JP2609120B2 - Acaricide for airless mites containing a quaternary ammonium salt as an active ingredient - Google Patents

Description

The present invention relates to an acaricide and an acaricide containing a quaternary ammonium salt.

[Conventional technology]

Indoor dust mites are found everywhere indoors, and their growing area extends only to tatami mats and carpets, to sofas, stuffed animals and bedding. Conventionally, as acaricides against such house dust mites, phosphorus compounds such as fenitrothion, fenthion, DDVP, and diazinon, propoxers, carbamate compounds such as NAC, and pyrethroid compounds such as resmethrin are known. .

<Problems to be Solved by the Invention> These known acaricides are used on tatami mats, insect-proof paper for carpets, or sprayed or sprayed as they are, but organophosphorus or carbamate acaricides are used. Since the agent is highly toxic and has low effect on Dermatophagoides, it is limited in its application range and application amount. Further, since pyrethroids are expensive and slow-acting, they have various drawbacks, such as being limited in their application method and application amount. The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems of the prior art, and as a result, the fourth surfactant, which is a cationic surfactant used in cosmetics and pharmaceuticals for the purpose of sterilization, disinfection, antistatic and the like, has been developed. When a quaternary ammonium salt is contained as an active ingredient, all the disadvantages of the conventional acaricide described above are eliminated,
The present inventors have found an acaricide with low toxicity and excellent safety for the human body, and which is effective against astigmatid mites such as Dermatophagoides and have completed the present invention.

[Means for solving the problem]

That is, the present invention provides: (Wherein R ₁ is C _m H _n , m = 8-18, n = 17-37,
R ₂ Or a _{C m H n, m = 8~18} , a n = seventeen to thirty-seven. Provided that one or both of C _m H _n of R ₁ and R ₂ are Wherein R ₃ is an alkyl or alkenyl group having ₄ to 14 carbon atoms, and R ₄ is an alkyl or alkenyl group having 2 to 14 carbon atoms. The present invention relates to an acaricide for acaricidae, which comprises a quaternary ammonium salt represented by the formula (1) as an active ingredient.

The mites to be controlled in the present invention are acarid mites, especially house dust mites such as Dermatophagoides farinae and Dermatophagoides pteronyssinus, mites mites such as Dermatophagoides farinae and Dermatophagoides farinae, and mites such as Chilinic mites and House dust mites,
Examples include the mites of the stag mite and the mites mites, and the parasitic mites of the animals such as the house dust mite and the sick mite.

Although the acaricide of the present invention can be used as it is,
Usually held on a liquid carrier and a solid carrier, and if necessary, a film forming agent, an emulsifier, a dispersant, a spreading agent, a wetting agent, a stabilizer,
It can be used in the form of oils, emulsions, wettable powders, aqueous solutions, sprays, aerosols, smokers, coatings, powders, granules, etc. by adding propellants, volatilization modifiers and the like.

Examples of the liquid carrier include water and alcohols such as methyl alcohol, ethyl alcohol and isopropyl alcohol, ketones such as acetone, methyl ethyl ketone and cyclohexanone, ethers such as tetrahydrofuran, dioxane and dimethyl ether, hexane, kerosene, normal paraffin and solvent. Aliphatic hydrocarbons such as naphtha, aromatic hydrocarbons such as benzene and toluene, halogenated hydrocarbons such as dichloromethane and dichloroethane, esters such as ethyl acetate and butyl acetate, and CFC-based solvents (CFC-113, CFC-114B2 , CFC 21, CFC 10, etc.). As the solid carrier, for example, mineral powders such as silicic acid, kaolin, activated carbon, bentonite, diatomaceous earth, talc, clay, calcium carbonate, ceramic powders, vegetable powders such as wood flour, soy flour, flour, starch, cyclodextrin And the like.

Examples of the coating film forming agent include cellulose derivatives, vinyl resins, alkyd resins, urea resins, epoxy resins, polyester resins, urethane resins, silicone resins, acrylic resins, chlorinated rubbers, polyvinyl alcohol, and the like. As emulsifiers, dispersants, and spreading agents, soaps, polyoxyethylene fatty alcohol ethers, polyoxyethylene alkyl allyl ethers, polyoxyethylene fatty acid esters, fatty acid glycerides, sorbitan fatty acid esters, sulfuric acid esters of higher alcohols, Examples of surfactants such as alkyl allyl sulfonates and propellants include liquefied petroleum gas, dimethyl ether, and fluorocarbon. Further, as a volatilization modifier, sublimable carriers such as tricyclodecane, cyclododecane, 2,4,6-triisopropyl-1,3,5-trioxane, trimethylene norbornene, and sublimable carriers such as paradichlorobenzene and naphthalene π-camphor. Using an insect repellent, the mite control composition can also be used as a sublimable solid agent, empenthrin,
A volatile insecticide such as DDVP can be combined and used as a volatile mite control agent.

