JPS58128309A - Insecticidal and tickicidal composition based on ethione and prethroid and treating method of plant to arthropod using these composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to synergistic insecticidal and acaricidal compositions for combating crop-destroying arthropods. Furthermore, the present invention relates to a method for treating plants for eradicating arthropods, and more particularly for eradicating plant-feeding mites.

The use of organic phosphorus pesticides in agriculture to eradicate crop-destroying arthropods is known. Of these compounds, nithione has been successfully used for a long time to combat plant-feeding mites.

It will be recalled that nithione is an active ingredient of the formula (■): and its chemical name is s,s'-methylene-bis-(0,0-diethyldithiophosphate). This is US Patent No. 2,8
No. 73,228. This compound is also known by the common name dinithione. In this specification, it is systematically described by the common name "Nithion".

Organophosphorus insecticides have been used successfully as industrial insecticides and acaricides for a long time. For several years, the emergence and reproduction of plant-feeding mite species that have become resistant to organophosphorus insecticides has been observed.

Eradication of these mites that are resistant to organophosphorus insecticides has resulted in increased treatment loads for agricultural horticulturists and thus increased costs of these treatments. Nevertheless, the results were often disappointing, resulting in increased residue on the treated plants.

Additionally, as agricultural insecticides and/or acaricides, in particular U.S. Pat.
It is also known to use compounds of the type described in No. 96.244 and designated by the general name Billesroy r. Although these compounds generally have excellent insecticidal activity, their acaricidal activity is generally considered to be insufficient.

This time, the combination of heel pyrethroid and nition (a
ssoclation) has been found to significantly improve its acaricidal activity, particularly against types of plant-feeding mites that have become resistant to organophosphorus insecticides.

It is truly this finding that constitutes the subject matter of the present invention. This improvement is quite surprising. This is because pyrethroids, when used by themselves, have virtually no acaricidal activity against these same types of mites at the time of application. This synergistic effect is explained more clearly with examples illustrating the invention.

The present invention relates primarily to a synergistic insecticidal and acaricidal composition for use in combating crop-destroying arthropods, which composition comprises as active ingredients nithione and nithione. General formula (■): [wherein R represents a hydrogen atom or a cyano group, 7 and R8 represent 2,2-dimethyl-3-
(2,2-dichlorovinyl)-cycloprop-1-k
M, 2,2-dimethyl-3-(2,2-dibromvinyl)-cycloprosy 1-yl group, 2,2-dimethyl-
3-(2-Methylzolobut-1-enyl)-cyclopropro-1-yl group or 1-(4-chlorophenyl)-isocyt-1-yl group].

The pyrethroids according to formula (II) often exist in different optically or geometrically isomeric forms and, if necessary, are mixed with one another. In the terminology used herein, the expression "Villethroy P according to the formula ■" encompasses the different isomeric forms of these compounds as well as mixtures thereof (melango).

As an example of a pyrethroid corresponding to formula (n), the following compound may be mentioned: (R8)-α-cyano-3-phenoxybenzyl (I
R8)-cis, trans-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopronononecal is gysylate (generic name cypermethrin, cypermet
hrine), 3niphenoxybenzyl (I R8)
-elm, trans -3-(2,2-dichlorovinyl)-2,2-dimethylcyclopronoguncalcexylate (generic name: vermethrin).

permethrine), (S)-α-cyano-
3-phenoxybenzyl (IR)-cig-3-(2,2-dibromvinyl)-2,2-dimethylcyclopropane urexylate (common name decamethrine, decam≦thrine and deltamethrine)
), and (R8)-α-cyano-3-phenoxybenzyl (R8
)-2-(4-chlorophenyl)-3-methylphthalate) (common name: phenonolerate).

fenvalerate).

In the terminology used herein, the term ``association 4'' refers not only to combinations that can be used as is (i.e., prepared in advance and intended for use after dilution), but also to 2 that are prepared for immediate use. Also meant is a mixture of the active ingredients of the seed (ie a mixture prepared immediately before application to the crop in question).

More specifically, the present invention provides 0 per 100 parts by weight of nithione.
．． 0.01 to 100 parts by weight of pyrethroi r(u), more preferably 0.1 to 100 parts of nithione
The present invention relates to a composition consisting of 10 parts by weight of Pyrethroy r.

Cypermethrin is preferably used as Viresthroy r(u).

