JP2024006087A - Insect repellent, insect repelling composition and insect repelling method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an insect repellent that exhibits superior insect repelling effect on various insects and effectively sustains the superior insect repelling effect for a long time.

SOLUTION: The present invention provides an insect repellent that contains caryophyllene dioxide as an active ingredient, an insect repelling composition that contains caryophyllene dioxide, and an insect repelling method that includes applying caryophyllene dioxide to an insect habitat.

SELECTED DRAWING: None

COPYRIGHT: (C)2024,JPO&INPIT

Description

The present invention relates to an insect repellent, an insect repellent composition, and an insect repellent method.

Cockroaches, ticks, mosquitoes, etc. cause real damage as sanitary pests that transmit viruses that cause diseases to humans, and it is meaningful to try to eliminate them.However, in recent years, as the concept of cleanliness has increased, opportunities for contact with insects have decreased. For these reasons, there is a strong tendency to treat insects as ``pests'' and prevent them for the subjective reason that their appearance or movement offends people, regardless of whether or not they cause actual damage.

Organophosphorus, carbamate, or pyrethroid insecticides, which have traditionally been used to control sanitary pests, have been used for a long time because they have excellent insecticidal power and are inexpensive. When insects are killed with insecticides, the carcasses of the insects remain in the area, which can make buyers who hate insects uncomfortable. is emphasized.

However, most of the insect repellents to date have targeted specific insect pests, and there are no known insect repellents that have a wide range of insect repellent effects against various insect pests, and there are no insect repellents that can maintain their effectiveness for a long period of time. It is no exaggeration to say that the drug is unknown.

However, pyrethroid household insect repellents that claim long-term insect repellent effects are commercially available. However, pyrethrins and synthetic pyrethroids are easily decomposed by light and oxygen, and do not maintain their effectiveness for a long period of time. Therefore, these household insect repellents do not require the pyrethroid to be adsorbed onto a carrier or are treated with decomposition inhibitors. The problem is that sustainability is imparted by using in combination with other materials, which inevitably increases production and cost burdens.

Regarding caryophyllene, an insect repellent for rice sap-sucking insects that contains caryophyllene oxide as an active ingredient is known, but although this insect repellent has excellent effects, it is not intended for domestic pests or nuisance insects. It cannot be said that it is sufficient to maintain the effect over a long period of time (Patent Document 1).

Japanese Patent Application Publication No. 2010-180163

As a result of extensive research, the present inventors surprisingly discovered that caryophylline dioxide has an excellent insect repellent effect against various insects, and also found that this excellent insect repellent effect is effective for a very long period of time. They discovered something and completed the present invention.

That is, the present invention is an insect repellent containing caryophyllene dioxide as an active ingredient.

Further, the present invention is an insect repellent composition containing caryophyllene dioxide.

Further, the present invention is an insect control method comprising applying caryophyllene dioxide to the insect growth area.

According to the present invention, caryophyllene dioxide has a low vapor pressure at room temperature, and therefore can maintain its effectiveness for an extremely long period of time without the need for formulation treatment for sustainability, and is therefore excellent as an insect repellent. ing.

Furthermore, caryophylline dioxide has high stability as a substance and is easy to handle even when used as an insect repellent. Furthermore, since it has an insect repellent effect against a very wide range of insect types, there is no need to use insect repellents with different active ingredients for each insect, and it is possible to easily maintain an insect-free living area.

Further, according to the present invention, the insect repellent effect against a very wide range of insect types is maintained for a long period of time, so the frequency of replenishing the insect repellent and the frequency of replacing the insect repellent can be significantly reduced.

Further, according to the present invention, many insects dislike the insect repellent of the present invention and do not approach, so no insects are seen, and unpleasant opportunities such as removing dead insects can be greatly reduced. .

FIG. 3 is a schematic diagram of the experimental equipment used in Example 3. FIG. 3 is a schematic diagram of the experimental equipment used in Example 4.

Taxonomically, the insect repellent of the present invention is classified into the above-mentioned insects of the superorder Cockroachiformes, order Cockroachidae, and order Isoptera, which belong to the suborder Ptera, order Protoroptera, and insects of the order Macroptera or Pteroptera of the suborder Ptera. The targets are insects belonging to the order Diptera, insects belonging to the order Lepidoptera, insects belonging to the order Hemiptera, Chemioptera, Hymenoptera, and Orthoptera. These insects are sometimes called nuisance pests, sanitary pests, and domestic pests based on the senses that humans experience in daily life, but nuisance pests, sanitary pests, and domestic pests are not academic classifications, and are based on the same insects. It is often divided into multiple categories.

In addition, in the present invention, insect repellent means that there are no insects living within a certain range where the insect repellent of the present invention exists, and its effects on insects include calcium channel inhibition, cholinesterase inhibition, and GABAergic inhibition. This means that it may be due to any of the insect repellent mechanisms such as nervous system inhibiting action, respiratory inhibiting action, insect repellent action, etc.

