JP2636880B2 - Agricultural insecticide and acaricide with enhanced potency - Google Patents

Description

The present invention relates to an agricultural pesticide with increased potency, and more particularly, a large amount of a surfactant and a small amount of a 16-membered macrolide-based natural compound or a derivative thereof, and
In some cases, it relates to an agricultural pesticide with increased potency characterized by comprising a solvent for dissolving them and / or a mineral oil, an animal or vegetable oil or a modified product thereof. Many 16-membered ring natural macrolides having insecticidal and acaricidal activity represented by milbemycin, avermectin, and the like, and a large number of derivatives thereof are known. For example, milbemycin natural products and their derivatives
JP-A-50-29742, 54-107550, 57-77686, 57-
120589, 57-136585, 57-139079, 57-139080
Nos. 57-139081, 59-16894, 59-20284, 59-20
No. 285, 59-33288, 59-33289, 59-36681, 59-
36682, 59-108785, 60-126289, 60-142911
No. 60-152490, 60-184085 and 61-103884.

Avermectin natural products and their derivatives are disclosed in
52-151197, 53-130695, 54-35293, 54-61197
No. 54-61198, 54-145699, 55-20797, 55-24
No. 165, 57-18684, 57-59892, 57-150699, 57
-206695, 58-52300, 58-59988, 58-167591
No., 59-15482, 59-205321, 60-94983, 61-2
2087, 61-36286, 61-200993, 61-233686, 6
1-257989, 61-267582, 62-29589 and 62-59
No. 291 and the like. In addition, 16 similar
Membered macroids are disclosed in JP-A-61-10589 and 61-11887.
Nos. 61-280496, 62-29590 and 62-67087. These macrolides are typically represented by the following general formula:

In the above formula, R ¹ represents, for example, a hydrogen atom, a halogen atom, an alkyl group, a hydroxyl group, a mercapto group or a sugar residue.

R ² represents, for example, a hydrogen atom, a hydroxyl group, or oxo. The dotted line indicates a single bond or a double bond, and may be a double bond only when R ² is a hydrogen atom. R ³ is, for example, an alkyl, alkenyl or alkynyl, alkoxy or alkylthioalkyl, cycloalkylalkyl, cycloalkyl or cycloalkenyl (both optionally substituted by methylene or one or more alkyl or halogen) Or a saturated or unsaturated heterocyclic ring (which may be substituted with one or more alkyl or halogen).

R ⁴ represents, for example, a hydrogen atom, a halogen atom or a hydroxyl group. R ⁵ represents, for example, a hydroxyl group or a hydroxyimino group. A represents an oxygen atom or a single bond. In each of the above definitions, the hydroxyl group, mercapto group, and hydroxyimino group may be etherified or esterified.

These compounds are known to have high activity against various agricultural pests. However, the common drawbacks of these compounds are that they are susceptible to photodegradation and have poor residual activity, and they also have a very high adulticidal activity against certain insect pests, such as spider mites and mandarin mites. Egg activity is weak, and in actual outdoor use scenes,
There was a problem that a high control efficiency could not be obtained unless a spraying liquid having a considerably higher concentration was used than a practical spraying concentration of the active ingredient determined from a laboratory test for evaluating the ovicidal activity.
The present inventors have conducted intensive studies to solve this problem, and as a result, the biological activity of these compounds is greatly affected by the concentration of the surfactant in the spray liquid, and a large amount of the surfactant is used in the formulation. It has been found that by adding the compound, the biological activity can be enhanced, the practical application concentration can be greatly reduced, and the residual effect is also greatly improved, thus completing the present invention.

The 16-membered ring macrolide-based natural compound or its derivative referred to in the present application is a generic name for a group of compounds having the above-mentioned structural skeleton, and includes derivatives derived from these compounds by various methods. The above substituents are illustrative and have the same basic skeleton, and all natural and synthetic compounds having the same kind of action are included in the present invention. In the present invention, the content of these compounds in the composition is 3% (% by weight,
The same shall apply hereinafter), preferably 2% or less, more preferably 1.5% or less.

