JPH03157303A - Insect repellent composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition, containing bis(2,3,3,3- tetrachloropropyl)ether as an active ingredient, usable in a state thereof held in a substrate and suitable for application to peripheries of human bodies due to no peculiar smell thereof. CONSTITUTION:The subject composition containing bis(2,3,3,3-tetrachloropropyl) ether (SA) as an active ingredient. Since the SA has no peculiar or unpleasant smell and is stable to light and temperature without any fear of coloring, etc., the composition is suitable for direct application to human bodies or peripheries thereof. To put it concretely, the composition can be applied to entrances, kitchens, dining rooms, etc., barns or agricultural and horticultural greenhouses or housing furniture such as 'TANSU' (a chest of drawers), food housing cabinets or clothing cases and human, animal, plant bodies, etc., to avoid cockroaches, flies, mosquitoes, clothes moths, webbing clothes moths, rice weevils, terminals, etc. In the coating use, the amount applied is 0.001-0.05mg/cm<2> (amount of the active ingredient) and >=1mg/m<3> for a solid agent or other forms.

Description

[Detailed description of the invention] Industrial applications The present invention relates to a new insect 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 aim to kill pests by killing or trapping insects, and can prevent damage such as feeding damage and blood sucking caused by the pests to some extent, but they do not harm the inside of furniture such as kitchens, livestock sheds, water sheds, chests of drawers, etc., or the human body, It is not possible to avoid the flying, approaching, contact, invasion, contamination, etc. of pests to animals and plants such as agricultural crops, and it is not possible to achieve a sufficient extermination effect. 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, as a pest extermination method that can prevent the above-mentioned pests from flying or invading, and of course does not require any treatment for living or dead, there is a method using a pest repellent, and recently it has a pest repellent effect that can be used in the above method. Various substances are being researched, developed and proposed. 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.

Problems to be Solved by the Invention In view of the above-mentioned eye shape, the present inventors have developed various methods for the purpose of providing a repellent that exhibits an excellent repellent effect against insects and can almost certainly prevent their invasion. I did a lot of research. As a result, bis(2,3,3゜3-tetrachloropropyl)
It has been found that ether can exhibit a repellent effect that meets the above objectives.

The present invention was completed based on this new knowledge.

Means for Solving the Problems, that is, the present invention relates to an insect repellent composition characterized by containing bis(2,3,3,3-tetrachloropropyl)ether as an active ingredient.

The insect repellent composition of the present invention has bis(2,3,3,3-tetrachloropropyl)ether (
(hereinafter referred to as rsAJ), it can exhibit an extremely excellent insect repellent effect. Its repellent effects include not only sanitary pests and blood-sucking pests such as cockroaches, flies, flies, horseflies, and bed bugs, but also clothing pests such as burrs and carp moths, grain storage pests such as the white beetle and weevil, as well as ants and termites. It is also powerful against various insects. Therefore, the insect 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, inside storage furniture such as chests of drawers, food storage cabinets, clothing cases, doll cases, etc., and on the human body. By applying it to animals, plants, etc., it is possible to reliably prevent insects from flying, approaching, contacting, invading, etc. to these places, and also prevent insects from living in, feeding damage, etc. and animals and plants within the above-mentioned specified areas. You can easily avoid body bites, blood sucking, etc., as well as contamination. In particular, the active ingredient compounds of the insect repellent composition of the present invention include N, N, which is commonly used at present.
-Different from diethyl-meta-toluamide, etc., it does not have a specific or unpleasant odor, is stable against light and temperature, and has no risk of coloring, so it cannot be applied directly to the human body or It is suitable for application to the surrounding area and does not cause any discomfort.