In the present invention, insects are defined according to the following definitions, but these do not mean that one insect falls under one definition, but also include cases where one insect falls under multiple definitions such as the above taxonomy. It is something that

The insect repellent of the present invention targets nuisance pests, sanitary pests, household pests, etc. nuisance pests are pests that do not cause actual harm to humans but are offensive due to their appearance, such as spiders. , ants, millipedes, green beetles, cicadas, beetles, and cockroaches.

In addition, sanitary pests are pests that can be the cause or remote cause of diseases in humans and pets, and include mosquitoes, flies, horseflies, fleas, lice, mites, bees, woolly beetles, centipedes, cockroaches, and brown moths.

Domestic pests are pests that feed on things necessary for human life, such as clothing, grains such as rice and flour, buildings, and books, such as the brown weevil, bean weevil, white beetle, bark beetle, brown beetle, cutlet beetle, black-and-white beetle, These include cockroaches, flies, leopard beetles, cutlet beetles, white beetles, oyster beetles, snail beetles, long-tailed moths, chatate beetles, springtail beetles, termites, carp beetles, burrs, white mites, ants, red beetles, ladybugs, and stink bugs.

The insect repellent of the present invention exhibits an insect repellent effect against a variety of insect pests, and can maintain the insect repellent effect for a long period of time.

Examples of spiders include Kabakikomachi spider, Redback spider, Jorou spider, Kusa spider, Ashidaka spider, Jumping spider, Jig spider, House spider, Hiratago spider, Hangetuosuna spider, etc.

Examples of ants include black carpenter ants, black carpenter ants, mikado carpenters, spiny ants, red wood ants, black carpenter ants, samurai ants, ants belonging to the Carpenterinae subfamily, such as black carpenter ants, black carpenter ants, red carpenter ants, Japanese carpenter ants, Japanese carpenter ants, yellow carpenter ants, caribou carpenter ants, and terracotta ants. Examples include ants that belong to the subfamily Dipterainae, such as the cylindrical ants, comb-eared ants, black-spotted ants, brown ants, and white ants; ants that belong to the subfamily Cateridae, such as the blue ants;

Examples of millipedes include yellow millipedes, yellow millipedes, yellow millipedes, and yellow millipedes.

Other examples of geji include geji and geji.
In addition to Kamadouma, examples of Kamadouma include Eragukamadoma, Yakukamadoma, Agnikamadoma, Kumekamadoma, Meshimakamadoma, and Amagikamadoma.

Examples of horseflies include the black-and-white fly, the black-and-white fly, the mountain fly, the black-and-white fly, the black-and-white fly, the black-and-white fly, the black-and-white fly, the black soldier fly, the black-and-white fly, and the golden fly.

Examples of cockroaches include black cockroach, American cockroach, small cockroach, Yamato cockroach, German cockroach, Japanese cockroach, Kyoto cockroach, Japanese cockroach, Japanese cockroach, Satsuma cockroach, Yaeyama cockroach, Ogasawara cockroach, and gray cockroach.

In addition, mosquitoes that are sanitary pests include the common mosquito, the yellowtail mosquito, the Culex mosquito, and the Culex mosquito.
Examples include Culex mosquito, Culex mosquito, Culex mosquito, Culex mosquito, Aedes aegypti, Aedes aegypti, Aedes albopictus, Aedes albopictus, Aedes albopictus, Aedes aegypti, Prosophora syriata, Anopheles anopheles, and Anopheles chinensis.

Flies include the hammer fly, the fruit fly, the fruit fly, the German fruit fly, the degas fly, the striped fly, the green leaf fly, the leafminer fly, the leafminer fly, the spiny fly, the fruit fly, the yellow fruit fly, the white fruit fly, the white fruit fly, the small black fungus fly, the giant fruit fly, the common fruit fly, the white fruit fly, the white fruit fly, the black leaf fly, and the black leaf fly. Mobae , house fly, black fly, sheep fly, and black fly.

Examples of horseflies include those mentioned above, and examples of fleas include human fleas, dog fleas, and cat fleas.
Examples of lice include human lice, body lice, and pubic lice.

Examples of mites include Dermatophagoides mites, Demodex mites, Demodex mites, Demodex mites, Ixodes mites, House dust mites, Red mites, Demodex mites, Demodex mites, Demodex mites, and Takara mites.

Examples of bees include sawflies, yellow-bellied hornets, wasps, and honey bees. Examples of wasps include the Japanese giant hornet, Japanese hornet, yellow hornet, small hornet, Japanese monster hornet, brown hornet, black hornet, black hornet, oriental hornet, black hornet, and yellow hornet. Examples include the long-tailed hornet and the Japanese hornet.

Examples of woolly caterpillars include the larvae of the larvae, the larvae of the Japanese white moth, the larvae of the Japanese snail moth, the larvae of the Japanese snail moth, the larvae of the Japanese gypsy moth, the larvae of the gypsy moth, the larvae of the Japanese gypsy moth, and the pine beetle. larvae).
Examples of centipedes include the black-spotted centipede, the giant centipede, and the red centipede.