In addition to the combination consisting of nithione and Villethroy r according to formula (It), the compositions according to the invention generally contain an agriculturally acceptable solid or liquid inert carrier.

Also contains 5uppot (or diluent).

If desired, these compositions may further contain one or more agriculturally acceptable surfactants and, if desired, other agriculturally acceptable additives, such as protective colloids, adhesives, thickeners, thixotrozo agents. , a penetrant, a stabilizer, a complex compound forming agent (5equestrant), etc., and, if necessary, other known substances having insecticidal properties (particularly insecticidal, acaricidal or fungicidal properties) or properties that promote plant growth. It also contains active ingredients.

Generally, the compositions according to the invention consist of a live weight content of 0.001 to 95 parts by weight, ie, a combination of nithione and pyrethroid.

[carrier (support) J
The term means any organic or inorganic, natural or synthetic material with which the combination of active ingredients is mixed to facilitate its application to the crop or soil, or to facilitate its storage or handling. The carrier is generally inert and agriculturally acceptable, especially for treated crops.

The carrier (or diluent) can be solid or liquid.

In particular solid carriers which can be removed are clays, natural or synthetic silicates, natural silicas such as diatoms, magnesium silicates such as talc, magnesium aluminum silicates such as attapulgitite, etc.
e) and Nono-Mikiyelite, aluminum silicate,
For example, kaolinite, montmorillonite and back mother,
Calcium carbonate, calcium sulfate, synthetic calcium or aluminum silicates, natural or synthetic resins such as polyvinyl chloride, styrene polymers and copolymers, and solid polychlorophenols, waxes such as beeswax and paraffin, solid fertilizers. , such as superphosphates.

Liquid carriers that may be mentioned in particular are water, alcohols such as isozolononol and glycols, ketones such as acetone, methyl ethyl ketone, methyl isodithyl ketone and cyclohexanone, ethers, aromatic or graphene hydrocarbons, toehabenzene, toluene, xylene. , petroleum fractions or distillates and kerosene, mineral oils, hydrogenated hydrocarbons such as carbon tetrachloride, perchlorethylene or trichloroethane, or, if necessary, liquefied gases. Mixtures of these various liquid carriers are also often used.

Surfactants can be emulsifiers, dispersants or wetting agents of ionic or nonionic type. Examples include salts of polyacrylic acid, salts of lignosulfonic acid, phenolsulfone [, L< is a salt of naphthalenesulfonic acid, polycondensation products of ethylene oxide and aliphatic alcohols, fatty acids or lipoamines, substitutions] These include phenols (especially alkylphenols and arylphenols), salts of sulfosuccinates, taurine derivatives (especially alkyltaurates), and phosphoric acid esters of condensates of ethylene oxide and alcohols or phenols. If the inert carrier is insoluble in water and the vehicle used is water, the presence of at least one surfactant is generally essential.

The compositions according to the invention can be in a very wide variety of solid or liquid forms.

As the form of the solid compositions, mention may be made of dusting or sprinkling powders with an active ingredient content which may range from 90%t.

Forms of liquid compositions which may be constituted during application include solutions, in particular water-soluble concentrates, emulsifiable concentrates, emulsions, suspension concentrates, aerosols, water-use powders (or sprayable powders) and One example is paste.

Emulsifiable or soluble concentrates, especially Shigeshige 10-80
Ready-to-apply emulsions or solutions containing 1% by weight of the active ingredient combination and are also called spray mixtures contain from 0.001 to 20% by weight of the active ingredient combination. In addition to the solvent, the emulsifiable concentrate can optionally contain 2 to 20 parts per weight of additives, such as stabilizers, surfactants, penetrants, corrosion inhibitors, dyes and adhesives. The compositions of several concentrates are given by way of example below. Hereinafter, A represents nithione and B represents cypermethrin. Combination of two bulk components (A/B=2.4) t5oy/4-alkylarylsulfonate calcium 307/II
.

-10:　1 ethylene oxide/aluminum Kylphenol condensate 50y/II.

- Aromatic solvent (petroleum fraction) Sufficient t lμ Compositions of other emulsifiable concentrates according to the invention are given below by way of example combinations of two bulk components (A/B=4.5) 5ooy/1-alkyl Calcium arylsulfonate 4oy/fl-
10:1 ethylene oxide/alkylphenol condensate 6oy/II.

-Cyclohexanone 1 '001! /
IV.

