JPS6228923B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a new pest repellent. Conventionally, methods for exterminating various sanitary pests such as cockroaches include methods of spraying insecticides such as pyrethroid insecticides and methods of using various insect traps. These methods kill pests by killing or trapping insects, and can prevent damage such as feeding damage and blood sucking caused by the pests to a certain extent, but they do not apply to the inside of furniture such as kitchens, livestock sheds, water sheds, chests of drawers, etc. It is not possible to avoid the flying, approaching, contact, invasion, contamination, etc. of pests to the human body, agricultural crops, and other animals and plants, and a sufficient exterminating effect cannot be achieved. Moreover, in the above method, it is necessary to dispose of pests after killing or capturing them, and it is particularly difficult to dispose of pests that die after entering furniture, etc., and this has the disadvantage of becoming a source of contamination. On the other hand, a method using a pest repellent is known as a pest extermination method that can prevent the above pests from flying or entering, and of course does not require any treatment of dead insects. Research and development and proposals are being made on various substances that have the same properties. However, none of the various substances proposed above can exhibit a sufficiently satisfactory pest repellent effect, and only a few substances, including N,N-diethyl-mettatoluamide, can be used as sprays, It is only used as a repellent for blood-sucking pests such as mosquitoes, fleas, bed bugs, and stable flies in the form of lotions and creams. In view of the above-mentioned current situation, the present inventors have conducted various studies with the aim of providing a repellent that exhibits an excellent pest repellent effect and can almost certainly prevent the invasion of pests. As a result, it has been found that a specific thiocyanate compound represented by the following general formula [] can exhibit pest repellent effects that meet the above objectives. The present invention was completed based on this new knowledge. That is, the present invention is based on the general formula 〓〓〓〓
[In the formula, n represents an integer of 2 to 7. ] This invention relates to an insect repellent characterized by containing a compound represented by the following as an active ingredient. The pest repellent of the present invention can exhibit extremely excellent pest repellent effects because it contains the specific thiocyanate compound represented by the above general formula [] as its active ingredient. Its repellent effects include not only sanitary pests and blood-sucking pests such as cockroaches, flies, mosquitoes, horseflies, fleas, and bed bugs, but also clothing pests such as burrs and carp moths, grain storage pests such as brown weevils, and even ants and slugs. It is also powerful against the like. Therefore, the pest repellent of the present invention can be used in specific areas of the home such as entrances, kitchens, dining rooms, livestock sheds, agricultural and gardening houses, inside storage furniture such as chests of drawers, food storages, clothing cases, doll cases, etc. By applying it to the human body, animal body, plant body, etc., it can reliably prevent pests from flying, approaching, contacting, or invading such places, and can also prevent pests from living in the specified areas, etc. Feeding damage and bites of animals and plants,
Blood-sucking and even contamination can be successfully avoided. The thiocyanate represented by the above general formula [] used as an active ingredient in the pest repellent of the present invention is a known compound, and specifically includes the following compounds. 2-Phenoxyethylthiocyanate, 3-
Phenoxypropylthiocyanate, 4-phenoxybutylthiocyanate, 5-phenoxypentylthiocyanate, 6-phenoxyhexylthiocyanate, 7-phenoxyheptylthiocyanate. Among these, 2-phenoxyethylthiocyanate, 3-phenoxypropylthiocyanate and 4-phenoxybutylthiocyanate are particularly preferred. In the pest repellent of the present invention, the above-mentioned active ingredient compound can be applied as it is to areas where pest repellency is required, but it is usually preferable to use a suitable carrier or other compounding agent to adjust the application area, application method, etc. It is prepared and used in various suitable forms, such as liquids and solids. Examples of carriers used in preparing liquid preparations include water, alcohols such as methyl alcohol and ethyl alcohol, ketones such as acetone and methyl ethyl ketone, ethers such as tetrahydrofuran and dioxane, hexane, kerosene, paraffin, and petroleum benzine. Examples include aliphatic hydrocarbons such as benzene and toluene, aromatic hydrocarbons such as benzene and toluene, esters such as ethyl acetate, and halogenated hydrocarbons such as dichloroethane. The insect repellent of the present invention in the form of a liquid may further contain conventional additives such as film forming agents, emulsifiers, dispersants, spreading agents, wetting agents, stabilizers, propellants, etc.
Paint form, adhesive form, emulsion, dispersant, suspending agent,
It can be used in the form of lotion, cream, spray, aerosol, etc. Examples of such additives include cellulose derivatives such as nitrocellulose, acetylcellulose, acetylbutyrylcellulose, and methylcellulose, vinyl resins such as vinyl acetate resin, alkyd resins, urea resins, epoxy resins, and polyester resins. , urethane resins, silicone resins, acrylic resins, chlorinated rubber, coating film forming agents such as polyvinyl alcohol, soaps, polyoxyethylene fatty alcohol ethers such as polyoxyethylene oleyl ether, polyoxyethylene nonyl phenyl ether, etc. polyoxyethylene alkyl allyl ether, polyoxyethylene fatty acid ester,
fatty acid glyceride, sorbitan fatty acid ester,
Examples include surfactants such as sulfuric esters of higher alcohols, alkylaryl sulfonates such as sodium dodecylbenzenesulfonate, propellants such as liquefied petroleum gas, dimethyl ether, and fluorocarbons, casein, gelatin, alginic acid, and CMC. In addition, examples of carriers used for preparation in solid form include silicic acid, kaolin, activated carbon,