Examples of cockroaches include those mentioned above.
Examples of the brown moth include the brown moth, the chado moth, the yellow moth, the white moth, the grape moth, the bean moth, the sedge moth, the apple moth, the red moth, the white moth, the Japanese cedar moth, the daisetsu moth, the gypsy moth, the yellow snail moth, the nonnne snail moth, the yellow snail moth, and the red snail moth.

Examples of the weevil include the brown weevil and the brown weevil.

Bean weevils include honey bean weevil, common bean weevil, Japanese bean weevil, small bean weevil, chavara bean weevil, white bean weevil, samurai bean weevil, long bean weevil, black bean weevil, Syrian black bean weevil, Japanese black bean weevil, pea weevil, broad bean weevil, and black bean weevil. Bean weevil, Azuki bean weevil , the Japanese bean weevil, the vertical bean weevil, the brown bean weevil, the long bean weevil, the bean weevil, the black bean weevil, the sauter bean weevil, and the Brazilian bean weevil.

Examples of the beetles include tobacco beetles, silver beetles, woolly beetles, pine beetles, long-tailed beetles, hair beetles (katsurakushigetsushi beetle), and black-throated beetles.

Bark beetles include pine bark beetle, Yachida monochrome bark beetle, Haruen bark beetle, pine tree bark beetle, Lewis's bark beetle, western bark beetle, giant bark beetle, cypress bark beetle, cypress bark beetle, hoopoe bark beetle, Ezo bark beetle, yellow bark beetle, and Japanese bark beetle. Yotsume Examples include bark beetles, yellow-eared bark beetles, and yellow-eared bark beetles.

Examples of Koknust include Kokubst, Hosochibi Koknust, etc. The cutlet beetles include the common cutlet beetle, the long cutlet fly beetle, the red-headed cutlet fly beetle, the yellow cutlet fly beetle, the long-tailed cutlet fly beetle, the long-tailed cutlet fly beetle, the long-tailed cutlet fly beetle, the black cutlet fly beetle, the black cutlet fly beetle, the striped cutlet fly beetle, the black cutlet fly beetle, the white cutlet fly beetle, the white cutlet fly beetle, the long-tailed cutlet fly beetle, and the red cutlet fly beetle. Darakatsuobushimushi , White-throated cutlet beetle, Japanese cutlet beetle, Red cutlet beetle, Japanese cutlet beetle, and Japanese red cutlet beetle.

Cockroaches and flies include those mentioned above. Examples of leopard bugs include false leopard bugs, semaru leopard bugs, kejiro leopard bugs, black leopard bugs, cabaret leopard bugs, naga leopard bugs, leopard bugs, hime leopard bugs, and konaga leopard bugs.

The cutlet beetle, the white beetle, and the brown beetle are as mentioned above.

As for the hirata beetles, there are saw-whet oyster beetles, giant saw-whet beetles, giant saw-whet oyster beetles, kado-kobuhoso hirata beetles, tactile oyster beetles, kakumune hiratamushi, haukakumune hiratamushi, haukakumune hiratamushi, and rust. Examples include the black-and-white beetle and the Turkish black-and-white beetle.

Examples of weevils include those mentioned above.

Examples of the Chibitake nagashin beetle include the Chibitake nagashin beetle, the large Chibitake nagashin beetle, and the Nihontake nagashin beetle.

Examples of the May moth include the Noshime Madara moth, the Common spotted moth, the Urinoma moth, and the Cotton borer moth.

Chatate beetles include Hirata chatate, Konachatate, Kochatate, Katsubushi chatate, Usubenichatatemushi, Kimonchatatemushi, Yotsumonhosochatatemushi, Hosochatatemushi, Nagakechatatemushi, Striped chatatemushi, Osujichatatemushi, Black chaatatemushi, Ochatatemushi, and Ourokochatatemushi. S , Hagurumachatatemushi, Idatenchatatemushi, etc.

Examples of collembolans include gray collembolla, purple collembolla, and white collembolla.

Examples of termites include the Japanese termite, the Japanese termite, the Japanese termite, the Japanese termite, the Japanese termite, and the American termite.

Examples of the grass beetles include those mentioned above, and examples of the burs include the carp moth as well as the burr.
Examples of mites include woolly mites. Examples of the ants, cutlet beetles, and Japanese cutlet beetles include those listed above.

As for ladybugs, the ladybirds include the southern ladybird, the red ladybird, the dandara ladybird, the turtle ladybird, the yellow ladybird, the yellow ladybird, the monstrous ladybird, the giant ladybug, the bedalia ladybird, the red ladybird, the red ladybird, the yellow ladybird, the yellow ladybird, the yellow ladybird, and the white ladybug. Examples include star ladybugs.

