JPH0161081B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a new pest repellent. BACKGROUND ART Conventionally, methods for controlling various sanitary pests such as cockroaches include, for example, 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-meta-toluamide, 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 was found that bis(2,3,3,3-tetrachloropropyl) ether 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 relates to a pest repellent composition characterized by containing bis(2,3,3,3-tetrachloropropyl)ether as an active ingredient. The pest repellent composition of the present invention has extremely excellent properties based on the fact that it contains bis(2,3,3,3-tetrachloropropyl) ether (hereinafter referred to as "SA") as its active ingredient. It can have a pest repellent effect. Its repellent effects include not only sanitary pests and blood-sucking pests such as cockroaches, flies, mosquitoes, horseflies, and bed bugs, but also clothing pests such as burrs and carp moths, grain storage pests such as brown weevils, and ants, termites, 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 entryways, kitchens, dining rooms, livestock sheds, agricultural and gardening houses, etc., in storage furniture such as chests of drawers, food storage cabinets, clothing cases, doll cases, etc.
By applying it to the human body, animal body, plant body, etc., it can prevent pests from flying into, approaching, coming into contact with, etc.
Invasion, etc. can be reliably prevented, and inhabitation of pests, feeding damage, etc., bites, blood sucking, etc. of animals and plants, and further contamination within the above-mentioned specific area can be effectively avoided. In particular, the active ingredient compound of the pest repellent composition of the present invention, unlike N,N-diethyl-meta-toluamide, which is currently frequently used, does not have a specific odor or an unpleasant odor, and is light-emitting. It is stable against temperatures and temperatures, and there is no risk of coloring, so it is suitable for direct application to the human body or around the human body, and does not cause any discomfort at all. In the pest repellent composition 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 an appropriate carrier or other compounding agents to determine the application area and application method. It is prepared and used in various forms suitable for use, such as liquids and solids. Examples of carriers used in preparing liquid preparations include 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 benzene. Examples include aliphatic hydrocarbons, aromatic hydrocarbons such as benzene and toluene, esters such as ethyl acetate, and halogenated hydrocarbons such as dichloroethane. The pest repellent of the present invention in the form of a liquid may further contain conventional film forming agents, emulsifiers, dispersants, spreading agents, wetting agents,
Additives such as stabilizers and propellants can be added, and the product can be used in the form of paints, adhesives, emulsions, dispersants, suspensions, lotions, creams, sprays, aerosols, etc. . Examples of such additives include cellulose derivatives such as nitrocellulose, acetylcellulose, acetylbutyrylcellulose, and methylcellulose, vinyl resins such as vinyl acetate resin, alkyd resins, ethylene vinyl acetate resins, urea resins, and epoxy resins. Resins, 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 Polyoxyethylene alkyl allyl ether such as nonyl phenyl ether, polyoxyethylene fatty acid ester, fatty acid glyceride,
Examples include surfactants such as sorbitan fatty acid esters, 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. can. 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,
It is also possible to form a sublimable solid agent by melt-mixing or grinding the above-mentioned active ingredient compounds using a sublimable carrier such as trimethylene norbornene, or a sublimable insect repellent such as paradichlorobenzene, naphthalene, or camphor. In addition, the pest repellent composition of the present invention can be microencapsulated by, for example, a spray drying 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 a form. Furthermore, the pest repellent composition of the present invention includes known pest repellents, efficacy enhancers, antioxidants, decomposition inhibitors, insecticides, rodent control and repellents, bactericides, fungicides, Herbicides, fertilizers, flavoring agents, coloring agents, etc. can be added. Other pest repellents that can be blended include N,N-diethyl-meth-toluamide (hereinafter referred to as AH), 2,3,4,5-bis(Δ ₂ -butylene)-tetrahydrofurfural (hereinafter referred to as AG), Di-n-propyl isocincomeronate (hereinafter referred to as AC), di-n-butyl succinate (hereinafter referred to as AD), 2-hydroxyethyloctylsulfide (hereinafter referred to as AE),
2-t-butyl-4-hydroxyanisole (hereinafter referred to as AA), 3-t-butyl-4-hydroxyanisole (hereinafter referred to as AB), 1-ethynyl-2-methyl-2-pentenyl 2,2,3,3 ―
tetramethylcyclopropane carboxylate,
1-ethynyl-2-methyl-2-pentenyl 2,
2-dimethyl-3-(2',2'-dichlorvinyl)
-Cyclopropane-1-carboxylate, 1-
Ethynyl-2-methyl-2-pentenyl 2,2-
dimethyl-3-(2'-methyl-1'-propipenyl)-cyclopropane-1-carboxylate,
Examples include N-hexyl-3,4-dichloromaleimide (hereinafter referred to as AF). In addition, the potency enhancers include N-(2-ethylhexyl)-bicyclo-[2,2,1]-5-heptene-2,3-dicarboximide, 6-(propylpiperonyl)-
Butylcarbitylethyl, N-(2-ethylhexyl)-1-isopropyl-4-methylbicyclo[2,2,2]oct-5-ene-2,3-dicarboximide, etc. are used as antioxidants. Butylated hydroxyanisole, dibutylated hydroxytoluene, tocopherol, γ-oryzanol, etc., phenyl glycidyl ether, etc. as a decomposition inhibitor, and pyrethroids such as the common name allethrin and its geometric and/or optical isomers as insecticides. α-naphthylthiourea, cycloheximide, etc. are used as rodent extermination and repellents, and salicylic acid, benzoic acid, sorbic acid, p-chloro-m-xylenol, 2-(4′-) are used as antibacterial and fungicidal agents.