Surfactants referred to in the present application may be any of generally known nonionic surfactants, anionic surfactants, cationic surfactants and amphoteric surfactants, but may be harmful to target crops or other agricultural chemicals. From the viewpoint of compatibility with the preparation, an anionic surfactant and a nonionic surfactant are desirable, and from the viewpoint of the properties of the resulting preparation, a liquid having a low viscosity is preferably obtained, or a liquid having a low viscosity is obtained by adding a small amount of a solvent. Things are desirable. These surfactants may be used alone or in combination of two or more. The larger the amount of these surfactants in the composition, the better, and although it depends on the type of surfactant, 13% or more, preferably 20% or more, more preferably 40% or more in the formulation. preferable. Preferred surfactants include
For example, sodium salt of dialkyl sulfosuccinate, polyoxyalkylene alkyl or alkyl allyl ether phosphate or its salt, salt of polyoxyalkylene alkyl or alkyl allyl ether sulfate, salt of higher alcohol sulfate, salt of alkylbenzenesulfonic acid, etc. Anionic surfactants, polyoxyalkylene alkyl or alkyl allyl ethers, polyalkylene glycol fatty acid esters, polypropylene glycol ethylene oxide adducts, fatty acid esters of sorbitan and fatty acid esters of polyoxyalkylene sorbitan, acetylene alcohol and acetylene glycol, glycerol borate or Fatty acid esters of polyoxyalkylene glycerol borate, glycerin Or nonionic surfactants such as fatty acid esters of pentaerythritol, alkylene oxide adducts of higher aliphatic amines and fatty acid amides, and cationic surfactants such as quaternary ammonium salts and salts of higher alkylamines. Amphoteric surfactants called amino acid type and betaine type, and
Various fluorine-based surfactants having a perfluoroalkyl group in the molecule can also be used.

The composition of the present invention may further contain an organic solvent necessary for dissolving the active ingredient. These organic solvents must dissolve the active ingredient and be compatible with the surfactant. The macrolide compound as an active ingredient has a relatively low solubility in a hydrophobic organic solvent used in ordinary pesticide emulsions. Therefore, the solvent used may be, for example, sillohexanone, N-methylpyrrolidone, dimethyl sulfoxide, dimethylformamide, propylene glycol, ethylene glycol or diethylene glycol and their ethers or esters, and alcohols such as isopropyl alcohol. Solvents having high polarities are preferred, but even aromatic solvents such as xylene and methylnaphthalene can dissolve about 10% of these active ingredients, and solvents such as perchlorethylene and trichloroethane also dissolve the active ingredients. It dissolves well and can be used satisfactorily depending on the combination. Of course, these solvents may be used alone or in combination of two or more. The content of these solvents in the composition is preferably as small as possible.If the active ingredient is dissolved in the surfactant and other auxiliaries, and the physical properties of the product are satisfactory, it is not always necessary to mix them. However, since the active ingredient is generally difficult to dissolve in these surfactants, it is often necessary to dissolve the active ingredient.

The composition of the present invention may contain a mineral oil, an animal or vegetable oil or a modified product thereof together with or instead of an organic solvent. As mineral oil, for example, liquid paraffin, isoparaffin, polybutene, machine oil, and as animal and vegetable oil, for example, rapeseed oil, soybean oil, sardine oil,
Examples of modified animal and vegetable oils include epoxidized soybean oil. These oils partially or completely dissolve the active ingredient and also serve as a solvent.

In the composition of the present application, if necessary, piperonyl butoxide, potency enhancer such as triphenyl phosphate, stabilizers such as various UV inhibitors and antioxidants, pigments such as ordinary agricultural chemicals Various additives that can be blended can be blended.

The composition thus obtained consists essentially of only a small amount of active ingredient, a large amount of surfactant, and optionally a small amount of organic solvents and / or mineral oils, animal and vegetable oils or modified products thereof, which are homogeneously dissolved. Liquid.
The ratio of surfactant to active ingredient in the composition is preferably
It is at least 50: 1, more preferably at least 100: 1.