Stink bugs include rice stink bugs (black stink bugs), quail stink bugs, spiny stink bugs, white stink bugs, spotted stink bugs, green stink bugs, southern stink bugs, rice stink bugs, giant stink bugs, rice black stink bugs, and brown stink bugs. Stink bugs, stink stink bugs, stink stink bugs, such as stink bugs, stink bugs, stink bugs such as stink bugs, stink bugs, stink stink bugs, and stink bugs, and red stink bugs. Examples of stink bugs include stink bugs belonging to the family Helicopteridae, such as the common stink bug, stink bugs belonging to the family Helicidae, such as the spotted stink bug, and stink bugs belonging to the family Nastylinidae, such as the red-throated stink bug, and the red-spotted stink bug.

Caryophyllene dioxide, which is the insect repellent component of the present invention, is a known compound (Canadian Journal of Chemistry, 54(9), 1372-1382, 1976), and is a crystalline white solid at room temperature, but becomes liquid when heated. It is a compound that has an aroma.

Caryophyllene dioxide is an extremely safe compound, and is included in the OECD Guideline for Testing of Chemicals 420, which is a collection of internationally agreed test methods for evaluating the safety of chemical substances. In an experiment conducted by the Japan Food Research Center using 6-week-old female rats in accordance with 2001), the _LD50 of caryophylline dioxide was 2000 mg/kg or more, making it an extremely safe substance. It has been confirmed that there is.

In addition, a 24-hour occlusive patch test was conducted on healthy subjects (20 to 60 years old) using a 0.5% caryophyllene dioxide aqueous solution (distilled water for injection), and the skin irritation index was 0. 0 and is classified as a safe product.

In the present invention, the amount of caryophyllendioxide used, which is an insect repellent component, varies depending on the target insect pest, but usually a sufficient insect repellent effect can be obtained by using 10 to 800 μg per 1 cm ² . Furthermore, it is preferable to use 50 to 500 μg per cm ² , particularly preferably 100 to 200 μg per cm ² . Even if the above-mentioned amount is exceeded, there is no particular problem since the amount of the insect repellent will be excessive; on the contrary, there is an advantage that the insect repellent effect can be maintained for a longer period of time.

The insect repellent of the present invention can be used as it is, or can be used by dissolving it in an appropriate solvent, but it can also be used in combination with appropriately selected formulation aids, such as solutions, emulsions, suspensions, solid preparations, aerosols, and more. The composition can be in various forms such as a sheet. For example, in the case of a solution, the insect repellent component of the present invention may be mixed with water, lower alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, and isopropyl alcohol, ketones such as acetone, methyl ethyl ketone, dioxane, tetrahydrofuran, and ethylene glycol monomethyl. Ethers such as ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, aliphatic hydrocarbons such as kerosene, kerosene, fuel oil, machine oil, etc., aromatic hydrocarbons such as benzene, toluene, xylene, solvent naphtha, methylnaphthalene, etc. , halogenated hydrocarbons such as dichloromethane, chloroform, and carbon tetrachloride; acid amides that are liquid at room temperature such as N,N-dimethylformamide and N,N-dimethylacetamide; esters such as ethyl acetate and butyl acetate; It can be used by appropriately dissolving it in a solvent appropriately selected from nitriles such as acetonitrile, propionitrile, and the like.

Furthermore, if the insect repellent composition of the present invention is an emulsion, for example, it can be produced by uniformly mixing the insect repellent component of the present invention, an emulsifier, an organic solvent, and the like.

Furthermore, when the insect repellent composition of the present invention is made into a solid preparation, it can be produced by impregnating or adsorbing caryophyllene dioxide onto a solid carrier. Examples of such carriers include vegetable powders such as soybean powder, tobacco powder, wheat flour, and wood flour; clays such as kaolin, bentonite, sepiolite, and acid clay; talcs such as talcum powder and waxite powder; diatomaceous earth; Examples include silica such as mica powder, and inorganic salts such as calcium carbonate, alumina, and calcium silicate, and it is more preferable to use porous materials. Further examples include sheet-like or spherical carriers made from pulp such as Viscopal.

Furthermore, when the insect repellent composition of the present invention is used as an insect repellent resin, it can be produced by blending caryophyllene dioxide into a synthetic resin, thermoplastic resin, or biodegradable polymer material. Such resins and polymer substances include, for example, vinyl acetate resin, polyethylene resin, polypropylene resin, polyethylene terephthalate, polybutylene terephthalate, polyvinyl acetate, polyamide, polymethyl methacrylate, acrylic resin, methacrylic resin, EVA (ethylene-acetic acid), etc. Any material can be suitably used as long as it does not react with the insect repellent component of the present invention, such as (vinyl copolymer) resin. Further, as the biodegradable polymer, in addition to chemically synthesized ones such as polylactic acid, polycaprolactone, and aliphatic polyester, biodegradable polymer substances such as starch, chitin, chitosan, and polyamide can be used.

The insect repellent resin can be produced by a conventional method. For example, the resin and caryophyllene dioxide may be kneaded under heating or in the presence of a plasticizer or solvent, and then cut into pellets, or made into a sheet. It can be manufactured by molding it into a desired shape, such as a plate, film, or fiber.