Furthermore, the acaricide of the present invention, various insect repellents, synergists,
Pest repellent, rodent repellent, antioxidant, anti-decomposition agent,
A bactericide, an antifungal agent, a fragrance, a coloring agent, and the like can be added. Insect repellents that can be compounded include 3-allyl-2-methylcyclopenta-2-en-4-one-1-yl dl-
Cis / trans-chrysanthemate, 3-allyl-2-
Methylcyclopenta-2-en-4-one-1-yl
dl-cis / trans-chrysanthemate, d-3-allyl-2-methylcyclopenta-2-en-4-one-1
-Yl d-trans-chrysanthemate, 3-allyl-2-methylcyclopenta-2-en-4-one-1-
Il d-trans-chrysanthemate, N- (3.4
* 5.6-tetrahydrophthalimide) -methyl dl-cis / trans-chrysanthemate, 5-benzyl-3-
Furylmethyl d-cis / trans-chrysanthemate, 5- (2-propargyl) -3-furylmethylchrysanthemate, 3-phenoxybenzyl 2.2-dimethyl-3- (2'-2'-dichloro) vinyl Cyclopropanecarboxylate, 3-phenoxybenzyl d-cis / trans-chrysanthemate, α-cyanophenoxybenzyl isopropyl-4-chlorophenylacetate, d-3-allyl-2-methylcyclopenta-2-
Ene-4-one-1-yl d-trans-chrysanthemate, (S) -α-cyano-3-phenoxybenzyl (1R · cis) -3- (2.2-dichlorovinyl) -2 ·
2-dimethylcyclopropanecarboxylate, (R.
S) -α-cyano-3-phenoxybenzyl (1R · 1
S) -cis / trans-3- (2.2-dichlorovinyl) -2-2.2-dimethylcyclopropanecarboxylate, α-cyano-3-phenoxybenzyl d-cis / trans-chrysanthemate, 1-ethynyl- 2-methyl-2-pentenyl cis / trans-chrysanthemate, 1-ethynyl-2-methyl-2-pentenyl 2
-2-dimethyl-3- (2-methyl-1-propenyl)
Cyclopropane-1-carboxylate, 1-ethynyl-2-methyl-2-pentenyl 2,2,3,3-tetramethylcyclopropanecarboxylate, 1-ethynyl-2-methyl-2-pentenyl 2,2-dimethyl −
3- (2.2-dichlorovinyl) diclopropane-1-
Carboxylates, 0.0-dimethyl 0- (2.2-
Dichloro) vinyl phosphate, 0-isopropoxyphenylmethyl carbamate, 0.0-dimethyl 0-
(3-methyl-4-nitrophenyl) thionophosphate, 0.0-diethyl 0-2-isopropyl-4-
Methyl-pyrimidyl- (6) -thiophosphate, 0
0-dimethyl S- (1.2-dicarbethoxyethyl) -dithiophosphate, benzylbenzoate and the like, and the synergistic agent is 6- (propylpiperonyl)-
Butyl carbyl ether, N- (2-ethylhexyl) -1-isopropyl-4-methylbicyclo (2,2,
2) Oct-5-ene-2,3-dicarboximide, isobornyl thiocyanoacetate, octachlorodipropyl ether and the like;
(Fluorodichloromethylthio) -phthalimide, N, N
-Dimethyl-N'-phenyl-N '-(fluorodichloromethylthio) sulfamide, 2,4,4'-trichloro-
Examples thereof include 2'-hydroxydiphenyl ether, 0-phenylphenol, P-chloro-m-xylenol, 4-chlorophenyl-3'-iodopropargyl, and formal.

The amount of the active ingredient in the acaricide of the present invention may be appropriately determined according to the dosage form, application method, application place, etc., but an aqueous solution, a wettable powder, an emulsion or a coating agent, a powder, a granule may be used. When used in the form of an agent or the like, the active ingredient is preferably 0.1 to 35% by weight, and when used in the form of a spray, smoke, oil or aerosol, the active ingredient is preferably 0.1 to 10% by weight, its dose is about the active ingredient in an area 1 m ² per be processed 10m
g or more, it is desirable to present the active ingredient from about 1mg or more per application space 1 m ^2.