In the insect repellent composition of the present invention, the above-mentioned active ingredient compound can be applied as it is to areas where insect repellency is required, but it is usually preferable to use an appropriate carrier or other compounding agent to determine the area and method of application. 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,
Examples include aliphatic hydrocarbons such as paraffin and petroleum benzine, 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 secondary solution further contains conventional film forming agents, emulsifiers, dispersants, spreading agents, wetting agents, stabilizers,
Additives such as propellants can be added, and the composition can be used in the form of paints, adhesives, emulsions, dispersants, suspensions, lotions, creams, sprays, aerosols, and the like. Examples of such additives include nitrocellulose, acetylcellulose, acetylbutyrylcellulose,
Cellulose derivatives such as methyl cellulose, vinyl resins such as vinyl acetate resin, alkyd resins, ethylene vinyl acetate resins, urea resins, epoxy 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 alkyl allyl ethers such as polyoxyethylene nonylphenyl ether, polyoxyethylene fatty acid esters, fatty acid glycerides , sorbitan fatty acid ester, higher alcohol ester sulfate, surfactants such as alkylaryl sulfonates such as sodium dodecylbenzenesulfonate, liquefied petroleum gas, dimethyl ether,
Examples include propellants such as fluorocarbon, casein, gelatin, alginic acid, and CMC.

In addition, examples of carriers used for preparation in solid form include silicic acid, kaolin, activated carbon, bentonite,
Examples include mineral powders such as 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, in preparing the solid form, for example, tricyclodecane, cyclododecane, 2,4.6-
Doliisoprobyl-1.3.5-1 After melt-mixing or shaking-mixing the above active ingredient compounds using a sublimable carrier such as rioxane or trimethylene norbornene or a sublimable insect repellent such as Balajichlorobenzene, naphthalene, or camphor, Mold and
It can also be a sublimable solid agent.

In addition, the insect repellent composition of the present invention can be microencapsulated according to a spray drying method using polyvinyl alcohol, CMC, etc., an in-liquid curing method using gelatin, polyvinyl alcohol, alginic acid, etc., a coacervation method, etc. It can also be prepared.

Furthermore, the insect repellent composition of the present invention may contain known pest repellents, efficacy enhancers, antioxidants, decomposition inhibitors, insecticides, rodent control and repellents, fungicides, fungicides, and herbicides. , fertilizer, flavoring agent, coloring agent, etc. can be added. Other pest repellents that can be blended include N,N-diethyl-meta-toluamide (hereinafter referred to as AH), 2,3.4.5-bis(Δ2-butylene)-tetrahydrofurfural (hereinafter referred to as AG), -n-propyl isocincomeronate (hereinafter referred to as AC), di-n-butyl succinate (
1
-ethynyl-2-methyl-2-pentenyl 2,3゜3
．． 3-tetramethylcyclopropanecarboxylate,
1-ethynyl-2-methyl-2-pentenyl 2.2-
Dimethyl-3-(2'2'-dichlorovinyl)-
Cyclopropane-1-carboxylate, 1-ethynyl-2-methyl-2-pentenyl 2,2-dimethyl-3
-(2'-Methyl-17-propenyl)-cyclopropane-1-carboxylate, N-hexyl-3,4-
Examples include dichlormaleimide (hereinafter referred to as AF).

Also, as a potency enhancer, N-(2-ethylhexyl)
-bicyclo-[2,2,1]-5-hebutene-2,3-
Dicarboximide, 6-(propylbiperonyl)-butylcarbityl ether, N-(2-ethylhexyl)
-1-isopropyl-4-methylbicycloC2,2,2
) oct-5-ene-2,3-dicarboximide, etc., butylhydroxyanisole,
Dibutylhydroxytoluene, tocopherol, γ-oryzanol, etc. are used as decomposition inhibitors, phenylglycidyl ether, etc. are used as insecticides, and as insecticides, pyrethroids such as the common name allethrin and its geometric and/or optical isomers are used. As animal control and repellents, α-naphthylthiourea, cycloheximide, etc. are used, and as antibacterial and fungicidal agents, salicylic acid, benzoic acid, sorbic acid, p-chloro-m-xylenol, 2-(4'-thiazoyl) ) benzimidazole, etc., and antifungal agents such as α-bromocinnamic aldehyde, N-dimethyl-N-phenyl-N
Examples include '-(fluorodichloromethyl)thiosulfamide and the like.