Examples include mineral powders such as bentonite, diatomaceous earth, talc, clay, calcium carbonate, and ceramic powder, vegetable powders such as wood flour, soybean flour, wheat flour, and starch, and clathrate compounds such as cyclodextrin. Furthermore, when preparing the solid agent form, for example, tricyclodecane, cyclododecane, 2,4,6-
triisopropyl-1,3,5-trioxane,
Using a sublimable carrier such as trimethylene norbornene or a sublimable insect repellent such as paradichlorobenzene, naphthalene, or camphor, the above active ingredient compounds are melt-mixed or mixed.
can also be molded after grinding and mixing to form a sublimable solid agent. The above-mentioned solid agent also includes the form of a resin molded product in which the active ingredient compound is kneaded into plastic. In addition, the pest repellent of the present invention can be microencapsulated in the form of a spray dry method using polyvinyl alcohol, CMC, etc., an in-liquid curing method using gelatin, polyvinyl alcohol, alginic acid, etc., a coacelvation method, etc. It can also be prepared in the form of a gel using a gelling agent such as benzylidene-D-sorbitol or carrageenan. Furthermore, the pest repellent of the present invention includes known pest repellents, efficacy enhancers, antioxidants, insecticides, rodent control and repellents, fungicides, fungicides, herbicides, fertilizers, and flavoring agents. , colorants, etc. can be added.
Other pest repellents that can be blended include N,N-diethyl-meth-toluamide (hereinafter referred to as DET),
2,3,4,5-bis(Δ ₂ -butylene)-tetrahydrofurfural, di-n-propyl, isocincomeronate, di-n-butyl succinate, 2-hydroxyethyloctylsulfide, etc., to enhance their efficacy. Examples of agents include N-(2-ethylhexyl)-bicyclo-[2,2,1]-5-heptene-2,3-dicarboximide, 6-(propylpiperonyl)-butylcarbityl ether, etc. As preventive agents, butylated hydroxyanisole, dibutylated hydroxytoluene, tocopherol, γ-oryzanol, etc. are used, and as insecticides, pyrethroids such as the common name allethrin and its geometric and/or optical isomers are used for rodent extermination and repellency. As the agent, α-naphthylthiourea, cycloheximide, etc. are used, and as the fungicide, salicylic acid, p
-Chloro-m-xylenol, 2-(4'-thiazoyl)benzimidazole, etc., and anti-mold agents include α-bromosinnamic aldehyde, N-dimethyl-N-phenyl-N'-(fluorodichloromethyl)thiosulfamide, etc. can be exemplified. The pest repellent of the present invention in various forms thus prepared can be used in areas infested by pests where a repellent effect is required, such as crop cultivation fields, orchards, general households, grain warehouses, cafeteria kitchens, and furniture. It can be applied by placing, scattering, spraying, coating, pasting, etc. in closets, entrances, washrooms, etc., or by scattering, spraying, coating, etc. on animals and plants themselves. In addition, the insect repellent of the present invention can be applied to a suitable sheet-like base material in advance by applying it, impregnating it, dropping it, kneading it, etc., and then placing it on the desired location in the form that it is retained on the base material. It can also be used by pasting them together. Examples of sheet-like substrates used in this case include synthetic resin sheets such as polyethylene, polypropylene, nylon, polyvinyl chloride, polyvinylidene chloride, and polyester, animal and vegetable or inorganic fiber sheets (paper, cloth, nonwoven fabric, leather, etc.) , mixed sheets or blended fabrics of synthetic resins and inorganic fibers or powders, blended fabrics or nonwoven fabrics of the above synthetic resins and animal and plant fibers, aluminum,
Examples include metal foils or films such as stainless steel and zinc, and laminated sheets of the above various sheets. Furthermore, the pest repellent of the present invention can be applied, impregnated, dropped, or kneaded in advance to natural wood such as awn, pencil fern, and oak, or plastic such as vinyl chloride resin, chlorinated polyethylene, polyethylene, polypropylene, etc., to be used as furniture parts. It is also possible to use it by holding it by etc. The amount of the active ingredient compound in the pest repellent of the present invention and the amount applied of the repellent may be appropriately determined depending on the dosage form, application method, application location, etc., and are not limited to the above. When used in the form of a liquid such as a wettable powder, the active ingredient compound may be contained in an amount of 1 to 80% by weight, preferably 5 to 40% by weight, and preferably 1 to 50% by weight when used in the form of a solid such as a powder. is 2~
It is sufficient that the content is 20% by weight, and when it is held in a sheet-like base material or a furniture member, it is sufficient that the content is approximately 1/2 of the saturated impregnated amount of the base material, etc. In addition, the applied amount of the pest repellent of the present invention is, for example, in case of application, the amount of active ingredient compound per 1 cm ² of area to be applied is about 0.001 mg or more, preferably about 0.001 mg or more.
The amount is preferably 0.001 to 0.05 mg, and when used as a solid or other form, it is appropriate that the active ingredient compound is present in an amount of about 1 mg or more per 1 m ³ of application space. Examples will be given below to explain the present invention in more detail. Example 1 The repellent effect of each compound represented by the following general formula [] against German cockroaches was investigated by the following method. i.e. 0.05 of each test compound
Impregnate a circular paper (diameter 11 cm) with mg/ ^cm2 , and inside it
One sugar cube was placed in the center and in the center of a control paper not impregnated with any test compound, and each pair of these was
Arrange them so that they do not overlap in a breeding box in which 25 adult male and female German cockroaches are kept, and measure the weight loss (eating amount) (X mg) of each paper sugar cube after leaving it for 3 days. The repellent effect of each test compound is
It is calculated according to the following formula based on the reduced amount of sugar cubes (eaten amount) (Amg) on the control paper. Repellent effect (%) = A (mg) - X (mg) / A (mg) x 10
0 The results obtained were judged according to the following criteria and are shown in Table 1 below. ＋＋＋……Repellent effect 90% or more ++…… 〃 70-90% ＋…… 〃 50-70% ±…… 〃 30-50% −…… 〃 30% or less