The present invention also provides a tick control material comprising the above-mentioned acaricide held on a substrate. The tick control material,
Utilizing the characteristics of the base material, it is used as a film, a sheet, a cushion, a filler for beddings, a building / construction material, etc., which have mite control properties. Here, examples of the base material include synthetic resin sheets such as polyethylene, polypropylene, nylon, polyvinyl chloride, polyvinylidene chloride, and polyester, animal and plant or inorganic fiber sheets (paper, cloth, nonwoven fabric, leather, etc.), and these synthetic resins. Examples thereof include a mixed sheet or mixed fabric of inorganic fibers or powder, a mixed fabric or nonwoven fabric of the synthetic resin and animal and plant fibers, a metal foil or film of aluminum, stainless steel, zinc, or the like, and a laminated sheet of the above various sheets. As cushions and bedding fillers, natural cotton (cotton, cotton, etc.), synthetic fiber cotton (polyester cotton, nylon cotton, acrylic cotton, etc.), feathers and other animal hair, buckwheat hull, rice hull, grain straw, foam plastic (Polyethylene foam, urethane foam, etc.). Further, as the base material, natural woods such as drills, pencil ferns, cousins, etc. and plastics such as vinyl chloride resin, chlorinated polyethylene, polyethylene, etc.
Molded products such as polypropylene can also be used effectively. Means for holding the mite control agent of the present invention on these substrates is not particularly limited, and may be performed by, for example, application, impregnation, dropping, spraying, kneading, or the like. The retention amount is not particularly limited and can be appropriately determined. However, in the case where the substrate is impregnated, the amount is preferably up to the saturated impregnation amount.

As a preferred embodiment of the mite control agent of the present invention,
A tick control carpet can be exemplified. The mite control carpet according to the present invention has a liquid form in which a normal carpet comprising, for example, a pile, a first base fabric, a backing agent, and a second base fabric is prepared, and a film-forming agent is added as necessary. Spray the agent or prior to making the carpet,
At least one of a pile, a first base cloth and a second base cloth
It is obtained by treating a seed with the acaricide of the present invention and using them to make a carpet.

The mite control carpet prepared as described above desirably holds about 0.1 to 10 g of the active ingredient per 1 m ² of carpet area. As another embodiment, a tick control futon and a pillow can be exemplified. The mite control duvet and pillow are made of natural cotton, synthetic fiber cotton, feathers and other animal hair, buckwheat husk, rice hull,
It can be obtained by spray-coating the acaricide of the present invention onto a filler such as cereal straw or foamed plastic. The mite control futon prepared as described above may hold about 0.1 to 10 g of the active ingredient per 1 kg of the filler weight.

(Operation)

The acaricide and the acaricide of the present invention exhibit extremely excellent effects based on the fact that they contain the quaternary ammonium salt represented by the general formula as an active ingredient.

〔Example〕

Hereinafter, the present invention will be described in more detail with reference to examples.

Example 1 Efficacy against Dermatophagoides farinae A nonwoven fabric (made of polypropylene, 230 μm in thickness) is cut into a size of 5 × 5 cm, and impregnated with an acetone solution of a test compound to a predetermined concentration. After removing the solvent, apply this impregnated paper to about 30
Put it in a polyethylene bag (6 × 6 cm) together with 0 test mites, and make it close to all sides. After 48 hours, life and death were determined under a stereoscopic microscope. The results were obtained as mortality (%) by Abbott correction of the following formula, and are shown in Table 1.

x; Percentage of surviving insects in untreated plot y; Percentage of surviving insects in treated plot The acaricide of the present invention showed a higher effect than resmethrin.

Example 2 Efficacy Against Acarina mites The same procedure as in Example 1 was followed to determine survival or death 24 hours later. The results were determined by the mortality (%) by Abbott correction as in Example 1, and are shown in Table 2.

The acaricide of the present invention showed a higher effect than resmethrin.

Example 3 For the purpose of controlling insects on carpets, specifications No. B and
D, F to G, and I to L produced carpet-shaped mite control materials of the present invention.

Mite control carpet sample No.B obtained above,
The following tests were performed for D, FG, and IL.

<Test Method> In the center of carpet samples No. B, D, FG, IL, and drug-untreated carpet (each 20 × 20 cm),
A mite culture medium containing about 10,000 Dermatophagoides farinae was placed and placed in the bottom of a container (41 x 31 x 22 cm).
After storage for 2 days under the condition of% RH, 200 mesh
The mite on the front or back of the carpet was sucked off with a vacuum cleaner sandwiching two nylon gows. Next, remove the nylon goose from the vacuum cleaner, brush off the mites into a 300 ml beaker containing 100 ml of Darling solution, and transfer to a centrifuge tube after stirring.
After centrifugation at rpm, the supernatant is transferred to a Buchner funnel on which a lip is placed and passed through a suction port. Surviving mites on this paper were counted, and the result was obtained as the mortality (%) from the following equation.

x: Number of surviving mites in the carpet untreated with drug y; Number of surviving mites in the mite-controlling carpet plot The above test was repeated three times, and the results are shown in Table 4 as average values.