Thiazoyl) benzimidazole, etc., and antifungal agents such as α-bromocinnamic aldehyde and N-
Examples include dimethyl-N-phenyl-N'-(fluorodichloromethyl)thiosulfamide. The pest repellent composition of the present invention having various forms thus prepared can be used in areas infested by pests where a repellent effect is required, such as agricultural fields,
By placing, scattering, spraying, coating, pasting, etc. on orchards, general households, grain warehouses, cafeteria kitchens, storage furniture, closets, entrances, washrooms, etc., and on animals and plants themselves. It can be applied by The amount of the active ingredient compound in the pest repellent composition of the present invention and the application amount of the repellent are determined by its dosage form, application method,
It may be determined as appropriate depending on the place of application, etc., and although it is not limited, usually when used in the form of a liquid such as a dispersant or a wettable powder, the active ingredient compound is 1 to 80% by weight.
Preferably, the content may be 5 to 40% by weight, and when it is in the form of a solid agent such as a powder, the content may be 1 to 50% by weight, preferably 2 to 20% by weight. In this case, the area to be coated is 1cm ²
It is preferable that the active ingredient compound be present in an amount of about 0.001 mg or more, preferably about 0.001 to 0.05 mg, and when used in solid form or other forms, it is appropriate that the active ingredient compound be present in an amount of about 1 mg or more per 1 m ³ of application space. be. The pest repellent composition of the present invention can also be used in the form of a pest repellent by holding it on a substrate. The pest repellent material is used as a film or sheet, a furniture member, etc. that has pest repellent properties by utilizing the characteristics of the base material. Here, examples of base materials include polyethylene, polypropylene, nylon,
Synthetic resin sheets such as polyvinyl chloride, polyvinylidene chloride, polyester, etc., animal/plant or inorganic fiber sheets (paper, cloth, non-woven fabric, leather, etc.), mixed sheets or blended fabrics of synthetic resins and inorganic fibers or powders. Examples include blended fabrics or nonwoven fabrics of the synthetic resins and animal and plant fibers, foils or films of metals such as aluminum, stainless steel, and zinc, and laminated sheets of the various sheets listed above. Further, as the base material, natural wood such as awn, pencil fern, oak, etc., and molded products of plastic such as vinyl chloride resin, chlorinated polyethylene, polyethylene, polypropylene, etc., which are used as furniture members, can also be effectively used. The means for retaining the pest repellent composition of the present invention on the substrate is as follows:
There are no particular limitations, and it may be carried out, for example, by coating, impregnating, dropping, kneading, etc. The amount retained is also not particularly limited and can be determined as appropriate; however, when impregnating furniture members etc., it is preferable to set the amount up to the saturated impregnated amount. A preferred embodiment of the pest repellent material is a pest repellent carpet. The pest repellent carpet is made by preparing, for example, a conventional carpet consisting of a pile, a first base fabric, a backing agent, and a second base fabric, and then applying the pest repellent composition of the present invention in a liquid form to the front and/or back surfaces of the carpet. Prior to the preparation of the above-mentioned carpet, the pest repellent composition of the present invention is kneaded into at least one of the pile, the first base fabric, and the second base fabric, and the carpet is prepared using the above method. Alternatively, it can be obtained by mixing the pest repellent composition of the present invention into a backing agent and using the same to prepare a carpet according to a pre-coat method or a jute bag method. In the above, the pre-coat method means that a backing agent is applied in advance to fix the pile to the first base fabric.
This is a method in which a backing agent is further applied to this treated area and a second base fabric is bonded to the treated area. The jute bag method refers to a method in which a backing agent is applied to a first base fabric into which pile is woven, and a second base fabric is bonded to the first base fabric. The pest repellent carpet prepared as described above usually preferably contains about 5 to 200 g of the active ingredient compound per square meter of the carpet, so that the desired effect can be sufficiently achieved. Examples will be given below to explain the present invention in more detail. Example 1 A paper (5 x 10 cm) was impregnated with a predetermined amount of the test compound, and this was paired with a paper not impregnated with the test compound, and one sugar cube was placed on each of the papers, and a sugar cube was placed on each paper.
Arrange them in a siere (30 cm in diameter) containing 200 fish, and place 10
After standing for 1 minute, 1 hour, and 6 hours, the number of ants on each paper was counted, and the repellent effect of the test compound was determined according to the following formula, based on the number on the non-impregnated paper. 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 The obtained results were judged according to the following criteria and shown in Table 1 below. Shown below. ＋＋＋…Repellent effect 90% or more ++ … 〃 70-90% + … 〃 50-70% ± … Repellent effect 30-50% − … 〃 Less than 30%

