rice) As in Test Example 7, rice plants grown in a greenhouse were sprayed with a chemical agent (added 0.01 w / v of rice leaf grinds) at a predetermined concentration. After the spray solution was dried, a single needle was inoculated on the uppermost leaf and the next leaf with a suspension of the leaf blight fungus that had been previously cultured in a leaf blight medium at 27 ° C. for 3 days.
The disease started 2 to 3 weeks after the inoculation, and the lesion length per stem was measured to calculate the control value. The control value was calculated according to the following formula.

The results are shown in Table 8.

The lesion length per stem in the untreated plot was 75 mm (many occurrences).

Test Example 9 (citrus black spot disease, change in drug concentration) The test method was carried out according to Test Example 3, and the reagent and each single agent formulated in accordance with Example 1 (milled leaves of Satsuma mandarin 0.01% w / v addition) was changed. The results are shown in Table 9.

Test Example 10 (Cucumber Spot Bacterial Disease / Change in Drug Concentration) The test method was carried out according to Test Example 6, and each of the single reagents prepared as in Example 2 (each cucumber leaf ground product.
The concentration of 01% w / v added) was changed. The results are shown in Table 10.

Test Example 11 (citrus black spot disease, spore formation amount and its pathogenicity) A citrus branch was placed in a test tube, sterilized by an autoclave, and then inoculated with a black spot disease bacterium. 25 test tubes after inoculation
After keeping it in the dark at 5 ° C for 5 days, it was transferred to a glass greenhouse to form stalks and spores, and then the following tests were conducted.

The above-mentioned black spot fungus culture branch was immersed in a test compound solution prepared to a predetermined concentration for 1 minute, air-dried indoors, and then kept in a test tube again, and the spore-forming amount and its pathogenicity were examined over time.

The spore formation inhibition test was performed using distilled water (10
ml), shake, and then collect the water.
And the number of spores was counted.

For the pathogenicity test, the spore suspension obtained by the above method was inoculated into citrus shoots and kept in a wet room for 2 days (RH 100%, temperature 25 ° C).
After keeping it at room temperature, it was cultivated in a glass greenhouse, and after 21 days, the number of lesions was measured and the control value was obtained.

The results are shown in Table 11.

Test Example 12 (citrus black spot disease) The black scab culture branches prepared in Test Example 11 were immersed in a test compound solution diluted to a predetermined concentration, air-dried and kept in a test tube again, and then taken out and potted every predetermined number of days. About planting citrus
It was hung at a position of 30 cm and rained with an artificial rainfall device (20 mm / hour, 3 hours). 25 citrus treated rain
After keeping it in a humidity chamber at ℃ for 2 days, it was cultivated in a glass greenhouse, and after 21 days, the number of lesions was counted and the control value was obtained. The results are shown in Table 12.

Test Example 13 (Kankanitsui Disease) A causal fungus overwinters winter due to lesions formed on citrus leaves, epidermis, fruits, etc., and is scattered and propagated with raindrops in the spring of the following spring. Therefore, in this test, the following method was used. That is, the citrus leaf in which the causal lesion was formed was dipped in a reagent solution diluted to a predetermined concentration, air-dried and kept in a moist chamber, and after 4 days of treatment, it was hung on a pot about 30 cm above the citrus plant. After that, it was rained with an artificial rain device (20mm
/ Hour, 2 hours). 2 days after rain treatment, wet room (RH100
%, Humidity 25 ℃), then grown in a glass greenhouse, 21
The number of lesions was measured after a day and the control value was obtained. This result is
Shown in Table 13.

Test Example 14 (Citrus scab) The citrus scab fungus overwinters and propagates like winter scab. Therefore, a control test was carried out in the same manner as in Test Example 13 using Scab to determine the control value. The results are shown in Table 14.

Test Example 15 (Pear branch wilt) The pear branch with pear branch wilt spots was dipped in a reagent solution diluted to a predetermined concentration, air-dried and kept in a moist chamber, and after treatment 4 days, about 30 cm of the pot pear planted. Hung up Then test example
A rain test was conducted in the same manner as 13 to determine the control value. The results are shown in Table 15.

Test Example 16 (Grapevine Cracking Disease) A pear branch with grapevine cracking lesion formed was dipped in a reagent solution diluted to a predetermined concentration, air-dried and kept in a humid chamber, and 4 days after the treatment, about 30 cm of pot planted grapes Hung up afterwards,
A rain test was conducted in the same manner as in Test Example 13 to determine the control value.

The results are shown in Table 16.

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Asamasa Misawa Hirosawa No. 2-1, Wako City, Saitama Prefectural Institute of Physical and Chemical Research (56) Reference JP-A-56-79610 (JP, A)

Claims (1)

[Claims] 1. An active ingredient comprising at least one component selected from group A, at least one component selected from group B, and at least one component selected from group C shown below. A sterilizing agent for agricultural and horticultural use and a plant disease controlling agent, characterized by being contained as. A: LiCl, NaHCO ₃ , Na ₂ CO ₃ , KHCO ₃ , K ₂ CO ₃ , CuSO ₄ , CuC
l ₂ , 8-oxyquinoline copper, CuSO ₃ , AgNO ₃ , AgCl, AuC
_{l 3, HAuCl 4, MgSO 4} , MgCO 3, 3MgCO 3 · Mg (OH) 2 · 3H
₂ O, CaCl ₂ , ZnCl ₂ , FeCl ₂ , FeCl ₃ , CoCl ₂ , NiCl ₂ , AlCl
₃ , MnCl ₂ , TiCl ₄ , P ₂ O ₅ , Ammonium molybdate, Ag ₂ CO
₃ , MgCl ₂ , MgSO ₃ , CaSO ₄ , ZnSO ₄ , FeSO ₄ , MnO ₂ , TiO ₂ and MoO ₃ B: 8-oxyquinolinol, crown ether, oxalic acid, citric acid, fumaric acid, polyphosphoric acid, tannic acid,
Alginic acid, phytic acid, or salts thereof, phytin,
Vegetable gums, wax and pullulan C: fatty acids, fatty acid esters of aliphatic polyhydric alcohols, sucrose fatty acid esters, and purified lecithin powder.