JPH021801B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention is applicable to livestock animals (cows, horses, sheep, goats,
This invention relates to an insecticide for animals that is not primarily intended for the treatment of animals, and that prevents and kills insects and mites that harm the growth of pigs, chickens, dogs, cats, etc. when raised. [Prior art] Examples of animal pests include blood-sucking pests such as ticks, red mites, and sand mites; insects such as horseflies, sand flies, midges, lice, and fleas; and livestock environmental hygiene pests such as flies, mosquitoes, and cockroaches. It will be done. Control agents for these pests include pyrethroid insecticides such as pyrethrin, allethrin, tetramethrin, resmethrin, and phenotrin, organic phosphorus agents such as coumaphos, trichlorfon, dichlorvos, fenitrothion, naled, marasion, calcufos, feniclophos, and prothiophos, carbaryl, and propiophos. Xur, ortho-sec-butyl phenyl-
Carbamates such as N-methyl carbamate (hereinafter abbreviated as BPMC) are used. In addition, pyrethroid compounds include octachlordipropyl ether [1,1-oxybis-(2,3,3,3
-tetrachloropropane), hereinafter abbreviated as S-421], piperonyl butoxide, N-(2-ethylhexyl)-1-isopropyl-4-methylbicyclo(2,2,2)-oct-5ene-2,3-
Synergists such as dicarboximide, N-(2-ethylhexyl)-bicyclo-(2,2,1)-hepta-5ene-2,3-dicarboximide, etc. are added to increase insecticidal power, repellent Insecticides for animals that increase their control effect by adding agents or attractants are used as insecticides for animals. As described above, most animal insecticides are made of a single insecticide, synergist, repellent, or attractant alone, and are mostly mixtures of a plurality of each component. However, the BPMC and S of the present invention
-421 has not yet been used as an animal insecticide, and mixtures with such various characteristics are not known even in the field of agricultural chemicals related to agriculture and forestry. However, one or two of pyrethrin, allethrin, and phthalthrin (tetramethrin) and 1-
An insecticide containing either naphthyl-N-methyl carbamate or phenyl-N-methyl carbamate and octachlordipropyl ether as active ingredients and having synergistic efficacy against general pests and low toxicity to humans and animals has been disclosed as a prior art ( Japanese Patent Publication No. 48-61633
Publication No.). Also 2,3,3,2',3',3'-hexachlor-
Diallyl ether [1,1-oxybis-(2,
3,3-trichloropropene-2)] or 2,3,
3,3,2',3',3',3'-octachlordiprolether [1,1-oxybis-(2,2,3,
3-tetrachloropropane)], (S-421) has been disclosed as a rice cultivation disease and soil treatment agent (JP-A-Sho
53-148524). In the detailed explanation of this technology, it is stated that carbamate insecticides can be used in combination with other insecticides as a general basic technology for pesticide formulations, but the combination of BPMC is not described at all, and the combination of these two types is not mentioned at all. The halogenated alkyl ether exhibits no insecticidal activity against either animal blood-sucking or non-blood-sucking pests. [Problems to be solved by the invention] Livestock animal pests are essentially different from other sanitary pests and agricultural and forestry crop pests, and include ticks, red mites, sand mites, fleas, lice, and horseflies that obtain their nutritional source by sucking the blood of livestock. It consists of mites and insects such as , stable flies, and midges. Furthermore, environmental pests such as flies, mosquitoes, and cockroaches infest the excreta and feed of livestock animals. In this way, ecological research on blood-sucking parasitic pests of livestock or the establishment of control methods for them is difficult because it is difficult to uniformly raise a large amount of biological pests necessary for the research. The current situation is that we are far behind the field of pharmaceuticals. Furthermore, a large number of tests are required, including direct toxicity to livestock animals and residue in livestock products obtained from them.
In this regard, BPMC has undergone many tests to check not only its insecticidal power, but also its residual transfer to meat and milk ingredients, and its safety as an animal drug has been confirmed and it has been put into practical use. From this point of view, only three carbamate insecticides are currently approved for use in animals: BPMC, propoxur, and carbaryl, but BPMC is the most suitable because of its insecticidal power and safety. It is an ingredient.
However, the insecticidal effect is not sufficient against pests with resistance factors that are targeted by animal insecticides, such as house flies, and the spectrum of pests that can be killed is still narrow. In particular, pests with resistance factors, i.e., so-called cross-resistance, which shows resistance to two or more insecticides at the same time when treated with a single insecticide.
Furthermore, for pests with multiple-resistance that appear hereditarily when treated with two or more insecticides, such as the house fly, which is an environmental health pest for livestock, DDT was used around 1953, and organic phosphorus was used from 1965. Since 1976, it has been reported that houseflies, which are resistant to pyrethroid insecticides and have a poor fall-over effect (KD effect), have appeared. In terms of insect genetics, this
