JP7291882B2 - Clothianidin-containing aerosol - Google Patents

Description

The present invention relates to a clothianidin-containing aerosol.

(E)-1-(2-chloro-1,3-thiazol-5-ylmethyl)-3-methyl-2-nitroguanidine (common name: clothianidin) is known as a kind of neonicotinoid insecticidal component. . Various preparations containing clothianidin as an active ingredient have been disclosed (Patent Documents 1 to 6).

JP 2014-159397 A JP 2014-51462 A JP 2013-173721 A Japanese Unexamined Patent Application Publication No. 2011-201780 Japanese Unexamined Patent Application Publication No. 2010-209001 JP 2016-98213 A

Various methods such as bait agents are available for exterminating insect pests at home, but the method of applying the agent directly to insect bodies is effective. In particular, if it is an aerosol or a hand spray, it can be easily used at home, but the carbon dioxide preparation containing clothianidin as an active ingredient disclosed in Patent Document 1 is a high-pressure gas cylinder, so it has a large capacity and can be used at home. Difficult to use on a daily basis. In addition, it cannot be said that the aerosol- or hand-spray-type aqueous formulations containing clothianidin as an active ingredient disclosed in Patent Documents 5 and 6 have a sufficient insecticidal effect. Accordingly, an object of the present invention is to provide an aerosol agent containing clothianidin as an active ingredient, which can be used at home and has an excellent insecticidal effect.

As a result of intensive studies, the inventors of the present invention have found that the following configuration is highly effective in achieving the above object.

That is, the present invention
[Invention 1] An aerosol preparation comprising (a) clothianidin, (b) polyethylene glycol, and (c) a paraffin solvent, and (d) dimethyl ether as a propellant.
[Invention 2] The aerosol according to [Invention 1], wherein the mass ratio [(a)/(b)] of (a) clothianidin to (b) polyethylene glycol is 1/39 to 1/147. agent.
[Invention 3] The aerosol agent according to [Invention 1] or [Invention 2], which contains polyethylene glycol having a number average molecular weight of 200 to 400 as determined from the hydroxyl value.
[Invention 4] An aerosol product comprising the aerosol agent according to any one of [Invention 1] to [Invention 3].
[Invention 5] A method for exterminating pests using the aerosol product according to [Invention 4].

INDUSTRIAL APPLICABILITY According to the present invention, a clothianidin-containing aerosol agent having sufficient insecticidal effect can be obtained, and its practical utility is extremely high.

The aerosol preparation of the present invention is an aerosol stock solution containing (a) clothianidin, (b) polyethylene glycol, (c) a paraffinic solvent, and (d) dimethyl ether as a propellant.

Further, in the configuration described above, the mass ratio [(a)/(b)] of (a) clothianidin to (b) polyethylene glycol is preferably 1/39 to 1/147. When the ratio of [(a)/(b)] is within this range, an aerosol agent with superior immediate effect can be obtained.

The amount of clothianidin to be blended may be appropriately determined in consideration of the purpose of use, method of use, etc., but it is 0.01 to 0.70 w/w%, more preferably 0.01 to 0.70 w/w% of the total amount of the aerosol agent. 30w/w% is suitable. If the blending amount is less than 0.01 w/w%, the desired effect cannot be obtained, while if the blending amount is 0.70 w/w% or more, there is no difference in the effect. The appropriate amount of polyethylene glycol to be blended is 1.0 to 27.0 w/w% with respect to the total amount of the aerosol.

Polyethylene glycol having a number average molecular weight of 200 to 400 determined from the hydroxyl value can be used. For example, commercially available products of polyethylene glycol include trade names “PEG-200”, “PEG-300” and “PEG-400” manufactured by Sanyo Chemical Industries, Ltd.