The composition of the present invention can be obtained by uniformly dissolving the entire composition while heating as necessary. The most efficient dissolution method is to dissolve the active ingredient in a small amount of a solvent and / or mineral oil, animal or vegetable oil or a modified product thereof, and then add a surfactant to uniformly dissolve the active ingredient. After dissolving in part or all of the agent,
A required amount of solvent may be added for dilution, or a surfactant and a solvent may be uniformly dissolved and mixed in advance, and then the active ingredient may be added and dissolved. At this time, the active ingredient can be more easily dissolved by pulverizing the active ingredient in advance using a suitable dry or wet pulverizer. In any of these steps, various additives such as an efficacy enhancer, a stabilizer, and a dye can be blended. As a production facility, it is generally sufficient to have a tank for producing an emulsion or solution of a pesticide, but as described above, since these active ingredients are relatively insoluble in a solvent, it is desirable to have a suitable heating device. .

Although the composition of the present invention is packaged in the same packaging form as general agricultural chemical emulsions and liquids, the active ingredient of the present application has a compound unstable to light, and in such a case, it is protected from light by using a colored bottle or the like. Packaging is desirable. As the container, glass, synthetic resin of various materials, or a metal bottle or can can be used.

The composition of the present invention is applied by diluting in water. The dilution ratio varies depending on the content of the active ingredient and the surfactant in the formulation, but it is difficult to extremely increase the dilution factor because the higher the surfactant concentration in the spray liquid is, the stronger the effect enhancing effect is. . The concentration of the surfactant in the spray liquid varies depending on the type of the surfactant, but it is usually desirable that the concentration be 400 ppm or more. However, if it is too high, there is a concern that surfactants may cause phytotoxicity, and this is economically disadvantageous.
The concentration is not more than 00 rpm.

Because the composition is ultimately diluted in water and sprayed, the product must be a low viscosity, homogeneous liquid that does not separate or solidify under normal conditions of storage under natural conditions. The state when diluted with water may be either transparently dissolved or emulsified cloudy, but it is not preferable that oily droplets or crystals separate during dilution and do not become a uniform diluent.

Although the mechanism of enhancing the efficacy of the composition of the present invention has not yet been elucidated, as shown in the test examples described below, the composition of the present invention significantly enhances the insecticidal activity against the red mite, the spider mite, the aphids and the cutworm, Spodoptera litura. Therefore, it is considered that the active ingredient is easily absorbed through the eggshell and the insect body surface by the large amount of the surfactant, and the pests and mites that survive in the spray area are completely eliminated from eggs to adults. Therefore, it is considered that the density in the spray area does not increase until new breeding starts due to invasion from outside at a later date, and it seems that the residual effect seems to be enhanced. However, on the other hand, because the active ingredient is absorbed into the plant body and stably retained by the large amount of surfactants, pests and mites that eat or suck it are killed, and the true residual effect increases It is also possible.

In order to further deepen the understanding of the present invention, examples,
The present invention will not be limited by these examples and test examples.

[Examples 1 to 17] Liquid preparations containing 0.40% of milbemycin and 40% of a surfactant were prepared according to the following formulation.

(Formulation) milbemycin A _3, A ₄ mixture (A ₃ and total content of 93% of A _4, A ₃
/ A ₄ = 3/7 ) 0.40% Surfactant 40.00 Organic solvent 59.60 Total 100.00 The surfactant and the organic solvent used in Table 1 were used.

[Examples 18 to 27] Milbemycin solution was prepared according to the formulation shown in Table 2 using Newcol 291EG as a surfactant.

Examples 28 to 34 Milbemycin solutions were prepared according to the formulation shown in Table 3 consisting of an active ingredient, a surfactant, a solvent (xylene), and optionally animal and vegetable oils.

[Comparative Examples 1 to 6] An ordinary emulsion of milbemycin and a solubilized solution were prepared according to the following formulation.

Comparative Example 8 A mixture of milbemycin A ₃ and A ₄ (93% active ingredient, mixing ratio A ₃ / A ₄ = 3 /
7) 0.30%, Triton X-100 12.00%, piperonyl butoxide 1.50%, and propylene glycol 86.20% were uniformly heated and dissolved to prepare a milbemycin preparation.