[Table] From Table 1 above, the compounds represented by the general formula [ ] that are used as active ingredients in the present invention (test compound No.
It is clear that all of 1 to 6) have excellent repellent effects. Example 2 A pest repellent of the present invention in the form of a lotion having the following composition is manufactured using each of the above active ingredient compounds (Test Compounds No. 1, 2, and 5). Active ingredient compound 10g Propylene glycol 5g Isopropyl myristate 2g Purified water 15g Fragrance Trace amount of ethanol Amount to make the whole 100g A control lotion is produced in the same manner as above except that the above active ingredient compound is not blended. Furthermore, for comparison, a comparative lotion was prepared in the same manner as above using test compound No. b listed in Table 1 instead of the active ingredient compound. For comparison, a comparative lotion is prepared in the same manner using 2-thiocyanatoethanol (hereinafter referred to as "test compound A") as a test compound. For each of the obtained lotions, a test for repellency against adult female Culex pipiens was conducted as follows. That is, the lotion of the present invention or the comparison lotion was applied uniformly (1 ml) to one arm, and the control lotion was similarly applied to the other arm, and after 1 hour and 6 hours had elapsed, 20 adult female Culex pipiens were applied to each arm. Mosquitoes in each cage were placed in a cage containing a lotion and allowed to suck blood for 30 minutes, then the mosquitoes in each cage were anesthetized and crushed on paper, and blood sucking was determined by the number of bloodstains on the paper.The number of bloodstains when using a control lotion was used as the standard. , determine the repellent efficacy of each test lotion according to the formula below. Repellent effect (%) = (Number of bloodstains when using the control lotion) - (Number of bloodstains when using the test lotion) / (Number of bloodstains when using the control lotion) x 100 The obtained results are listed in Table 2 according to the following criteria. . ＋＋＋……Repellent effect 90% or more ＋＋…… 〃 70-90% ＋…… 〃 50-70% ±…… 〃 30-50% −…… 〃 30% or less〓〓〓〓