Incidentally, the hydroxyl value is determined by the hydroxyl value measuring method described below. The hydroxyl value of polyethylene glycol determined by the following method is, for example, 534 to 590 for a number average molecular weight of 200, 356 to 393 for a number average molecular weight of 300, and 268 to 294 for a number average molecular weight of 400.
(Hydroxyl value measurement method)
(1) About 1 g of a sample is precisely weighed in a conical flask with a grounding, and 5 ml of a mixed reagent of acetic anhydride and pyridine is added with a whole pipette.
(2) Immerse the Erlenmeyer flask in an oil bath at 95° C. to 100° C., attach a drop-in cooler equipped with a grinder, and react for 1 hour.
(3) After cooling, add 1 ml of water from the top of the cooler, stir well, and heat on an oil bath for 10 minutes.
(4) Remove from the oil bath and allow to stand for an additional 10 minutes.
(5) Titrate with 0.5 mol/L potassium hydroxide standard solution using 0.5% phenolphthalein as an indicator.
(6) Carry out a blank test in the same manner, and obtain the hydroxyl value according to the following formula.
Hydroxyl value = {(ab) x 28.05 x f}/d + C
a: Number of ml of 0.5 mol/L potassium hydroxide standard solution required for blank test
b: Number of ml of 0.5 mol/L potassium hydroxide standard solution required for this test
c: Acid value
d: Sample collection amount (g)
f: titer of 0.5 mol/L potassium hydroxide standard solution

Paraffinic solvents include isoparaffinic solvents and normal paraffinic solvents. Examples of isoparaffin-based solvents include IP Solvent 2028 and IP Solvent 1620 manufactured by Idemitsu Kosan. On the other hand, examples of normal paraffin-based solvents include Neothiosol manufactured by Chuo Kasei Co., Ltd., and the like.

The aerosol stock solution of the present invention may contain a wood preservative/antifungal agent, an auxiliary component other than polyethylene glycol, and various solvents within a range that does not impair the effects of the present invention.

Examples of wood preservatives and fungicides include 3-iodo-2-propynyl-N-butylcarbamate, p-chlorophenyl-3-iodo-2-propynylformal, 3-bromo-2,3-diiodo-2-propenylethyl carbonate, hexaconazole, cyproconazole, propiconazole, tebuconazole, ipconazole, azaconazole, epoxiconazole, metconazole, tetraconazole, penconazole, triadimefone, bitertanol, microbutanil, diniconazole, difenoconazole, imibenconazole, tri Adimenol and the like can be used.

In addition, the aerosol stock solution of the present invention may appropriately contain an insecticidal component other than clothianidin. Examples of insecticidal components other than clothianidin include neonicotinoid compounds other than clothianidin, pyrethroid compounds, organophosphorus compounds, carbamate compounds, and IGR agents.

Examples of neonicotinoid compounds other than clothianidin include imidacloprid, thiamethoxam, nitenpyram, acetamiprid, thiacloprid, dinotefuran, and the like.

Examples of pyrethroid compounds include acrinathrin, allethrin, beta-cyfluthrin, bifenthrin, cycloprothrin, cyfluthrin, cyhalothrin, cypermethrin, empentrin, deltamethrin, esfenvalerate, etofenprox, fenpropathrin, fenvalerate, flucitri flufenprox, flumethrin, fluvalinate, halfenprox, imiprothrin, permethrin, prallethrin, pyrethrin, resmethrin, sigma-cypermethrin, silafluofen, tefluthrin, tralomethrin, transfluthrin, tetramethrin, d-tetramethrin, monfluorothrin, Phenothrin, alpha-cypermethrin, zeta-cypermethrin, lambda-cyhalothrin, gamma-cyhalothrin, furamethrin, taufluvalinate, metofluthrin, mepafluthrin, dimefluthrin, 2,3,5,6-tetrafluoro-4-(methoxymethyl)benzyl = 2,2-dimethyl-3-[(1Z)-3,3,3-trifluoro-1-propenyl]cyclopropanecarboxylate), 2,3,5,6-tetrafluoro-4-(methoxymethyl) benzyl = 2,2,3,3-tetramethylcyclopropanecarboxylate, 2,3,5,6-tetrafluoro-4-(2-propynyl)benzyl = 2,2,3,3-tetramethylcyclopropanecarboxy rates and the like.

Examples of organic phosphorus compounds include acephate, aluminum phosphide, butathiophos, cadosaphos, chlorethoxyphos, chlorfenvinphos, chlorpyrifos, chlorpyrifos-methyl, cyanophos (CYAP), diazinon, DCIP (dichlorodiisopropyl ether), diclofenthion (ECP). , dichlorvos (DDVP), dimethoate, dimethylvinphos, disulfotone, EPN, ethione, etoprophos, etrimphos, fenthion (MPP), fenitrothion (MEP), fosthiazate, formothion, hydrogen phosphide, isofenphos, isoxathion, malathion, mesulfenphos, methidathione ( DMTP), monocrotophos, nared (BRP), oxydeprofos (ESP), parathion, fosarone, fosmet (PMP), pirimiphos methyl, pyridafenthion, quinalphos, phenthate (PAP), profenophos, propafos, prothiophos, pyraclophos, salichione, sulprofos, tebpylimphos, temephos, tetrachlorbinphos, terbufos, thiometone, trichlorfone (DEP), vamidothione, folate, and cassaphos.