[Comparative Examples 9 to 12] Blank solutions containing no milbemycin were prepared according to the following formulation.

[Test Example 1] Ovicidal activity test of Citrus red mite The compositions of Examples 1 to 17 and Comparative Examples 3, 7 and 9 to 12
The composition of Comparative Example 8 was diluted 2000 times with water and the composition of Comparative Example 8 was diluted 1500 times with water, and these chemicals were spawned on mulberry leaves with a Mizuho-type rotary sprayer (manufactured by Mizuho Physical and Chemical Instruments KK). The eggs were sprayed on the 3 day old eggs at 5 c.c., air-dried, and allowed to stand in a constant temperature room at 25 ° C., and the egg killing rate and the mortality of hatched larvae after 10 days were determined. The number of test eggs was about 100 in each treatment group. The test results are shown in Table 5.

The compositions of the examples showed high ovicidal activity, and most hatched larvae died. For this reason, the survival rate at the time of the survey was close to 0%, but Comparative Examples 3, 7, 8
The composition has an ovicidal effect when the concentration of milbemycin is 2 ppm,
The effect on the larva was low, and no remarkable effect was observed. In Comparative Examples 9 to 12, which did not contain milbemycin, only the ovicidal activity was equal to or slightly higher than that of the control group, and finally the survival rate was not different from that of the control group. These results indicate that the composition of the present invention significantly enhances the effect of the composition of the present invention on eggs and hatched larvae of Citrus spider mites by adding a large amount of a surfactant.

[Test Example 2] Field effect test on Citrus red mites A comparative test of the effects of the compositions of Examples 18 to 34 and Comparative Examples 1, 2, 4, 5, 6, 6, 8 and 11 was conducted at the 7th grade Miyakawa Unshu mandarin orchard. . That is, the drug diluted to a predetermined concentration was evenly sprayed on a tangerine tree with a power sprayer. Immediately before spraying and every week after spraying, 50 leaves per tree were randomly extracted, and the number of living female adults was counted. The test was conducted in two trees in one plot. In addition, the control efficiency for 6 weeks (see Study on drug resistance of fruit tree spider mites, see Plant Protection Association (1984), page 3) was determined. Table 6 shows the results.

All the compositions of the examples showed higher control efficiency than the comparative examples. In particular, the composition of Example 26 still showed a high control efficiency even at an active ingredient concentration as low as 2 ppm. on the other hand,
The compositions of Comparative Examples 1, 2, 4, 5, 6, and 8, which contained a low amount of surfactant, did not have sufficient control efficiency even when the active ingredient concentration was high.
The composition of Comparative Example 11, which did not contain milbemycin, showed a slight decrease in population density immediately after the treatment, but the control efficiency after 6 weeks was low and almost no effect was observed.

Examples 35 to 44 16-membered macrolide natural products other than milbemycin A ₃ and A ₄ mixtures and derivatives thereof were prepared according to the following formulations. The 16-membered macrolide natural products and their derivatives used are as follows.

B) milbemycin D (Example 35) b) a mixture of milbemycin C ₁ and _{C 2 (C 1 / C 2} = 30/70)
(Example 36) c) A mixture of avermectin B _1a , and B _1b (B _1a / B _1b = 93
/ 7) (Example 37) d) LL-F-28249α (Example 38) e) 13- (2-Phenylpropionyloxy) milbemycin A ₄ (Example 39) f) 13-Pivaloyloxymilbemycin A ₄ (Example
40) g) 8,9-epoxy -5-O-aceto creaking behenate My Shin A ₄ (Example 41) h) 26- (3-methyl crotonyl-oxy) - Mirubema leucine A ₄ (Example 42) Li) 13-Fluoromylbemycin A ₄ (Example 43) nu) 13-pivaloyloxy-5-ketomylbemycin
The A ₄ 5-oxime (Example 44) (Formulation) compound a) to j) 0.30% Niyukoru 291EG 40.00% Cyclohexanone 59.70% Comparative Example 13 to 22] The following formulations, usually in the a) to j) of the compound An emulsion was prepared. (Comparative Examples 12 to 21) Compounds a) to nu) 0.60% Paracol KPS (combined emulsifier of Nippon Emulsifier Co., Ltd.) 10.00% Xylene 89.40% [Comparative Example 23] A mixture of 10.0% paracol KPS and 90.0% xylene After dissolution, a blank emulsion containing no active ingredient was prepared.