[Table] Example 3 The following test compound was applied to a pure wool cloth (10cm x 10cm).
Impregnated at a rate of 0.01 mg/cm ² , this was paired with an unimpregnated cloth and placed side by side in a 30 cm diameter shear containing 30 carp moth larvae, and after being left for 7 days, the degree of feeding damage on each cloth was examined. The repellent effect of each test compound is calculated using the following formula based on the amount of food consumed on unimpregnated cloth. Repellent effect (%) = Amount of consumption of control fabric (mg) - Amount of consumption of sample fabric (mg) / Amount of consumption of control fabric (mg) x 100 The obtained results are summarized in Table 3 below according to the same criteria as Table 1. Shown below.

[Table] Example 4 Each of the following test compounds was placed on a circular paper (5 cm in diameter).
Impregnated at a rate of 0.05mg/cm ² , pair this with non-impregnated paper, place one sugar cube on each, arrange them in a shear dish (diameter 30cm) containing 200 red-eared ants, and leave for 10 minutes. Count the number of ants on each paper,
Based on the number on non-impregnated paper, the repellent effect of each test compound is determined according to the following formula. Repellent effect (%) = Number of ants on non-impregnated paper (number of ants) - Number of ants on test paper (number of ants) / Number of ants on non-impregnated paper (number of ants) x 100 Based on the same criteria as in Table 1, the obtained results were calculated according to the following table. It is shown in Table 4.

[Table] Example 5 House fly bait was mixed with 0.1% of each of the following test compounds and 0.01% of an insecticide ("Sumithion", an organophosphorus insecticide manufactured by Sumitomo Chemical Co., Ltd.), or only the above insecticide, respectively. , etc. were placed separately in two breeding boxes containing 100 male and 100 male and female house flies, and after 1 hour, the number of attracted flies in each box was counted, and the results were compared with the poisoned bait containing only insecticide (control). As a standard,
The repellent effect of each test compound is calculated using the following formula. Repellent effect (%) = Number of control dead insects (heads) - Number of sample dead insects (heads) / Number of control dead insects (
head) x 100 The results obtained are shown in Table 5 below according to the same criteria as in Table 1.

[Table] Example 6 0.01 of each of the following test compounds on circular paper (diameter 5 cm)
mg/cm ² , make a pair of this and unimpregnated paper, place white rice in the center of each pair, arrange them in a siere (diameter 30 cm) containing 10 male and 10 male and female Coconut flora adults, and After standing for a period of time, count the number of brown fleas on each paper, and use the results on non-impregnated paper as the standard to prepare each sample in the same manner as in Example 4.
Calculate the repellent effect when using the compound. The results obtained are shown in Table 6 below.

[Table] Example 7 Using each of the test compounds listed in Table 7, an pest repellent of the present invention in the form of an oil having the composition shown below is produced. Active ingredient compound 5g Ethyl cellosolve 20g Odorless kerosene Amount to make the total amount 100g Similarly, in place of a control oil solution containing no active ingredient compound and an active ingredient compound, test compounds No. b and c listed in Table 1 above were used. Comparative fluids containing the following amounts are prepared. Each of the oils obtained in this way was
Spray and apply the test compound in an amount of approximately 3 mg/cm ² (an equivalent amount for the control oil) on each of the five inner walls of a cm plywood box (inner dimensions 20 x 30 x 4 cm).
Each box obtained is left overnight (12 hours) in a case housing 400 German cockroaches, and the number of German cockroaches that have invaded and resided in the box is counted. Based on the obtained results, the repellent effect of each oil agent was judged according to the following criteria. 0... Number of residents 0 +... 〃 1 to 4 animals ++... 〃 5 to 9 animals +++... 〃 10 or more animals The results are shown in Table 7 below.