The insect repellent compositions of the present invention having various forms thus prepared can be used in areas infested with pests where a repellent effect is required, such as crop cultivation fields, orchards, general households, grain warehouses, and cafeterias. It can be applied to kitchens, storage furniture, closets, entrances, washrooms, etc. by placing, scattering, spraying, coating, pasting, etc., and it can also be applied to animals and plants themselves by scattering, spraying, coating, etc.

The amount of the active ingredient compound in the insect repellent composition 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, but usually dispersed When used in the form of a liquid agent such as a powder or 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 when used in the form of a solid agent such as a powder, 1 ~
The content may be 50% by weight, preferably 2 to 20% by weight. For example, in the case of application, the amount of the active ingredient compound is about 0.001 cm per ICllI2 area to be coated.
The above is preferably about 0.001 to 0.05 cm, and when used as a solid or other form, the applicable space is 1 m3.
It is suitable that about 1 inch or more of the active ingredient compound is present per serving.

The insect repellent composition of the present invention can also be used in the form of an insect repellent by holding it on a substrate.

The insect repellent material is used as a film or sheet, a furniture member, etc. that has insect repellent properties by utilizing the characteristics of its base material. Here, the base material includes, for example, a synthetic resin sheet such as polyethylene, polypropylene, nylon, polyvinyl chloride, polyvinylidene chloride, polyester, etc., an animal/plant material or inorganic fiber sheet (paper, cloth, nonwoven fabric, leather, etc.), 2
Mixed sheets or blended fabrics of synthetic resins and inorganic fibers or powders, blended fabrics or nonwoven fabrics of synthetic resins and animal and plant fibers, foils or films of metals such as aluminum, stainless steel, zinc, etc., laminated sheets of the various sheets listed above, etc. can be exemplified. Furthermore, as the above-mentioned base material, natural wood for furniture parts, such as awn, pencil fern, oak, etc., and molded products of plastics, such as vinyl chloride resin, chlorinated polyethylene, polyethylene, polypropylene, etc., can also be effectively used. . The means for retaining the insect repellent composition of the present invention on the secondary substrate is not particularly limited, and may be carried out, for example, by coating, impregnating, dropping, kneading, or the like. 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 insect repellent material is an insect repellent carpet. The insect repellent carpet is
For example, after preparing a conventional carpet consisting of pile, first base fabric, backing agent, and second base fabric, the insect repellent composition of the present invention in liquid form is sprayed onto the front and/or back sides of the carpet. , Prior to creating the carpet, the insect 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 created using the above. can be obtained by mixing the insect repellent composition of the present invention into a backing agent and using this to create a carpet according to the precoat method or jute back method. In the above, the pre-coat method refers to a method in which a backing agent is applied in advance to the first base fabric to fix the pile, and then a backing agent is further applied to this treated area to adhere the second base fabric. . In addition, the jute pack 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 made as above is
Usually preferably from about 5 to 5 per square meter of carpet.
It is preferable to retain 200 g of the active ingredient compound, so that the desired effect can be sufficiently achieved.

EXAMPLES Hereinafter, examples will be given to explain the present invention in more detail.

Example 1 A filter 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 them. After standing for 10 minutes, 1 hour, and 6 hours, the number of ants on each filter paper is counted, and the repellent effect of the test compound is determined according to the formula below, based on the number of ants on the non-impregnated filter paper. .

...Repellent effect less than 30% The results obtained were judged according to the following criteria and are shown in the table.

＋＋＋・・・Repellent effect of 90% or more ++ ・・・ 70-90% ＋ ・・・ 50-70% 30-50% The results below are the same as in Table 1 Table 2 below shows the criteria.

Table 2 Example 2 A pure woolen cloth (muslin cloth 10×10an) was impregnated with the test compound as shown in Table 2 below, and this was paired with a non-impregnated cloth in a 30 cm diameter petri dish containing 30 carp moth larvae. After placing them in rows and leaving them for 7 or 14 days, the degree of feeding damage in each city was investigated, and the repellent effect of the impregnated cloth was calculated using the following formula based on the amount of feeding damage of the non-impregnated cloth.

The results are shown in Table 3 below, similar to Table 1.