- Aromatic solvents (petroleum fractions) sufficient i1 [1 Starting from these concentrates, emulsions of the desired concentration, particularly suitable for application to crops, can be obtained by dilution with water.

Aqueous powders (or sprayable powders) are generally manufactured to contain 20 to 95 parts of active ingredient, and these generally include, in addition to a solid carrier, a wetting agent of θ to 5 parts and a dispersing agent of 3 to 10 parts. If necessary, one or more stabilizers and/or other additives in the range θ to IO, such as penetrants,
Contains adhesives, anti-caking agents, dyes, etc.

Combinations of active ingredients (A/B=10) 30 parts 9f calcium nosulfonate (anti-agglomerating agent) '・ 5 parts-
Calcium alkylarylsulfonate (anionic wetting agent) Part 1 - Anti-caking silica 30 Width - Kaolin (filler) Part 34 The composition of the powder for spraying is as follows: Combination of two bulk ingredients using ingredients (A/B=100) 4ooy-sodium dibutylnaphthylsulfonate 50y-3
: 2:1 naphthalene sulfonic acid/phenolsulfonic acid/formaldehyde condensate 30p-kaolin 120y-anticaking silica 400y The composition of the spray powder (in this case 25% fel&) is a bulk mixture using the following ingredients: Combination of sexual components (A/B=6.66) 250F-calcium lignosulfonate 45y-isomorphic t
s Champs Gunne Chalk (crate de c
hampagne) and hydroxyethyl cellulose Sodium 19y-Cusitylinaphthalenesulfonate
15y-silica
250y-kaolin
Another composition of the 421y spray powder (this time at 1o% concentration) is a bi-bulk component combination (A/B = 200) using the following components: 100F - Mixture of sodium salts of saturated fatty acid sulfate esters 307- Naphthalenesulfonic acid/formaldehyde condensate 50y-Silica 100y-Kaolin 720yTo obtain these sprayable or aqueous powders, the active ingredient is intimately mixed with the additional substances in a suitable mixer and the mixture is
or other suitable grinder. This gives sprayable powders with advantageous wettable or suspendable properties, which can be suspended in water at the desired concentration,
This suspension can be used with particular advantage for applying to the leaves of plants.

As mentioned above, aqueous dispersions and emulsions,
For example, compositions obtained by diluting water-containing powders or emulsifiable concentrates according to the invention with water are included within the general scope of the compositions for use in the invention. Emulsions can be water-in-oil or oil-in-water, e.g.
It can have a high consistency, like "mayonnaise."

For so-called ultra-low volume (ULV) applications, which involve spraying as very fine droplets, solutions of the two active ingredients in suitable solvents are prepared and a mixture of these solutions is applied at a rate of about 1 to 5 β/h a Apply at the rate of UL according to the invention
The composition of the V solution is given below as an example of a combination of active ingredients (A / B = 10) 200
f/It-Aromatic solvent (petroleum fraction) well attached
Furthermore, the present invention combats crop-destroying arthropods, more particularly eg spider mites (tetranyq).
The present invention relates to a method for treating plants to eradicate plant-feeding mites such as P. ue). The method consists in infusing these plants with an effective amount of a composition containing as active ingredients a combination of nithione and a pyrethroid corresponding to formula (π). The term "effective amount" is understood to mean sufficient protection to suppress and destroy arthropods present on or in the immediate vicinity of these plants. ,,The processing method according to the present invention includes:
It is possible to use aqueous dispersions or emulsions, for example compositions obtained by diluting the above-mentioned hydratable powders or emulsifiable concentrates with water. This treatment can also be carried out using ultra-low volume t (ULV) solutions, such as those described above.

Advantageously, this treatment according to the invention is carried out using a composition, the formulation and application 1 of which contains 100 to 5 nithione.
000P/ha and pyrethroid (II) is 0
．． It is a type of wood that is harvested at a rate of 1 to about 500 plha. As mentioned above, advantageously the composition comprises from 0.01 to 100 parts of bile, preferably cypermethrin, per 100 parts of nithione.

The compositions and treatment methods according to the invention can be used to protect a variety of perennial or annual crops from arthropods, such as those grown in warm or tropical climates, in particular Primary annual crops (cereals, potatoes, beets, berries, cotton, soybeans, sugar cane, etc.), one agricultural or tropical crop, one orchard, and one flower and tribute crop. .

They are not meant to be limiting.