【table】

[Table] Example 2 A paper similar to that used in Example 1 was prepared and its repellent effect on woolly mites was investigated.
That is, cardboard paper (6 x 6 cm) was placed on top of about 1 g of mite-saturated medium placed in a shear dish (diameter 11 cm), and on top of this, black wood-free paper (6 x 6 cm) and supporting paper (5 x 5 cm) were placed. , black high-quality paper (4 x 4 cm) was stacked one after another and left at 25°C and 80% RH. After 24 and 48 hours, count the number of mites on the top black quality paper. In addition, the number of mites on a blank with untreated paper was counted to determine the repellent effect. Repellent effect (%) = Number of mites on untreated paper (number of mites) - Number of mites on test paper (number of mites) / Number of mites on untreated paper (number of mites) x 100 Based on the same criteria as Table 1, the obtained results were calculated according to the following table. It is shown in Table 2.

【table】

[Table] Example 3 A pure wool cloth (muslin cloth 10 x 10 cm) was impregnated with the test compound as shown in Table 3 below, and this was paired with a non-impregnated cloth and placed in a 30 cm diameter cloth containing 30 carp moth larvae. After placing them side by side in a shear dish and leaving them for 7 or 14 days, the degree of feeding damage on each fabric is examined, and the repellent effect of the impregnated fabric is calculated using the following formula based on the amount of feeding damage on the non-impregnated fabric. Repellent effect (%) = Blank fabric feeding damage amount (mg) - Test fabric feeding damage amount (mg) / Blank fabric feeding damage amount (mg) x 100 The results were evaluated in the following 3 table using the same criteria as Table 1.
Shown in the table.

【table】

[Table] Example 4 One sugar cube was placed in the center of each of a circular paper (diameter 11 cm) impregnated with the test compound and an untreated paper, and each pair was reared for 25 male and female adult German cockroaches. After arranging the paper sugar cubes so as not to overlap them and leaving them for 12 or 24 hours, the amount of weight loss (feeding damage) of each paper sugar cube was measured and the repellent effect was calculated using the following formula. Repellent effect (%) = Amount of feeding damage in the blank plot (mg) - Amount of feeding damage in the test plot (mg) / Amount of feeding damage in the blank plot (mg) x 100 The results are shown in Table 4 below, similar to Table 1.

[Table] Example 5 Add odorless kerosene to 5g of the test compound to make a total of 100g
A pest repellent in the form of a soybean oil is produced.
The effectiveness of the thus obtained oil agent was determined by the following method using odorless kerosene as a control. That is, each oil was applied to each of the five inner walls of a plywood box (inner dimensions 20 x 30 x 4 cm) with an entrance of 4 x 30 cm in an amount that would give a test compound amount of approximately 2 mg/cm ² (this amount was applied to the control oil). Each box was left in a case housing 400 German cockroaches for 6 or 12 hours, and the number of German cockroaches invading the box was determined. Count. Based on the obtained results, the repellent effect of each oil agent was judged according to the following criteria. +++...Very effective when the number of residents is 0++... 〃 Quite effective when 1 to 4 animals live + ... 〃 Effective when 5 to 9 animals live - ... 〃 Ineffective when there are 10 or more animals The results are shown in Table 5 below.

【table】

[Table] Example 6 A paulownia wood board (15 x 150 x 2 cm) was immersed in a solution in which the test compound was added to dichloromethane at a concentration of 15%, and the above solution was applied to the board by applying pressure at 15 kg/cm ² . was impregnated to make insect repellent wood, and this was used to manufacture pest repellent material in the form of a furniture drawer (115 x 42 x 15 cm).
The resulting drawer was used to test its effectiveness against burs. i.e. about 80% of the clothes normally used in the drawer.
A nylon bag containing 10 35-day-old burr larvae is placed in each of the upper, middle, and lower parts of the divided and stacked clothes, and after 2 weeks and 1 month, the insect repellent effect is evaluated according to the following criteria. was determined. +++...100% lethal++...80-99% lethal+...50-79% lethal-...Less than 50% lethal The results are shown in Table 6.