When the insect repellent composition of the present invention is made into an aerosol agent, for example, caryophyllene dioxide, an organic solvent, and a stabilizer, etc., which are appropriately blended as necessary, are filled into an aerosol container, and an aerosol valve is attached to the container. It can be manufactured by filling the container with a propellant, shaking it, and then attaching an actuator.

Examples of the organic solvent used in the aerosol agent include lower alcohols, normal paraffinic solvents, isoparaffinic solvents, and mixtures thereof, as well as chain saturated hydrocarbons and saturated hydrocarbon solvents, which may be contained in the aerosol of the present invention. Examples of propellants used include liquefied gases having a boiling point of -50°C to 0°C, such as liquefied petroleum gas (LPG), dimethyl ether, propane, n-butane, and isobutane.

The content of caryophyllendioxide in the insect repellent composition of the present invention is determined by taking into account the content of the insect repellent composition so that the insect repellent effect of the caryophyllendioxide is effectively exhibited during use. However, to give one example, in the insect repellent composition, caryophyllene dioxide is present in an amount of 0.1 to 5% by weight, preferably 0.3 to 5% by weight, more preferably 0.5 to 3% by weight. , most preferably in an amount of 0.8 to 1.5% by weight.

Furthermore, a surfactant can be added to the insect repellent composition of the present invention as an emulsifier, a spreading agent, a penetrating agent, a wetting agent, a dispersing agent, etc. Such surfactants include nonionic surfactants. For example, soaps, polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene nonylphenyl ethers, polyoxyethylene polyoxypropylene ethers, polyoxyethylene Common pesticides or insect repellents such as distyrenated phenyl ether, polyoxyethylene alkyl esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, higher fatty acid alkanolamides, alkylmaleic acid copolymers, polyhydric alcohol esters, etc. Examples include surfactants used in

Further, as the cationic surfactant, for example, an alkylamine salt, a quaternary ammonium salt, etc. can be used, and as the anionic surfactant, for example, a naphthalenesulfonic acid polycondensate metal salt, a naphthalenesulfonic acid polycondensate metal salt, naphthalenesulfonate, etc. can be used. Polymer compounds such as formalin condensates of acid salts, alkylnaphthalene sulfonates, lignin sulfonate metal salts, alkylaryl sulfonates, alkylaryl sulfonate sulfates, polystyrene sulfonic acid sodium salts, polycarboxylic acid metal salts, polyoxy Examples include ethylene histidyl phenyl ether ammonium sulfate, higher alcohol sulfonate, higher alcohol ether sulfonate, dialkyl sulfosuccinate or higher fatty acid alkali metal salt.

Furthermore, in the insect repellent of the present invention, stabilizers, antioxidants, etc. can be blended, and the stabilizers include dibutylhydroxytoluene (BHT), butylhydroxyanisole (BHA), tetrakis[3-(3 , 5-di-tert-butyl-4-hydroxyphenyl)propionyloxymethyl]methane, DL-tocopherol, propyl gallate, erythorbic acid, sodium erythorbate, isopropyl citrate, etc., polyphosphoric acid, cyclodextrin (Toyoderin P), etc. Examples of antioxidants include BHT, 4,4-thiobis-6-tert-butyl-3-methylphenol, BHA, and paraoctylphenol.

The insect repellent method of the present invention can be carried out by applying the insect repellent or insect repellent composition of the present invention to areas where insects grow.
In the present invention, application means to cause the insect repellent or insect repellent composition of the present invention to be present in an insect growth area in order to exhibit an insect repellent effect, and specifically, for example, in an insect growth area. , means to make the insect repellent or insect repellent composition of the present invention present by known means such as coating, spraying, spraying, leaving still or fixing.
When applied, the insect repellent effect can be obtained by adjusting the amount of caryophyllene dioxide to be such that the insect repellent effect of the present invention can be exhibited.

EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto.

Reference example 1
4.4 g (20 mmol) of caryophyllene oxide was dissolved in 100 mL of dichloromethane, cooled to 0° C. with ice cooling, and 26.2 g (30 mmol) of 8.7% peracetic acid was added with stirring. Thereafter, the mixture was stirred at room temperature for 4 hours. After the reaction was completed, the reaction solution was washed three times with 200 mL of saturated brine, three times with 100 mL of saturated sodium bicarbonate solution, and three times with 100 mL of saturated brine. After adding sodium sulfate to the solution and drying it, dichloromethane was distilled off and the resulting crude product was purified by vacuum distillation (121°C, 0.2 kPa) to obtain 3.8 g (16 mmol) of caryophyllene dioxide. Obtained. The yield was 80% and the purity was 94% (GC).