The compositions and methods according to the invention can be used primarily to combat plant-feeding mites and have a synergistic effect against these mites as shown by the examples below. Furthermore, these compositions can be advantageously used to combat different types of plant-feeding insects, such as those of the orders Homoptera, Coleoptera, Lepidoptera and Diptera.

The present invention will be explained below with reference to Examples, but is not limited thereto.

Aqueous dispersions of Nithion, Cypermethrin and the combination of Nithion+Cypermethrin were prepared. These dispersions were then diluted with distilled water to the desired concentration.

``Rot des Belgea J Types of Bean Plants''
) At stage J, mites of the type "Tetranychus urticae", which are thought to be resistant to phosphorus insecticides and cypermethrin, were planted.

Forty-eight hours after planting, each σ plant was sprayed with an aqueous dispersion containing the active ingredient or combination of active ingredients at the dose in question (4 experiments/dosage). Comparative plants were treated with distilled water without active ingredients.

One leaf was removed from each bean plant proboscis just before treatment.

The mites present on each leaf were knocked off onto a piece of white paper using a Vlasov. Next, these S2 leaves were crushed on paper and the number of mites present on each leaf was visually counted before treatment.

The treated and comparison plants were placed in a greenhouse under normal temperature, light and humidity conditions.

Twenty-one days after treatment, one leaf was removed from each bean plant. The mites present on each leaf were knocked off onto a piece of white paper using a Vlasov and crushed on this paper. The number of mites present on each leaf was measured in the same manner. The % mortality for comparative plants treated with distilled water without active ingredient was thus determined.

The results were as follows: 1 15 0 0 2
0 12.5 0 Section 3
0 25 0 Section 4 0
50 95 Section 5 5 12-
5 100 Section 6 5 25 1
00%7 10 115 10048
These results demonstrate a very clear synergistic effect from the combination of cypermethrin and nithione. Especially sy/
The combination of cypermethrin at hl and nithione at 1 z s y/ht resulted in a kill rate of 100 orders of magnitude, whereas cypermethrin alone at a rate of 15 p/ht showed no kill and also Only Nichion 2
It will be observed that the administration of sy/hx used also shows no killing.

An experiment was conducted on a phosphorus male garden of Star King species that is about 20 years old and planted in different areas.

Cypermethrin was used as an aqueous emulsion containing 2 p/h1 of Cypermethrin diluted with water from an emulsifiable concentrate having the following composition: Cypermethrin 1005E
-Ethylene oxide/alkylphenol m compound 5ay
-Calcium alkylarylsulfonate 30
y- Sufficient amount of petroleum fraction (aromatic solvent) i o o
Otz Nithion is Rhodosi P (trademark) with the following composition:
5oop - mixture of anionic and nonionic surfactants 8oy - oxidation By mixing the above two emulsifiable concentrates and diluting the resulting mixture with water, 2 y/hl of cypermethrin and 7 s
An emulsion was prepared containing a combination of two active ingredients in y/hx nithione.

Seven consecutive treatments were performed using these emulsions on the following days: April 8th (TI), April 24th (T2),
May 7th (T3), May 21st (T4), June 5th (T
), June 16th (To) and July 8th (T,).
These processes are about 10,001! , /ha, and the treatment was repeated four times for each dose.

Fifteen days after the first treatment ('r, +15), 25 leaves were harvested from each area corresponding to one dose of active ingredient. The number of surviving mites was counted and the average number of mites per leaf was calculated.

Processing the same measurement TR+T3! 'r41 'r and T, 6 days after each treatment, and further treatment T,
It was also carried out 10 days after. The results obtained are shown in the table below.

Cypermethrin, used by itself at a dose of 2 P/hl, showed no acaricidal activity in this experiment, and the same number of mites present in the experiment treated with cypermethrin, each 4 often compared to untreated pox v. It is observed that the number is much larger than that in .

This phenomenon is probably due to the effect of cypermethrin on insects that compete with and/or prey on mites, and this effect indirectly has a positive effect on mite reproduction. Furthermore, nithione used by itself at a rate of 75y/h 1 showed only a slight miticidal activity on mites and, according to the final measurements (T7+19), also had an indirect positive effect on mite reproduction. (more ticks than in the comparison). Finally, the Cypermethrin+Nithion 9 combination was observed to have excellent acaricidal activity in all cases.