Examples of carbamate compounds include alanicarb, bendiocarb, benfuracarb, BPMC, carbaryl, carbofuran, carbosulphan, cloetocarb, ethiophenecarb, phenocarb, phenothiocarb, fenoxycarb, furatiocarb, isoprocarb (MIPC), metolcarb, methomyl, methiocarb, NAC, oxamyl, pirimicarb, propoxur (PHC), XMC, thiodicarb, xylylcarb, and aldicarb, and the like.

Examples of IGR agents include pyriproxyfen, methoprene, and diflubenzuron.

These insecticidal components can be used singly or in combination of two or more. In addition, some of the above compounds have optical isomers, stereoisomers, geometric isomers, etc., and the insecticidal component used in the present invention includes active isomers and mixtures thereof.

The propellant used for filling the aerosol container with the aerosol formulation of the present invention is dimethyl ether (DME). As for the amount of dimethyl ether, the volume ratio of the aerosol stock solution to the propellant in the aerosol formulation is 50:50 to 10:90, more preferably 40:60 to 20:80.

Also, the aerosol agent of the present invention can be filled into an aerosol container to form an aerosol product. The aerosol container to be filled is not particularly limited, and for example, a known aerosol container equipped with a pressure container, an aerosol valve, an actuator, etc. can be used.

The aerosol product filled with the aerosol agent of the present invention can be used to exterminate pests by spraying them directly on pests or at habitats of pests.

Examples of pests to be exterminated by the present invention include the following.
Lepidopteran pests: Plodia moths such as Plodia interpunctella, Tinea translucens, Tineola b.
Culex pipiens pallens, Culex tritaeniorhynchus, Culex aegypti (Cul
ex quinquefasciatus), etc., Aedes aegypti (Aedes
aegypti), genus Aedes such as Aedes albopictus, genus Anopheles such as Anopheles sinensis,
Chironomids, Musca domestica, Musci
na stabulans), blow flies, flesh flies, leaf flies, seed flies (Delia platura), onion flies (Delia antiqu
a), flies such as flies, fruit flies, flea flies such as Megaselia spiralis, and Clogmia alb
ipunctata), blackflies, blackflies, biting midges, and the like.
Tepidoptera pests: German cockroach (Blattella germanica), black cockroach (Periplaneta fuliginosa), American cockroach (Perip
laneta americana), brown cockroach (Periplaneta b.
runnea), Eastern cockroach (Blatta orientalis), and the like.
Hymenoptera pests: Monomorium pharaosis, Formica fusca japonica, Ochetello
s glaber), Mystic ants (Pristomyrmex pungens), Giant ants (Pheidole noda), Leaf-cutting ants (Acromyrmex spp.
), fire ants (Solenopsis spp.), Argentine ants (Lin
ants such as Epithema humile), wasps, and wasps.
Cryptoptera pests: cat flea (Ctenocephalides felis), dog flea (C
tenocephalides canis), human flea (Pulex irritan
s), Xenopsylla cheopis and the like.
Louse pests: Body lice (Pediculus humanus corporis)
), head lice (Pediculus humanus humanus), pubic lice (Phthirus pubis), cow lice (Haematopinus eur
ysternus), sheep lice (Dalmalinia ovis), pig lice (
Haematopinus suis), dog lice (Linognathus set
osus) and the like.
Isoptera pests: Reticulites speratus, Coptotermes formosanus, Incisitermes minor, Cryptotermes domesticus, Odontotermes formosanus, N eotermes koshunensis), Satsuma termite (Glyptotermes satsumensis), Nakajima termites (Glyptotermes nakajimai), Katan termites (Glyptotermes fuscus), Kodama termites (Glyptotermes kodamai), Kushimoto termites (Glyptotermes kushimensis), Termites (Hodotermopsis japonica), Termites (Coptotermes guangzhoensis), Amami Termites ( Reticulitermes miyatakei), Reticulites flaviceps amamianus, Reticulites SP., Nasutitermes takasagoensis, Pericapriterme nitobei, Termites (Sinocapritermes mushae) Hemiptera pests: Laodelphax striatellus), brown planthopper (Nilaparvata lugens), brown planthopper (Sogatel
la furcifera), leafhoppers (Nephotettix
cincticeps), green leafhopper (Nephotettix vi
leafhoppers such as Rescens), bed bugs (Cimex lectularius)
, Bed bugs such as Cimex hemipterus, etc. Coleoptera pests such as Pheasants corne) and other beetles, flounder bark beetle (Lyctus brunneus), pine bark beetle (Tomi
cus piniperda) and other bark beetles, long beetles, leopard beetles, etc. Acarina pests: Acarina pests such as Tyrophagus putrescentiae, Dermatophagoides farinae, Dermatophagoides ptrenyssnus) and other leopard house dust mites, Cheyletus eruditus ), Cheyletus malaccensis, Cheyletus moorei, Cheyletiella yasguri and other cheylet mites, Leptotrombidium akamushi and other chiggers, Ticks Woodlice such as ticks (Haemaphysalis longicornis): Porcellio scaber, Porcellionides pruinosus, Armadillidium vulgare, etc. Centipedes: Scolopendra subspinipes mutilans, Scolopendra subspinipes japonica), Scolopendra subspinipes multidens, Thereuopoda hilgendorfi, etc. Millipedes: Oxidus gracilis, Parafontaria laminata laminata, etc. Spiders: Chiracantium japonicum, Latrodectus hasseltii, etc. Although it shows insecticidal effect against the above pests, It is preferably used for termites such as Yamato termites and Formosan termites, bark beetles, and German cockroaches.