【table】

[Table] Example 8 Using each of the test compounds listed in Table 7 above, a pest repellent of the present invention in the form of a formulation having the following composition is produced. Active ingredient compound 5g Polyoxyethylene oleyl ether (15 mol) 10g Water Amount to bring the total amount to 100g Similarly, in place of the control preparation containing no active ingredient compound and the active ingredient compound, test compound No. listed in Table 1 above was used. Comparative formulations containing the same amounts of each of b and c are prepared. A circular paper with a diameter of 15 cm is impregnated with 2 ml of these drops and air-dried to obtain a sample of the present invention, a control sample, and a comparative sample. Fifty slugs were released in a plywood box measuring 30 cm long x 40 cm wide x 20 cm high, and two sheets each of the above-mentioned inventive sample or comparison sample and control sample were placed side by side on the bottom of the plywood box. A plastic shear dish (diameter 5 cm x height 1 cm) containing vegetable scraps was placed on each sample, and the number of slugs on the vegetable scraps was counted on the first and third day of installation. As a result, the slugs did not approach the dish containing vegetable scraps placed on the sample of the present invention at all, and all slugs were present in the dish containing vegetable scraps placed on the control sample. It was clear that it had a slug repellent effect. Example 9 To 10 g of each of the test compounds of the present invention used in Example 7 above, a trace amount of fragrance, 20 ml of ethyl cellosolve, and an amount of odorless kerosene to bring the total to 150 ml were added, and this was mixed with a mixture of liquefied petroleum gas and dimethyl ether (50:
50 volume ratio) into an aerosol pressure-resistant can (content: 400 ml), which is attached to an injection device and sealed to obtain the pest repellent of the present invention in the form of an aerosol. Using each of the aerosols thus obtained, a repellent effect test against German cockroaches was conducted in the same manner as in Example 7, and the results were the same as those listed in Table 7〓〓〓〓
The results were obtained. Example 10 5 of each of the test compounds of the present invention used in Example 7
g, 25 g of nitrocellulose, 25 g of thinner and 2 g of dibutyl phthalate are mixed and dissolved to obtain the pest repellent of the present invention in the form of a paint. Using each of the paints thus obtained, a repellent effect test was conducted in the same manner as in Example 7, and results similar to those shown in Table 7 were obtained. Example 11 5 of each of the test compounds of the present invention used in Example 7
g and 5 g of N-(2-ethylhexyl)-bicyclo-[2,2,1]-5-heptene-2,3-dicarboximide as a potency enhancer were diluted in 1 part of n-hexane, and a nonwoven fabric (polyethylene-cotton (3:1 weight ratio), thickness 300 μ, area 1 m ² ),
After impregnation with 30g of the test compound, dry it.
A sheet-like pest repellent of the present invention is obtained. The obtained sheet was cut into a size that matched each of the five inner walls of a plywood box (inner dimensions 20 x 30 x 4 cm) with an entrance inner dimension of 4 cm x 30 cm, and then pasted, and a repellent effect test was conducted in the same manner as in Example 7. When subjected to the test, results almost equivalent to those shown in Table 7 were obtained. Example 12 3 parts by weight of the test compound of the present invention used in Example 7, 1 part by weight of silicon oxide, and 96 parts by weight of cyclododecane were thoroughly ground and mixed and then placed under a pressure of 300 kg/m ² .
The pest repellent of the present invention in tablet form is obtained by compressing into 10 g/tablet. The obtained tablets were placed in the plywood boxes described in Example 7, 2 tablets in each box, and the same repellent effect test was conducted, and almost the same results were obtained. Example 13 Each of the test compounds of the present invention used in Example 7 is sufficiently stirred and mixed with the same weight of silicon oxide, and then pulverized to obtain a powdered pest repellent of the present invention. Fill 3g of each of the obtained powders into cloth bags and
The bag was placed in a plywood box in the same manner as in Example 12 and subjected to the same repellent effect test, and almost the same results were obtained. Example 14 6 parts by weight of the test compound of the present invention used in Example 7 was added to 2,4,6-triisopropyl-1,3,5-
A paulownia wood board (15cm x 150cm x 2cm thick) was mixed with 94 parts by weight of trioxane and heated to about 90°C.
The pest repellent of the present invention in the form of pest repellent-retaining wood is obtained by soaking the wood and applying a pressure treatment at 15 kg/m ² to impregnate the wood with a liquid in an amount of about 25% of the weight of the wood. A box with the same dimensions as the box described in Example 7 was made using each of the obtained woods, and a similar pest repellent effect test was conducted on this box (active ingredient holding amount: approximately 15 g). Got the results. 〓〓〓〓

Claims (1)

[Claims] 1. General formula [In the formula, n represents an integer of 2 to 7. ] An insect repellent characterized by containing a compound represented by the following as an active ingredient.