The mass spectrum (EI method, 70 eV, m/z) of the obtained caryophyllene dioxide was as follows.
43, 55, 67, 79, 93, 108, 121, 137, 145, 163, 175, 191, 205, 221, 236 (M+)

Example 1
<Insect repellent effect against red-eared ants>
Near the nest of red-eared ants under the eaves of a house, 1 mL of a mixture of equivalent amounts of 20% sugar water and honey was applied to the center of a circular filter paper with a diameter of 9 cm as an attraction source for red-eared ants. Then, after spraying 5 mL of an acetone solution containing 1% or 3% of caryophyllene dioxide (hereinafter simply referred to as caryophyllene dioxide) produced in the same manner as in Reference Example 1, the test plots were dried at room temperature. .

As a control group, a control group was prepared in the same manner as the test group, except that only acetone was sprayed instead of the acetone solution containing caryophyllene dioxide.
The number of reticulated ants attracted to the filter paper in the test plot and control plot was observed, and the insect control rate was calculated.
The test was conducted three times at the same location, and the filter paper was left as it was after the test, and 24 and 48 hours later, 1 mL of an aqueous honey solution was sprayed as the attractant sugar onto the center of the filter paper, and evaluation was performed in the same manner. . The test results are shown as the average value of three tests. The results are shown in Table 1.

The insect control rate was determined as follows.
Insect control rate = (1 - number of individuals invading the test area/number of individuals invading the control area) x 100 (%)

Example 2
<Insect repellent effect against carp moth larvae>
An acetone solution containing 1% caryophyllene dioxide was applied to wool fabric (JIS L0803 compliant white cloth attached for dyeing fastness test "Wool") cut into 2.0 cm x 2.0 cm (processing amount: 0.16 mg) /cm ² ) and used as a test area.
In addition, a control plot was prepared in the same manner as in the test plot, except that acetone was used instead of the caryophyllene dioxide-containing acetone solution.
Test plots and control plots were set up in rectangular plastic containers, 20 carp moth larvae were released, and the number of individuals after 24 hours and the amount of feeding damage after 7 days were measured under dark conditions to measure the insect control rate.
The insect control rate was determined by removing the carp moth larvae after 7 days, pasting the infested test plots and control plots on a black mount, and scanning them in black and white. This was digitized in pixel units using image analysis software (Image J), and comparison processing of the feeding damage area of the wool fabric was performed.
As a result, for the test plot, the area of feeding damage in the test plot after 4 repetitions was 20 to 228 pixels for the wool fabric area of 5286 pixels, and the damage damage area of the control plot was 3513 to 4660 pixels, and the following formula was used. The average value of the insect control rate calculated was 97.2%.
Insect control rate = (1 - feeding damage area in test area / feeding damage area in control area) x 100 (%)

Example 3
<Insect repellent effect against brown weevil>
As shown in Figure 1, the bottom is an aluminum cup (diameter 3.8 cm, height 1 cm) that is chopped leaving a 2-3 mm high part from the bottom. An aluminum cup made into a tunnel by cutting out two sides of the aluminum cup was placed over the bottom to serve as a shelter.

Apply 0.2 mL of acetone solution containing caryophyllene dioxide at concentrations of 0.10%, 0.20%, and 0.50% to a filter paper with a diameter of 3.8 cm (processing amount: 16 μg/cm ² , 31 μg /cm ² and 70 μg/cm ² ) were used as the test plots, and those coated in the same manner as the test plots except that an acetone solution containing 0.50% β-caryophyllene was used instead of caryophyllene dioxide were used as the comparison plots. , and those to which only acetone was applied were placed on the bottom of the shelter as a control, 0.1 g of brown rice was placed on top of the shelter, and a tunnel-shaped cup was placed on top.

A shelter was set up in a rectangular plastic container, 20 adult brown weevils that had been fasted for 24 hours were released, and the number of individuals invading each area was measured after 24 hours under dark conditions to calculate the insect control rate. This operation was repeated four times and the average insect control rate was determined.
The results are shown in Table 2.

Insect control rate = (1 - number of individuals invading the test area or comparison area/number of individuals invading the control area)
×100(%)

Example 4
<Insect repellent effect against fruit flies>
As shown in Figure 2, a square opening (5cm x 5cm) is provided in the lid of a plastic cup with a lid (top surface: diameter 10cm, bottom surface: diameter 8cm, height: 4.5cm), and a square opening (5cm x 5cm) is made from acrylic as shown in the figure below. I made one with a container fitted into it. Aluminum was placed on the bottom of the cup, and 1.5 g of commercially available bananas cut into approximately 5 mm squares was placed on top of the aluminum.
0.5 mL of a solution prepared by diluting caryophyllene dioxide to a concentration of 5% with acetone was applied to a filter paper (5 cm x 5 cm) (processing amount: 1.0 mg/cm ² ) to prepare a test area. Those to which only acetone was applied were used as a control group.