Table 3 Example 3 One sugar cube was placed in the center of each of a round filter paper (diameter 11 cm) impregnated with the test compound and an untreated filter paper, and 25 adult male and female German cockroaches were raised in pairs. After arranging them in a rearing box so as not to overlap them and leaving them for 12 or 24 hours, the amount of weight loss (feeding damage) of each filter paper sugar cube was measured and the repellent effect was calculated using the following formula.

Example 4 Odorless kerosene was added to 5 g of the test compound to make a total amount of 100 g to produce an insect repellent in the form of an oil solution.

The effectiveness of the thus obtained oil agent was determined by the following method using odorless kerosene as a control.

That is, each oil solution was stored in a plywood box (
An amount of the test compound (approximately 2 cm/d (equivalent amount for the control oil)) was sprayed onto each of the five inner walls of a container (with internal dimensions of 20 x 30 x 4 cm), and the resulting container box was used to hold 400 German cockroaches. The specimen is left in the case for 6 or 12 hours, 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.

＋＋＋・・・Very effective when the number of residents is O++ ・・・〃 Quite effective when there are 1 to 4 animals＋ ・・・
... Valid for 5 to 9 animals... /l Ineffective for 10 or more animals The results are shown in Table 4 below.

Table 4 Example 5 A paulownia wood board (15x150x2an) was immersed in a solution of 15% of the test compound added to dichloromethane.
The chain plates are impregnated with the above solution by pressure treatment at 5 kg/cm2 to make insect-proof wood, and this is used to make furniture drawers (115 x 42
A pest repellent material in the form of (x15cm) was produced. The resulting drawer was used to test its effectiveness against burs. That is, about 80% of the clothes are placed in a drawer as is normally used, and 10 35-day-old burr larvae are placed in the upper, middle, and lower parts of the stacked clothes.
A nylon goose bag containing each head was placed, and after 2 weeks and 1 month, the insect repellent effect was evaluated according to the following criteria.

+++・・・100% lethal ++...80-99% lethal ＋・・・50-79% lethal ・・・Less than 50% fatality The results are shown in Table 5.

Example 6 The surface of a carpet (commercially available, untreated insect repellent) cut into 10×5 sizes was treated by spraying 3 zll of an acetone solution of the test compound (the amount of the agent was 0.6 g/m 2 ).

This treated carpet and an untreated carpet of the same size were joined together along the long sides without any gaps, and a plastic cylinder was placed on top of them. Separately, a small petri dish with a diameter of 3 cm containing 30 ants was prepared and placed face down on an untreated carpet. After leaving the carpet for a while to stabilize ant activity, the petri dish was removed and the number of ants that invaded the treated carpet was observed over time to determine the repellent effect.

The results are shown in Table 6.

No. 6 table No. table (carpet specification) Example carpera For the purpose of insect repellent, Table 7 below Specifications N.

Carpella with A-N Insects of the present invention in the form of Created a repellent.

Notes (Note 1) to (Note 5) in Table 7 above indicate that the following insect repellents and other chemicals were mixed, respectively.

(Note 1)... Rose fragrance l g/m2 (Note 2) = AH30g/m2 (Note 3) -AB 30 g/m2 (Note 4)...p-chloro-m-xylenol 10g/
m2 (Note 5)...2-(4'-thiazolyl)benzimidazole 3 g/m2 Insect repellent carpet sample No. obtained above.

The following tests were conducted for A-N.

<Test method 1> Ant repellent test 50 red-eared ants were released in a 16 x 22 x 8 cm vat, and 2 samples each cut into 5 x 5 an sizes and 2 blank carpet samples were placed at the bottom of the vat alternately in each corner, and a total of 4 pieces were placed on the carpet. A small piece of absorbent cotton soaked in 5% sugar water was placed on the carpet, the number of ants gathered on the carpet was counted, and the repellency rate was determined using the following formula.

<Test method 2> German cockroach repellent test Carpet sample (15 x 15 cm) Place 1 sugar cube whose weight was measured in advance in the center, pair it with a blank carpet set in the same way, and put 625 adult German cockroaches of both sexes in the bottom of a vat (35 x 40 x 23 cm). After arranging the carpets so that they do not overlap and leaving them for two 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 results are shown in Table 8 below.