The present invention will be described in more detail below with reference to examples and test examples, but the present invention is not limited to these examples.

1. Manufacture of aerosol preparations Seventeen kinds of aerosol preparations (Formulation Examples 1 to 14, Comparative Examples 1 to 3) having the compounding ratios shown in Table 1 were prepared.

Further, using the following members, an aerosol product filled with 100 mL of each aerosol agent was produced.
・Pressure pressure can for aerosol AE180YNG (manufactured by Hokkai Seikan)
・Valve: stem hole diameter Φ1・0×0.5×3, housing hole diameter Φ2.0mm (manufactured by Mitani Valve)
・Injection button: Injection hole diameter Φ0.8mm (manufactured by Mitani valve)

The following aerosol preparation examples are also provided.
Formulation example 15
Put PEG-300 (manufactured by Sanyo Chemical Industries) 3.397 w / w% in a can, clothianidin (manufactured by Sumitomo Chemical) 0.011 w / w% and monfluorothrin (Sumifreeze: manufactured by Sumitomo Chemical) 0.010 w / w% Add 41.10w/w% IP Solvent 2028 (manufactured by Idemitsu Kosan Co., Ltd.) and attach the valve, then fill with 55.43w/w% dimethyl ether (manufactured by Koike Chemical) and attach the injection button. Get an aerosol product.

Formulation example 16
Put 10.042 w/w% of PEG-300 (manufactured by Sanyo Chemical Industries) in a can, and add 0.003 w/w% clothianidin (manufactured by Sumitomo Chemical) and 0.101 w/w% of monfluorothrin (Sumifreeze: manufactured by Sumitomo Chemical). In addition, IP Solvent 2028 (manufactured by Idemitsu Kosan) 14.55w / w% is added to this and the valve is attached, then dimethyl ether (manufactured by Koike Chemical) 74.76w / w% is filled, and an injection button is attached to aerosol get the product.

Formulation Example 17
Put PEG-300 (manufactured by Sanyo Chemical Industries) 3.447 w / w% in a can, clothianidin (manufactured by Sumitomo Chemical) 0.035 w / w% and monfluorothrin (Sumifreeze: manufactured by Sumitomo Chemical) 0.0026 w / w% , then add 40.13w/w% normal paraffin solvent (Neothiosol: manufactured by Chuo Kasei) and install the valve, then fill with 56.26w/w% dimethyl ether (manufactured by Koike Chemical) and press the injection button. Wear it to get an aerosol product.