Those with a slow-acting kd gene (kdr gene) for DDT on chromosome 3 exhibit so-called cross-resistance, which means that they become slow-acting down to pyrethroid insecticides, which have a completely different chemical structure from DDT. It was clarified. The fact that one gene is involved in the resistance of multiple, and moreover, completely different chemical structures, means that a new insecticide may have resistance genes acquired from insecticides used in the past. This is due to other effects, namely cross-resistance. This is because, as in the case of DDT and BHC, the frequency of development of resistance to insecticides used in the past is
When a new insecticide is initially effective, the frequency of occurrence of resistance genes increases, and after a while it loses its practical value as an insecticide. This will cause great confusion at the pest control site.
Furthermore, in 1976, super-kdr was identified as multiple alleles of one resistance gene kdr in house flies.
Populations with what are called factors appear,
It is said that some species have even emerged that are even more resistant to pyrethroid insecticides. Furthermore, in 1967, for some organophosphorus insecticides, the ratio of the LD ₅₀ (half-lethal concentration) to that of the susceptible HI type, that is, the resistance ratio, was over 10 for Culex larvae.
The emergence of NA species has become a problem as it is said to exhibit cross-resistance to pyrethroids. Such various complex resistance factors are not limited to house flies, but also include Musca benzii, Musca benzii, M.
Hervel), M. tempesliva, and M. Saishueosis, which congregate on grazing cattle and degrade the environment, are also appearing as genetic factors in blood-sucking stable flies (Stomoxys caleitrans), and their control is becoming more and more common. There was a problem that made it difficult. The present invention solves the above problems, has a strong insecticidal effect against pests with resistance factors and various pests that harm the growth of animals, has a wide pest spectrum, is completely harmless to humans and livestock, and has little toxicity to fish. The purpose is to provide insecticides. [Means for Solving the Problems] The present inventors tested and researched various efficacy synergists in order to enhance the excellent insecticidal power of BPMC and at the same time expand the spectrum of insect pests that can be killed.
Obtain an animal insecticide with various characteristics containing S-421, which is already considered to be safe in terms of toxicity as an insecticidal synergist for animals as an alkyl ether having a chlorine atom substituted at a higher position than the above position. Furthermore, they discovered that this drug has strong insecticidal power even against insect pests with resistance factors, has characteristics not found in other drugs, and has low toxicity to fish, and completed the present invention. did. The present invention is an animal insecticide characterized by containing BPMC and S-421. BPMC used in the present invention is a lower monoalkyl phenyl-N-methyl carbamate insecticide, and its monoalkyl group is bonded to the ortho position, which is considered to have strong insecticidal power, and has a secondary butyl group. Among these ortho-substituted lower alkyl derivatives, BPMC has the lowest melting point, at 32℃ and
Industrial grade raw materials are almost liquid at room temperature below 30°. If the alkyl group and melting point are shown, (methyl, -CH ₃ , 101~2℃), (ethyl-
C ₂ H ₅ , 76-7℃), [isopropyl, -CH
( _CH3 ) ₂ , 96-7℃], [tert-butyl, -C
(CH ₃ ) ₃ , 96-6°C]. Also, Japanese Patent Application Publication No. 1973-
1-naphthyl-N-methyl carbamate shown in Publication No. 61633 has a melting point of 142°C, and phenyl-N-methyl carbamate has a melting point of 85-6°C. As described above, BPMC has the lowest melting point among these carbamate insecticides, and is characterized by its original insecticidal power as well as a number of major advantages in terms of insecticide formulation. The chemical properties are as follows. That is, boiling point 115~6℃/0.02mmHg, vapor pressure 3.0mm
Hg/130℃, flash point 142℃, specific gravity ^d304 : _1.041 , viscosity 250CPS (35℃), specific heat 0.42cal/g・℃) heat of fusion
25-30Kcal/Kg, thermal conductivity 0.15Kcal/M・HR
°C, stable under weak acidity, unstable under strong acidity and alkali.
Also, the solubility (%) at 20℃ is
10ppm or less, hexane 16.6, methanol, ethanol, benzene each 100 or more, ethyl acetate, ether, acetone, chloroform each 200 or more,
Furthermore, it is freely miscible with other components of the present invention, such as S-421, dimethylformamide, dimethyl sulfoxide, and N-methylpyrrolidone. Being easily soluble in hexane is also easily soluble in aliphatic saturated hydrocarbons such as kerosene, which is advantageous for producing liquid preparations, and being freely miscible with S-421 facilitates the transition to the point of action for killing pests. As a result, it exhibits strong insecticidal power. Also, S-421 has the chemical name 1,1-oxybis(2,