The test area and the control area were each placed in a container and covered with a lid, placed in a cage (40 cm x 40 cm x 40 cm) surrounded by mesh, and 100 Drosophila melanogaster adults were released into the cup. The number of insects was measured. This operation was repeated four times and the average insect control rate was determined.
As a result, 1 to 8 Drosophila melanogaster adults were confirmed in the test area, 46 to 94 in the control area, and 5 to 53 in the external area. Based on this, the average insect control rate was 93.2%. there were.
Insect control rate = (1 - number of individuals invading the test area/number of individuals invading the control area) x 100 (%)

Example 5
<Insect repellent effect against chatate beetles>
A piece of cardboard with a thickness of 3 mm was cut into a size of 2 cm x 2 cm, and 0.1 mL of caryophyllene dioxide diluted with acetone to a concentration of 1% was applied to the front and back sides respectively (treatment amount: 0.1 mL each). 2 mg/cm ² ) was used as a test area, and the area to which only acetone was applied was used as a control area. A test area and a control area were set up at both ends of a glass petri dish with a diameter of 9 cm, and 50 adults of Oysterfish were released into the dish.The dish was covered with a lid and allowed to stand in the dark at 25°C for 24 hours. Thereafter, the number of individuals in each of the test plots and control plots was measured. This operation was repeated four times and the average insect control rate was determined.
As a result, 0 to 1 adult flycatcher was confirmed in the test area, 40 to 48 adults in the control area, and 2 to 10 adults in the external area. Based on this, the average insect control rate was 99.4%. there were.
Insect control rate = (1 - number of individuals invading the test area/number of individuals invading the control area) x 100 (%)

Example 6
<Insect repellent effect against German cockroach>
An aluminum dish (11.5 cm in diameter x 3.5 cm in height) was placed upside down as a shelter for German cockroaches, which do not like light, in a plastic container with a diameter of 30 cm and a height of 15 cm, the inner side of which was coated with Vaseline. At that time, two parts of the aluminum plate were cut out to serve as entrances and exits for the German cockroach.
A filter paper with a diameter of 9 cm was coated with 1 mL of an acetone solution containing caryophyllene dioxide at a concentration of 0.05% (treatment amount: 8 μg/cm ² ) as a test group, and a filter paper coated with only acetone was used as a control group.

German cockroaches (30 in total, 10 each of male adults, female adults without egg pods, and larvae) were released into the plastic container and allowed to acclimate under light conditions for 24 hours with food and water provided.
Next, the test and control filter papers were placed separately at the bottom of the plastic container, each was covered with a shelter, and the number of insects was measured after 2, 4, and 6 hours under light conditions, and the insect control rate was calculated. .
This operation was repeated four times and the average insect control rate (%) was determined.
In addition, when measuring the effects of each concentration, food and water were removed at the beginning to prevent the attraction of individuals. The results are shown in Table 3.

Insect control rate = (1 - number of individuals invading the test area/number of individuals invading the control area) x 100 (%)

Example 7
<Sustainability of insect repellent effect>
In order to demonstrate that the insect repellent of the present invention has excellent sustainability, β-caryophyllene, caryophyllene oxide, and caryophyllene dioxide were used as insect repellent ingredients, and the insect repellent ingredients were added to 0.50% in the same manner as in Example 6. Test and control filter papers prepared by applying 1 mL of an acetone solution containing a ^{concentration} of An insect control test was conducted. This operation was repeated four times and the average insect control rate (%) was determined.
The results are shown in Table 4.

Insect control rate = (1 - number of individuals invading the test area/number of individuals invading the control area) x 100 (%)

Example 8
<Stability of insect repellent effect>
Caryophyllene dioxide was kneaded in polyethylene resin (Novatec LS880, manufactured by Japan Polyethylene Co., Ltd.) to contain caryophyllene dioxide at a concentration of 5%, and then formed into a 1 mm thick sheet using a hydraulic heat press (manufactured by Toyo Seiki Co., Ltd.). Molded.
This was cut into a size of 5 cm x 5 cm and used as a test section. In addition, a control group was prepared by cutting a vinyl chloride sheet with the same texture as the polyethylene into the same size as the test group.
Next, an accelerated test at 40°C was conducted to confirm how long the insect repellent effect lasted.
The insect repellent effect experiment was conducted in the same manner as in Example 6. The test was repeated four times, and the average insect control rate (%) was determined.
The results are shown in Table 5.

Insect control rate = (1 - number of individuals invading the test area/number of individuals invading the control area) x 100 (%)
As is clear from Table 5, the insect repellent sheet of the present invention was excellent in that it could maintain a high insect repellent effect even after 360 days at room temperature (25° C.).