[Test Example 3] Ovimicidal activity test of the spider mite, Teeth spider mite The composition of Examples 35-44 and the composition of Comparative Example 11 were used in 1000
2 times, the compositions of Comparative Examples 13 to 23 were diluted with water so as to be 2000 times, and these drug solutions were sprinkled on cowpea leaves by a Mizuho-type rotary sprayer. After spraying, air-dried and allowed to stand in a constant temperature room at 25 ° C, the ovicidal rate after 10 days was determined. The number of test eggs was about 100 in each treatment group. The test results are shown in Table 7. Each of the compositions of the examples significantly improved the ovicidal rate of the spider mite, as compared with the corresponding compositions of the comparative examples. The blank emulsion containing no active ingredient did not show any ovicidal activity.

[Test Example 4] Pesticidal activity test against peach peach aphid Komatsuna, which was well infected with peach peach aphid (Myzus persicae), was placed in an automatic spraying room, and Examples 1, 3, 6, 10, 10
2 times the composition of Comparative Example 2 and 2000
The compositions of Comparative Examples 9 to 12 were diluted 8000 times and sprayed.
Investigation of mortality took place one day later. Table 8 shows the test results.

[Test Example 5] Insecticidal activity test on Spodoptera litura larvae After releasing the third larva of Spodoptera litura on the leaves of cabbage, it was put into an automatic spray chamber, and the composition of Examples 3, 6, 10, 12, and 22 was increased 1000 times. The compositions of Comparative Examples 2 and 6 were diluted 2000 times, and the compositions of Comparative Examples 9 to 12 were diluted 8000 times and sprayed. Investigation of mortality took place three days later. Table 8 shows the test results.

 ──────────────────────────────────────────────────の Continued on the front page (72) Inventor Keiji Tanaka 1041 Yasu-cho, Yasu-cho, Yasu-gun, Shiga Prefecture Sankyo Co., Ltd. Document JP-A-60-132989 (JP, A) JP-A-60-158191 (JP, A) JP-A-61-130292 (JP, A) JP-A-59-219206 (JP, A)

Claims (14)