3,3,3-tetrachloropropane) in 1958
Published as a synergist of pyrethrins by Adolphi.H. [Pyrethrum post43 (1958)] This S-
421 (boiling point 144-150℃/1mmHg) or 1,1-
Oxybis(2,3,3-trichloropropene-
2) (boiling point 90.5-91.8°C), it is effective as an insecticidal synergist against house flies and as a synergist with pyrethrin, allethrin, or rotenone, and the latter can also be used in place of S-421 of the present invention. but,
The former has greater killing power against resistant pests. S-421 is a colorless liquid that is synthesized by reacting paraformaldehyde and trichlorethylene at 30°C using hydrochloric acid and aluminum trichloride as catalysts, or by reacting trichlorethylene and dichloromethyl ether in dichloromethane in the presence of aluminum trichloride. be. Specific gravity 1.64-1.66 (20℃), refractive index n ²⁰ _D 1.52
~1.53, flash point 177℃, acute toxicity: oral LD ₅₀ (8 days) rat approx. 4.1g/Kg, mouse approx. 5.8g/Kg. It is a stable compound with low toxicity, almost insoluble in water, Being highly soluble in organic solvents, especially aliphatic hydrocarbons, is a feature that allows the liquid preparation of the present invention to be easily manufactured, which greatly improves formulation stability, compatibility with other insecticidal and fungicidal ingredients, and economic efficiency. It is profitable. The present invention is a mixture of BPMC and S-421 having the above-mentioned characteristics, and the formulations used include powder, fine granules,
Granules, tablets, wettable powders, emulsified wettable powders, emulsified granules, oils, sol, emulsions, aerosols, pastes,
Any convenient form, such as a smoke agent, may be prepared in combination with component stabilizers, property modifiers, or other potency-enhancing synergists such as piperonyl butoxide. In addition, other active insecticides, fungicides, herbicides, plant growth regulators, fertilizers, soil conditioners, etc. can also be contained. The blending ratio of BPMC and S-421 is preferably 1:0.5
When blended at a ratio of ~10, a sufficient synergistic effect can be achieved. Next, examples of the present invention and test examples showing the effects thereof will be given. Example 1 2 g of BPMC, 3 g of S-421, anhydrous nitric acid (45 μm
(below) 2.5 g, 0.2 g of phosphoric acid, and 92.3 g of kaolin (45 μm or less) are mixed and pulverized to obtain a powder. Example 2 3 g of BPMC, 3 g of S-421, and 0.3 g of isopropyl acid phosphate were mixed into pumice grains (0.297-0.105
mm) 92.7g and impregnated with pearlite fine powder (45μm
Below) 1g is coated in powder to obtain fine granules. Example 3 Dissolve 0.2g of BPMC and 1.0g of S-421 in kerosene.
Obtain the oil solution as 100ml. Example 4 BPMC 20g, S-421 30g, emulsifier (polyoxyethylene nonyl phenyl ether 40%, polyoxyethylene styryl phenyl ether 25%,
8 g of a 35% mixture of calcium dodecylbenzenesulfonate, 12 g of kerosene, and 30 g of xylene were uniformly mixed to obtain an emulsion. Example 5 BPMC 2g, S-421 20g, emulsifier (Example 4
5 g of the mixed solution (same as above) is impregnated into 55 g of fine perlite powder (63 μm or less) and crushed to obtain an emulsified wettable powder. Example 6 A mixed solution of 20 g of BPMC, 20 g of S-421, and 1.5 g of emulsifier (same as in Example 4) was uniformly dissolved and dispersed in an aqueous solution of 3% polyvinyl alcohol (low viscosity partially saponified product), 1% sodium alginate, and 96% water.
g and emulsify it to make a sol. Example 7 A mixed solution of 4 g of BPMC and 6 g of S-421 was mixed with 5% silicic anhydride (63 μm or less), 1% sodium lignin sulfonate, 30% bentonite, 0.5% sodium polyoxyethylene phenylphenol sulfate, and 63.5% kaolin. Add water to the mixed powder and granulate it (0.7mm or less)
Granules are obtained by soaking in 90 g of air-dried base grains. Test Method and Results The effects of the present invention will be tested and explained using different test pests. In addition, Comparative Examples 1 to 7 were obtained by replacing S-421 with a filler excipient in the respective formulations of Examples 1 to 7, and compared to Example 1 of the animal insecticide of the present invention. - 7 was used for comparison of insecticidal effect. Test example 1 (Insecticidal test against horseflies) 1 Test insect: Tabancs nipponicus
Adult female fly 2 Test method On the day of the test, horseflies collected by trap in Makino were anesthetized with dry ice, their wings were cut off, and 10 flies in each group were treated as samples. In other words, the test insects were placed in a polycup with a diameter of 8 cm and approximately 200 ml in the bell jar duster.
Put 10 fish in there, sprinkle 5g, 3g, and 1g per ^square meter, then remove the polycup.
Give cotton wool soaked in 5% sucrose water for 20 minutes.
The insect mortality rate was determined after 6, 12, and 24 hours after being left at ℃ and 70% RH, and the insect mortality rate (%) was calculated using Abbott's correction formula using the results of the untreated plot. 3 Test results