Table 8 Insect repellent carpet samples J and M obtained above
The antifungal efficacy of the antibacterial and antifungal agent mixed into each sample was also tested as follows.

That is, Aspergillus niger (Asp, njgerA).
106/77' spore suspensions of TCC9642') and Penicillium citrinum (P, cilrina)
m ATCC9849) spore suspension 106/yl
After applying 2 zl of each to the tatami surface (10 x 10 cm) and inoculating it, place a carpet sample (5 x 5 an) on the tatami surface.
was placed on the plate and maintained at 25° C. and 70% RH for one week.

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 was observed. As a result, a rating of 10 was obtained for the blank, but when carpet samples J and M were used, both were rated -.

Example 8 Ten of each of the test compounds of the present invention used in the above implementation fs4
Add a small amount of fragrance, ethyl cellosolve 2011, and odorless kerosene to 150 zl, and add this and 150 yl of a mixture of liquefied petroleum gas and dimethyl ether (50:50 volume ratio) to an aerosol pressure can (400 zl content).
The insect repellent of the present invention in the form of an aerosol was obtained by filling the container into an injector and sealing it.

Using each of the aerosols thus obtained, a repellent effect test against German cockroaches was conducted in the same manner as in Example 4, and results equivalent to those shown in Table 4 were obtained.

Example 9 5 g of each of the test compounds of the present invention used in Example 4, 25 g of nitrocellulose, 25 g of thinner, and 2 g of dibutyl phthalate were mixed and dissolved to obtain an insect 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 4, and results similar to those shown in Table 4 were obtained.

Example 10 5 g of each of the test compounds of the present invention used in Example 4 and N-(2-ethylhexyl)-bicyclo-(2,2,1)-5-heptene-2,3-di as a potency enhancer. 5 g of carboximide was mixed with 1.0 g of n-hexane. / diluted with
The sample compound was impregnated with 30 g of the test compound into a sample of 0.0 μm and an area of 1 m 2 ), and then dried to obtain a sheet-like insect repellent of the present invention.

The sheet obtained in this way was placed at the entrance with inner dimensions of 4 cm x 30
Example 4 After cutting to a size that matches each of the five inner walls of a plywood box (inner dimensions 20 x 30 x 4 cm) of AN, it was pasted together.
When subjected to a repellent effect test in the same manner as above, results almost equivalent to those shown in Table 4 were obtained.

Example 11 3 parts by weight of the test compound of the present invention used in Example 4, 1 part by weight of silicon oxide, and 96 parts by weight of cyclododecane were thoroughly crushed and mixed, and then pressed into Log/tablets under a pressure of 300 kg/an2. The insect repellent of the present invention in tablet form was obtained.

The obtained tablets were placed in each box 2 in the plywood boxes described in Example 4.
When a similar repellent effect test was conducted by inserting tablets one by one, almost the same results were obtained.

Example 12 Each of the test compounds of the present invention used in Example 4 was sufficiently stirred and mixed with the same weight of silicon oxide, and then pulverized to obtain a powdered insect repellent of the present invention.

3 g of each of the obtained powders was filled into cloth bags, and each bag was placed in a plywood box in the same manner as in Example 4 and subjected to the same repellent effect test, and the same results as Habo were obtained.

Example 13 6 parts by weight of the test compound of the present invention used in Example 4 was added to 2.4 parts by weight.
．． 6-Dolyisoprobyl-1.3.5 After mixing with 9 parts by weight of trioxane, a paulownia wood box (15 cm x 150 cm x 2-thickness) was immersed in the solution heated and dissolved at about 90°C.
The wood was pressurized at 5 kg/cm2 and impregnated with a liquid in an amount of about 25% of the weight of the wood to obtain the insect repellent of the present invention in the form of insect repellent-retaining wood.

A box with the same dimensions as the box described in Example 4 was pasted together using each piece of wood obtained, and this box (active ingredient retention amount: approx. 1
When a similar repellent effect test was conducted on 5g), similar results were obtained.

(that's all)

Claims (2)

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