Formulation Example 18
Put PEG-300 (manufactured by Sanyo Chemical Industries) 3.447 w / w% in a can, add clothianidin (manufactured by Sumitomo Chemical) 0.035 w / w% and monfluorothrin (manufactured by Idemitsu Kosan) 0.0026 w / w%, IP Solvent 1620 (Neothiosol: manufactured by Chuo Kasei) 40.13w/w% is added to this and the valve is attached, then dimethyl ether (manufactured by Koike Chemical) is filled with 56.26w/w%, and an injection button is attached to aerosol get the product.

2. Residue contact test for German cockroach (Test Example 1)
Formulation Examples 1 to 14 and Comparative Examples 1 to 3 were sprayed onto a glass plate (15 cm × 15 cm) from a distance of 30 cm so that 4 g was treated on the surface of the glass plate, and then air-dried at room temperature for 1 week to obtain a test specimen. . A cylindrical plastic ring with a diameter of 12 cm was placed on the test specimen, and 10 male and female German cockroaches were placed in the ring to investigate the number of knockdown (KD) insects over time, and KT ₅₀ was recorded by the probit method. The test was performed 3 times and the average value was adopted.

Table 2 shows the results.

As a result of the test, an aerosol agent filled with (d) dimethyl ether as a propellant in an aerosol stock solution containing active ingredients (a) clothianidin, (b) polyethylene glycol, and (c) paraffin solvent was excellent against German cockroaches. showed a knockdown effect.

3. Efficacy test against termites (Test Example 2)
Of the formulation examples, Formulation Example 3, Formulation Example 8 and Formulation Example 13 and Comparative Example 4 (competitor's product 1 for termite-control aerosol agent), Comparative Example 5 (competitor's product 2 for termite-control aerosol agent), and Comparative Example 6 ( An efficacy test against termites was conducted using a third-party termite extermination aerosol agent 3).

For Comparative Examples 4 to 6, qualitative analysis and quantitative analysis of active ingredients were performed. As a result, in Comparative Example 3, the main solvents were alcohols, containing 0.227 w/w% tralomethrin, 0.114 w/w% empenthrin, and 0.114 w/w% cyproconazole. It was confirmed. Comparative Example 4 confirmed that the main solvent was kerosene and contained 0.97 w/w% of etofenprox. In Comparative Example 5, the main solvent was kerosene, and it was confirmed that 0.199 w/w% of etofenprox was contained.

Test method for efficacy test against termites Formulation Example 4 and Comparative Examples 3 to 5 were sprayed onto cedar wood pieces of 1 cm x 1 cm x 2 cm, and air-dried at 40°C for 24 hours to prepare test specimens. A test specimen and a piece of cedar wood of the same size as the test specimen were placed in a rearing container made by putting gypsum in a plastic cup and hardening them so that they would not come into contact with each other. 150 Formosan termite worker ants and 15 soldier ants were released as test insects into a breeding container, and observed over time to investigate behavioral cessation, knockdown (KD), and the number of dead insects. The test was performed 3 times and the average value was adopted.

Table 3 shows the results. With the aerosol formulations of Formulation Examples 3 and 8, it was confirmed that all animals died after 7 days. That is, compared with the aerosol formulations of Comparative Examples 4 to 6, the efficacy was higher one day after the test, and the time until all animals died was shorter. As described above, the aerosol agents of Formulation Examples 3 and 8 exhibit higher efficacy against termites than the aerosol agents of Comparative Examples 4 to 6, and can be used at home as aerosol products with high insecticidal efficacy. .

Claims (5)

An aerosol containing (a) clothianidin, (b) polyethylene glycol, (c) a paraffinic solvent and a propellant, wherein the propellant consists only of (d) dimethyl ether,
An aerosol agent characterized in that the mass ratio [(a)/(b)] of (a) clothianidin to (b) polyethylene glycol is 1/39 to 1/147. 2. The aerosol agent according to claim 1, which contains polyethylene glycol having a number average molecular weight of 200 to 400 as determined from the hydroxyl value. An aerosol product for pest control, filled with the aerosol agent according to claim 1 or 2 . 4. The pest-control aerosol product according to claim 3 , wherein the pests to be exterminated are at least one of termites, bark beetles and German cockroaches. A method of controlling pests using the aerosol product according to claim 3 or 4 .