【table】

[Table] Test Example 2 (Insecticidal test against ticks) 1. Test insect: Wagyu beef tick (Haemaphysalis longicornics) 2. Test method: Using a sponge, diluted solutions of various concentrations were applied all over the body of a grazing female black Japanese cow. Before application, 2 days, and 6 days after application, 5 x 5 cm sections were defined on the left side of the cow's body in two places on the neck (upper part of the vein and in the vein area) and around the oral cavity, and the body hair therein was trimmed to count the number of insects living in the epidermis. The approximate number of insects was investigated in units of 10, the total number of living insects was calculated, and the acaricidal effect of each concentration was examined. One adult cow was placed in each of the untreated area and each concentrated solution area for testing. 3 Test results

【table】

[Table] Test example 3 (Insecticidal test against house fly) 1 Test insects Gunma pyrethroid knockdown resistant species (abbreviated as KDR species) Denken pyrethroid susceptible species (abbreviated as S species) 2 Test method Continuous contact method Ivy. That is, a circular filter paper (diameter 9 cm) was placed in a Petriciale (diameter 9 cm, height 2 cm) in a constant temperature room at 25°C, and 0.32 ml of the sample oil was poured into it (1 m ²
(at a rate of 50 ml per bottle). After 30 minutes of air drying, release 10 test insects and bring the test insects into contact with the residue surface. Next, according to the supine rate (%) with elapsed time.
Calculate the KT ₅₀ value (half supine time) (minutes) using the probit method. Contact is continued, the number of dead insects is investigated after 24 hours, and the mortality rate (%) is calculated using Abbott's correction formula. 3 Test results

[Table] Test example 4 (Insecticidal test against pig lice) 1 Test insects 10 female Landrace pigs and 10 male pigs in each area Pig lice (Heamatopinus suis) in adult pigs 2 Test method A diluted test chemical solution for each area was used. Sprayed all over the pig body. The chemical solution in each area was sprayed sufficiently uniformly. A visual survey of the population was conducted 1 and 7 days after spraying. 3 Test results

[Table] Test example 5 (Insecticidal test against Culex pipiens final instar larvae) 1 Test insects Amagasaki type organophosphorus resistant species (abbreviated as NA type) Hiyoshi type sensitive species (abbreviated as HI type) (Culex pipiens pallens) 2 Test method Waist-high shearlings (diameter 9cm, height
7.5cm), put 200ml of each concentration diluted solution using water,
Ten final instar Culex Culex larvae were released into the larvae, and the mortality rate (%) after 24 hours was investigated. Each section was repeated three times. 3 Test results

[Table] Test example 6 (Insecticidal test against field mites) 1. Test insect: Haemaphysalis longicornis, which occurred in a field. 2. Test method: Insecticide test against grass field mites. 2. Test method. A test area was set up, and chemicals were sprayed using a backpack-type power duster or a granulator at a rate of 30 kg per ha. The extermination effect of the test chemicals on Makino mites was determined by dragging a white flannel (80 cm x 100 cm) diagonally across each test plot, and judging the effectiveness by the number of mites attached to it. 3 Test results

【table】

[Table] From the above test results, the present invention has a strong synergistic insecticidal effect against various pests of livestock animals, and at the same time, it is superior to various insecticides against pests with complex genetic factors. It is clear that it is an animal insecticide with a control effect. Furthermore, the present invention is also excellent as a pesticide for agriculture and forestry, and reference test examples are shown below. Reference test example (insecticidal test against resistant Nymph) 1 Test insects Kagawa organic phosphorus resistant species (abbreviated as R-p species) Organic phosphorus sensitive species (abbreviated as S-p species) 2 Test method 10,000 minutes Paddy rice with 5 stalks was cultivated in a 1-are pot with water submerged at a depth of 1 to 2 cm.
Apply 30mg. On the 3rd day after application, the test insect larvae were ingested, and 5 days after ingestion, the survival or death of the leaf sheaths was investigated, and the mortality rate (%) was calculated. 3 Test results

〔Effect of the invention〕

The animal insecticide of the present invention includes blood-sucking animal pests,
It has a wide insecticidal pest spectrum and excellent insecticidal effect against livestock environmental and sanitary pests, and also has a strong insecticidal effect against pests with resistance factors that are difficult to control. It is also an animal insecticide with low toxicity to humans and animals, and low toxicity to fish.

Claims (1)

[Claims] 1 ortho-sec-butylphenyl-N-methylcarbamate and 1,1-oxybis-(2,
3,3,3-tetrachloropropane).