(57) [Claims] 1. A 16-membered macrolide natural product or a derivative thereof as an active ingredient, which contains at least 13 parts by weight of a surfactant in 100 parts by weight of a composition, and has an interface with the active ingredient in the composition. A pesticidal and acaricide composition for pesticides, wherein the ratio of the activator is 50 times or more. 2. The composition according to claim 1, wherein the 16-membered macrolide-based natural compound or a derivative thereof is represented by the following general formula: (In the formula, R ¹ represents a hydrogen atom, a halogen atom, an alkyl group, a hydroxyl group, a mercapto group or a sugar residue. R ² represents a hydrogen atom, a hydroxyl group or an oxo group. The dotted line represents a single bond or a double bond. , R ² may be a double bond only when R ² is a hydrogen atom R ³ is an alkyl group, alkenyl or alkynyl group, alkoxy or alkylthioalkyl group, cycloalkylalkyl group, cycloalkyl or cycloalkenyl group (both optionally or indicating one or may be substituted with more alkyl or halogen), or a saturated or unsaturated heterocyclic ring (optionally substituted with one or more alkyl or halogen). R ⁴ is hydrogen atom, a is .R ⁵ showing a halogen atom or a hydroxyl group a hydroxyl group or a hydroxyimino group shown .A is an oxygen atom or a single bond. Further, in the above definition, a hydroxyl group, a mercapto group, hydroxyimino group etherified may be esterified.) 3. The method according to claim 1, wherein the 16-membered macrolide natural compound is at _{least one} selected from milbemycins A ₃ , A ₄ , D, C ₁ and C _2. Composition. 4. The method according to claim 1, wherein the 16-membered macrolide natural compound is one or more selected from avermectin B _1a and avermectin B _1b .
The composition according to Item. 5. In the general formula, R ¹ is a hydrogen atom, R ² is a hydroxyl group or a hydrogen atom, a dotted line is a single bond, and R ³ is 1-methyl-1-propenyl, 1-methyl-1-butenyl or 1,3-dimethyl-1-butenyl, R ⁴ is a hydrogen atom, R
3. The composition according to claim 2, wherein the active ingredient is one or more of a 16-membered macrolide-based natural compound or an ester thereof, wherein ⁵ represents a hydroxyl group and A represents a single bond. 6. In the general formula, R ¹ is a hydrogen atom, R ² is a hydrogen atom, a dotted line is a single bond, R ³ is methyl or ethyl, R ⁴ is isopentanoyl, 2-methylpentanoyl or 3. The method according to claim 2, wherein the active ingredient is 2-isopentenoyl, one or more of a 16-membered macrolide natural compound or an ester thereof, wherein R ⁵ represents a hydroxyl group and A represents a single bond. Composition. In the general formula, R ¹ is a hydrogen atom, R ² is an oxo group, a dotted line is a single bond, and R ³ is 1-methyl-1-propenyl, 1-methyl-1-butenyl or 1, 3-dimethyl-1-butenyl, R ⁴ is a hydrogen atom, an R ⁵ is hydroxyl, and claims to one or more of the active ingredient a is a single bond a 16-membered ring macrolide natural compounds respectively 3. The composition according to item 2, wherein 8. In the general formula, R ¹ is pivaloyloxy,
α-methylbenzylcarbonyloxy or α, α-
Dimethylbenzylcarbonyloxy, R ² is a hydrogen atom, a dotted line is a single bond, R ³ is methyl or ethyl,
^{4. A method according} to claim 2, wherein R ⁴ is a hydrogen atom, R ⁵ is a hydroxyl group or hydroxyimino, and A is a single bond, one or more of a 16-membered ring macrolide derivative or an ester thereof. The composition according to Item. In the general formula, R ¹ is a hydrogen atom, R ² is a hydrogen atom, a dotted line is a single bond, R ³ is methyl or ethyl, R ⁴ is a hydrogen atom, and R ⁵ is acetoxy or propionyl. 16 represents oxy and A represents an oxygen atom, respectively.
3. The composition according to claim 2, wherein one or more membered macrolide derivatives are used as an active ingredient. In the general formula, R ¹ represents a hydrogen atom or 4 '-(α-L-oleandrosyl) -α-L-oleandrosyloxy, R ² represents a hydrogen atom or a hydroxyl group,
The dotted line represents a single bond or a double bond, and R ³ is an α-branched C _3-8 alkyl, alkenyl, alkoxyalkyl or alkylthioalkyl, C _3-8 cycloalkyl-α-branched C _2-5
Alkyl, C _3-8 cycloalkyl or C _5-8 cycloalkenyl (both may be substituted with methylene or C _1-4 alkyl or halogen), or a 3-6 membered oxygen or sulfur containing heterocycle ( C _1-4 alkyl or halogen may be substituted), R ⁴ represents a hydrogen atom,
3. The composition according to claim 2, wherein R ⁵ represents a hydrogen group or methoxy, and A represents a single bond, and one or more of 16-membered macrolide derivatives as active ingredients. 11. The composition according to claim 1, wherein the surfactant in 100 parts by weight of the composition is at least 20 parts by weight. 12. A pesticidal and acaricidal composition for agricultural use, comprising a 16-membered ring macrolide-based natural compound or a derivative thereof as an active ingredient, and containing 40 parts by weight or more of a surfactant per 100 parts by weight of the composition. 13. The composition according to claim 1, wherein the surfactant is at least 40 parts by weight in 100 parts by weight of the composition. 14. The composition according to claim 1, comprising at least one of a mineral oil, an animal or vegetable oil or a modified product thereof, and an organic solvent.