【table】

[Table] Example 7 The surface of a carpet cut to 10 x 5 cm (commercially available product that has not been treated with insect repellent) is treated by spraying 3 ml of an acetone solution of the test compound (dose amount: 0.6 g/m ² ). This treated carpet and an untreated carpet of the same size are joined together along the long sides without gaps, and a plastic cylinder is placed on top of them. Separately, prepare a small 3 cm diameter sieve containing 30 worker ants and place it face down on an untreated carpet. After leaving it for a while to stabilize the ant activity, the shear was removed and the repellent effect was determined by observing the number of ants that invaded the treated carpet over time. The results are shown in Table 7.

[Table] Example 8 For the purpose of insect-proofing carpets, pest repellents of the present invention in the form of carpets were prepared according to specifications Nos. A to N in Table 8 below.

【table】

[Table] Pest repellent carpet sample No. obtained above.
The following tests were conducted for A to N. <Test method 1> Ant repellent test 50 Ants were released in a 16 x 22 x 8 cm vat, and a sample cut into 5 x 5 cm pieces and 2 pieces of blank carpet were placed at the bottom of the vat alternately in each corner for a total of 4 ants. After installing the sheets, place a small piece of absorbent cotton soaked in 5% sugar water on the carpet, count the number of ants gathered on the carpet, and calculate the repellency rate using the following formula. Repellency rate (%) = Number of ants on blank - Number of ants on sample / Number of ants on blank x 100 <Test method 2> Woolly moth mite repellency test Cardboard paper (6
x 6 cm), black wood-free paper (6 x 6 cm), carpet sample (5 x 5 cm), and black wood-free paper (4 x 4 cm). After 48 hours, remove the black wood-free paper on the carpet, the black wood-free paper, and the black wood-free paper under the carpet (center 4).
Count the number of mites (within 4 cm) and calculate the repellency rate using the same method as for ants. <Test method 3> Ceramic cockroach repellent test Place 1 cube of pre-weighed sugar in the center of a carpet sample (15 x 15 cm), pair it with a blank carpet set in the same way, and place 25 male and female adult German cockroaches each. Bat with head (35×40×23
cm) Arrange the sugar cubes so that they do not overlap on the bottom and leave them for 2 days. Measure the amount of sugar cubes remaining on each carpet and calculate the amount of reduction. The repellency rate is determined from the amount of each reduction using the same method as for ants. Each test was repeated three times, and the average values of the results obtained are shown in Table 9 below.

[Table] In addition, pest repellent carpet sample J obtained above
Regarding M and M, the antifungal efficacy of the antibacterial and antifungal agent mixed into each sample was also tested as follows. That is, Aspergillus niger (Asp. niger).
10 ⁶ spore suspensions/ml of P. citrinum (ATCC 9642) and P. citrinum (P. citrinum ATCC 9849)
2 ml of each spore suspension of ¹⁰⁶ spores/ml was placed on a tatami surface (10×
10 cm), place a carpet sample (5 x 5 cm) on top of the tatami surface and leave it at 25℃ for one week.
It was maintained under conditions of RH70%. After holding, it was observed whether mold was growing on the tatami surface under the sample, and the anti-mold effect of each sample was judged according to the following criteria. +...Mold generation -...No mold observed As a result, a positive rating was obtained for the blank, but a negative rating was obtained for both carpet samples J and M. Example 9 To 10 g of each of the test compounds of the present invention used in Example 5 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 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 5, and results equivalent to those shown in Table 5 were obtained. Example 10 5 of each of the test compounds of the present invention used in Example 5
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 5, and the same results as those listed in Table 5 were obtained. Example 11 5 of each of the test compounds of the present invention used in Example 5
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 5. When the sample was subjected to the same procedure, results almost the same as those shown in Table 5 were obtained. Example 12 3 parts by weight of the test compound of the present invention used in Example 5, 1 part by weight of silicon oxide, and 96 parts by weight of cyclododecane were sufficiently ground and mixed, and then the mixture was placed under a pressure of 300 kg/cm 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 plywood boxes as described in Example 5, 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 5 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
When the bag was placed in a plywood box in the same manner as in Example 5 and subjected to the same repellent effect test, almost the same results were obtained. Example 14 6 parts by weight of the test compound of the present invention used in Example 5 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/cm 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 5 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)

[Scope of Claims] 1. An insect repellent composition characterized by containing bis(2,3,3,3-tetrachloropropyl)ether as an active ingredient. 2. The pest repellent composition according to claim 1, which is used in the form of being held on a substrate.