As shown in Table 4 above, each sample showed sufficient mite control.

Example 4. No. B, D, FG, I to
To 10 g of each L, add a trace amount of fragrance, 20 ml of ethyl alcohol, and further add distilled water to make a total of 150 ml, a mixture of liquefied petroleum gas and dimethyl ether (1: 1 volume ratio)
Was filled in a pressure-resistant can for aerosol (content: 400 ml), attached to an injection device, and sealed to obtain a tick control material of the present invention in the form of an aerosol.

Using each of the aerosols thus obtained, the mite control effect was tested in the same manner as in Example 1.

<Test method> Spray each aerosol on a high-quality paper (30 x 30 cm) for 3 seconds so as to be as uniform as possible. After storing at room temperature for 1 day,
A sheet having a size of 5 × 5 cm was cut out, and the mite control effect was tested according to the test method of Example 1 below.

The above test was repeated three times, and the results are shown in Table 5 as average values.

As shown in Table 5 above, each sample showed sufficient mite control.

Example 5. Nos. B to C and E to of the sample containing the test compound shown in Table 6 below
G was sprayed onto futon cotton so that the test compound became 1 g / kg cotton, and then dried to obtain a tick controlling material of the present invention.

No. B, D ~
The following test was performed for G.

<Testing Method> 1 g of each of the futon cotton samples Nos. A to E is placed in a sample tube (30 ml), and about 500 Dermatophagoides farinae are placed in the tube and covered with the lid, and placed at 25 ° C. After 48 hours, cotton was taken out of the sample tube, and live mites were collected by a heat expulsion method, and the insect repellency (%) was determined by the following equation.

x: Percentage of collected mites in the untreated area y; Percentage of collected mites in the treated area As a result, all the samples were able to obtain almost 100% insect repellency and showed sufficient mite control.

Example 6 The test composition of the present invention used in Example 4 was mixed with the same weight of silicon oxide, sufficiently stirred and mixed, and then powdered to obtain a powdered mite control material of the present invention.

The powder thus obtained was tested for its mite control effect by the following test method.

<Test method> After heat-killing a straw cut to a length of about 2 cm, put 5 g of the straw in a 100 ml Erlenmeyer flask, then add and mix 0.05 g of each powder and mix at 25 ° C and 85 to 90% RH. Save for one day. Approximately 400 mites were placed in the Erlenmeyer flask, and after storage for 2 days under the same conditions, living mites were expelled by a heat expulsion method, the number was counted, and the mortality was determined according to the test method of Example 3. Calculated.

As a result, all powders were able to obtain almost 100% mortality and showed sufficient mite control.

Example 7 A cleaner paper pack was impregnated with a test compound acetone solution shown in Table 7 below and dried to obtain a tick control material of the present invention.

Sample packs No.B and D for mites control paper pack obtained above
The following tests were performed on F to IL.

<Test method> As shown in Table 8 above, each sample showed sufficient mite control.

〔The invention's effect〕

Since the acaricide of the present invention is low-toxic and safe for the human body, it can be used for rugs such as tatami mats and carpets, furniture such as sofas and closets, bedding such as futons and beds, and toys such as stuffed toys. Can be used safely even in places where they frequently come in contact, and the target mites are airless ticks, especially to the house dust mites such as Dermatophagoides pteronyssinus and Dermatophagoides pteronyssinus; It is valid.

Claims (2)

(57) [Claims] (1) General formula (Wherein R ₁ is C _m H _n , m = 8-18, n = 17-37,
R ₂ Or a _{C m H n, m = 8~18} , a n = seventeen to thirty-seven. Provided that one or both of C _m H _n of R ₁ and R ₂ are Wherein R ₃ is an alkyl or alkenyl group having ₄ to 14 carbon atoms, and R ₄ is an alkyl or alkenyl group having 2 to 14 carbon atoms. ) A miticide for acarid mites, which comprises a quaternary ammonium salt represented by the formula (1) as an active ingredient. 2. The general formula (Wherein R ₁ is C _m H _n , m = 8-18, n = 17-37,
R ₂ Or a _{C m H n, m = 8~18} , a n = seventeen to thirty-seven. Provided that one or both of C _m H _n of R ₁ and R ₂ are Wherein R ₃ is an alkyl or alkenyl group having ₄ to 14 carbon atoms, and R ₄ is an alkyl or alkenyl group having 2 to 14 carbon atoms. ) An airless phytoseiid mite control material comprising a substrate, on which an acaricide for airless ticks containing a quaternary ammonium salt represented by the formula (1) is retained.