Example 9
<Insect repellent effect against adult Aedes albopictus mosquito>
A filter paper (ADVANTEC No. 2) with a diameter of 185 mm was placed on an aluminum foil folded into a bellows shape, and an acetone solution containing caryophyllene dioxide prepared so that the amount of caryophyllene dioxide treated on the filter paper was 1.5 mg/cm ² was added. 4.5 mL was dropped and air-dried for 4 minutes in a fume hood to prepare a test section.
A control plot was prepared by dropping the same amount of acetone onto a filter paper of the same size and air drying it.
A test plot and a control plot were each hung on the side of a nylon goose cage (20 cm x 20 cm x 30 cm), and immediately after installation, about 100 female adult Aedes albopictus mosquitoes were released into the cage. At 0 (immediately after the start of the test), 1, 3, 6, and 24 hours later, the number of test insects settled on the test and control plots was counted. The test was repeated three times, and the insect control rate and its average (%) were calculated using the following formula. The above test was conducted in a laboratory maintained at 25+1°C.
Insect control rate = (1-T/C) x 100 (%)
T: Average number of colonized insects in the test area from 0 hours to 24 hours C: Average number of colonized insects in the control area from 0 hours to 24 hours As a result, the number of colonized insects in the test area was 0 to 2, and in the control area. The number of established insects was 13 to 22, and the average insect control rate (%) based on this was 99.2%.

Example 10
<Insect repellent effect against the larvae of the beetle beetle>
An acetone solution containing 1% caryophyllene dioxide was applied to wool fabric (JIS L0803 compliant white cloth attached for dyeing fastness test "Wool") cut into 2.0 cm x 2.0 cm (processing amount: 0.16 mg) /cm ² ) and used as a test area.
In addition, a control plot was prepared in the same manner as in the test plot, except that acetone was used instead of the caryophyllene dioxide-containing acetone solution.

A test plot and a control plot were set up in a rectangular plastic container, 20 larvae of the larvae were released, and the amount of feeding damage was measured 14 days later under dark conditions to determine the insect control rate.
To determine the insect control rate, after 14 days had elapsed, the larval beetles were taken out, the damaged fabric was pasted on a black mount, and the material was scanned in black and white. This was digitized in pixel units using image analysis software (Image J), and comparison processing of the eating damage area of the disk was performed. This operation was repeated four times and the average insect control rate (%) was determined.

As a result, the feeding damage area in the test area was 16 to 312 pixels for the wool fabric area of 5883 pixels, and the feeding damage area in the control area was 2464 to 4924 pixels, and the average insect protection calculated using the following formula. The rate was 96.9%.
The insect control rate was calculated using the following formula.
Insect control rate = (1 - feeding damage area in test area / feeding damage area in control area) x 100 (%)

Example 11
<Insect repellent effect against Dermatophagoides mites>
A filter paper (ADVANTEC No. 2) with a diameter of 36 mm was placed on an aluminum foil folded into a bellows shape, and the amount of caryophyllene dioxide treated on the filter paper was adjusted to be 0.03 mg/cm ² and 0.6 mg/cm ² . 0.2 mL of an acetone solution containing caryophyllene dioxide was added dropwise and air-dried for 4 minutes in a fume hood to prepare a test section.
A control plot was prepared by dropping the same amount of acetone onto a filter paper of the same size and air drying it.
A test plot was placed in a petri dish (diameter 38 mm), and 0.01 g of a mite breeding medium (MF powder feed (manufactured by Oriental Yeast Co., Ltd.) mixed in a ratio of 1:1 with dry yeast) was placed in the center as an attraction source.

Inside the resin container (inner dimensions 42cm x 32cm, height 15cm) is an adhesive sheet (14.8cm x 21.0cm strong adhesive double-sided adhesive sheet A4, VAN-SONIC CO. LTD) to prevent dust mites from escaping and for humidity adjustment. A saturated saline solution was installed.
Put 6g of a mite culture medium prepared at 5,000 ticks/g into a petri dish (diameter 90 mm), place the above-mentioned small petri dish in the center on an adhesive sheet inside a resin container, cover with a plastic bag, and conduct the test. It started. During the test, the room temperature was 25±1°C, and the test was kept in total darkness.
24 hours after the start of the test, the number of surviving mites that had invaded the petri dish was investigated. Each treatment area was tested four times, and the average insect control rate (%) was calculated using the following formula.
Insect control rate = (1 - average number of invading mites in test area/average number of invading mites in control area)
×100(%)
(However, if it is a negative value, it will be treated as 0%)
The results are shown in Table 6.

That is, the present invention is a persistent insect repellent for any one or more of the following insects: ants, burrs, weevils, flies, chatter beetles, cockroaches, mosquitoes, cutworms, and mites, which contains caryophyllene dioxide as an active ingredient.

The present invention also provides a persistent insect repellent composition for any one or more insects such as ants, burs, weevils, flies, chatter beetles, cockroaches, mosquitoes, cutworms, and mites, which contains caryophyllene dioxide.

Further, the present invention provides a method for controlling the insects in the growth area by applying caryophyllene dioxide to the growth area of one or more insects such as ants, burrs, black weevils, flies, chatter beetles, cockroaches, mosquitoes, cutworms, or mites. This is an insect control method that includes sustaining the insect repellent effect .

Claims (3)

An insect repellent containing caryophylline dioxide as an active ingredient. An insect repellent composition containing caryophylline dioxide. An insect control method comprising applying caryophyllene dioxide to the insect growth area.