Field Experiment This experiment was carried out in the same phosphorus garden, and followed the same method and used the same composition as in Example 2, and the treatments were carried out for the number of days indicated in Example 2.

The insecticidal activity against the following parasites was then determined: 15 days after treatment To, the number of caterpillars surviving on the shoots was counted;
The number of caterpillars surviving per 100 buds was calculated. The results were as follows: Knee untreated comparison
10.3-Cypermethrin (2y/ht)
1.6-nithione (7sy/ht)
5-cypermethrin + nithion (2+7 s y/h1) o,
a Treatment T, 010 Day Condition 1 The number of nine branches eroded by this parasite was counted in each area, and the average number of branches eroded in one area was determined. The results were as follows: knee untreated comparison 82.6-Cypermethrin (2P/hl) 2.3
-Nithion (7sy/h1).

-Cypermethrin + Nithion (2+75 y/hx).

After 20 days of treatment T, the number of eroded branches and the number of uneroded branches were counted, and the ratio of eroded branches was determined as full. The results were as follows: Knee untreated comparison
24.7%-cypermethrin (2y/
hx) 81.74-nithione (75y/hl
) 4.7L) h-cypermethrin+
Nichion 1.7 悌This experiment was conducted on a Linza garden with Saalden species that was about 20 years old.

Starting from the emulsifiable concentrates described in Example 2, cypermethrin alone (ay/ht) or nithione alone (75P/hl) - or the combination of nithione plus cypermethrin (75y/h1+3y/ht) respectively
An aqueous emulsion was prepared.

Using commercially available acaricide tetrasul (tθtragul) as a comparison compound, this compound 40y
An aqueous suspension was prepared containing /ht.

Treatment was carried out by spraying these emulsions or dispersions on May 15th (T-0) at a rate of 1500 fl/ha.

Immediately before treatment, the number of live mites present on 25 leaves in each area was measured and the average number per leaf was calculated. The same measurements were carried out 3, 7 and 17 days after treatment T (T+3, T+7 and T+17), respectively. The results are shown in the table below.

As is clear from the measurement example at the end of the table, the combination of cypermethrin and nithione exhibits excellent acaricidal activity.
This activity is much better than that of the comparison compound, and when only the comparison compound is used in the same application as the combination, cypermethrin and nithione show results very similar to the untreated comparison.

Representative Patent Attorney Moto Imamura

Claims (9)

[Claims] (1) As an active ingredient, Nithion and the formula (■): [In the formula, R represents a hydrogen atom or a cyano group, and R8 represents a 2,2-
Dimethyl-a-, (2,2-dichlorovinyl)-cycloprot-1-yl group, 2,2-dimethyl-3-(2,2
-dibromvinyl)-cycloprot-1 group, 2゜2-dimethyl-3-(2-methylprop-1-enyl)
- cycloprop-1-yl group or 1"l:1-(4-chlorophenyl)-isobut-1-yl group] in combination with pyrethro-P. A method for treating plants for eradicating crop-destroying arthropods, in particular for eradicating prophylactic mites, characterized by: (2) The method according to claim 1, wherein Villethroy P is selected from cypermethrin, permethrin, decatri/and fennolerate. (3) The method according to claim 2, wherein Villethroy P is cypermethrin. (4) The treatment is carried out using a composition, the formulation and application rate of which is 100 to 500 y/ha of nithione and 0.1 to 500 y/ha of pyrethroid.
Claims 1 to 3 are characterized in that the amount is such that it is applied at a ratio of /ha, and the weight ratio of pyrethroy P / nithione is 0.0001 to 1.
The method described in any of the paragraphs. (5) The weight ratio of Billesroy P/Nithion is 0.00
5. The method according to claim 4, wherein the ratio is 1 to 0.1. (6) Claims characterized in that the active ingredient contains a combination of nithione and a pyrethroid of the formula: [wherein R and R1 have the same meanings as described in claim 1] Insecticidal and acaricidal compositions that can be used to carry out the method according to paragraph 1. (7) The composition according to claim 6, comprising 0.01 to 100 parts of pyrethroid per 100 parts of nithione. (8) The composition according to claim 6 or 7, wherein the pyrethroid is selected from cypermethrin, permethrin, decamethrin, and fennolerate. (9) The composition according to claim 8, wherein the pyrethroi P is cypermethrin. 9. The composition according to any one of claims 6 to 8, further comprising (lO) an agriculturally acceptable inert carrier and optionally a surfactant.