JP2019069934A - Pest repellent - Google Patents

Abstract

To provide a pest repellent having excellent safety and a high pest repellent effect.SOLUTION: A pest repellent contains hexyl 4-hydroxybenzoate represented by formula (1).SELECTED DRAWING: None

Description

  The present invention relates to pest repellents comprising hexyl 4-hydroxybenzoate.

  Recently, various damage caused by pests have been reported. For example, gastropod pests such as slugs and snails poison new shoots and flower buds of plants, and vectors such as mosquitoes spread diseases such as malaria and zika fever by mediating pathogens, and pests such as ticks and cockroaches are allergic It can be a cause. Therefore, various methods using a control agent, a repellent agent, etc. are examined as these pest control measures.

  As measures against gastropod pests such as slugs, a method is known in which an attractive poison bait containing metaaldehyde as an active ingredient is placed in the habitat of gastropod pests (Patent Document 1). However, there is a danger that gastropod pests can not be effective unless they feed on the bait, and there is a risk of poisoning death if they adversely affect neighboring plants, or if dogs or cats mistakenly lick on the bait.

  In addition, cast products or sheets that carry or contain a copper compound that has an repellent effect against gastropod pests are installed in the bottom of a flowerpot, the top of a flowerpot stand, the lower wall of a house, a kitchen, etc. A method is disclosed (Patent Document 2). However, repellents using copper compounds are less effective, and there is concern that copper ions may flow out when it rains, which may adversely affect the environment.

  As a countermeasure against mosquitoes, for example, a method of spraying a repellent agent such as DEET (N, N-diethyl-1,3-methylbenzamide) is known. DEET has a very high repellent effect against mosquitoes, and as of 2017, high concentration (DEET 30%) products have been approved in Japan for pest repellents for humans. However, when repellent containing DEET is repeatedly used in the skin at high concentration, health damage causing allergy and rough skin have been reported, and it is also reported that continuous high intake in animals has shown neurotoxicity. There is also a report.

  On the other hand, parabens (4-hydroxybenzoic acid esters) widely used as preservatives for cosmetics and pharmaceuticals have high safety and low skin irritation, and not only antibacterial and antifungal effects but also mites Is also known to have a repellent effect (Patent Document 3).

  However, although parabens having a lower alkyl group having 1 to 4 carbon atoms such as methylparaben and butylparaben are excellent in safety, the repellent effect against pests such as mites has been insufficient.

JP-A-8-175906 JP-A-8-59417 Japanese Patent Application Laid-Open No. 60-008202

  An object of the present invention is to provide a pest repellent agent which is excellent in safety and has a high pest repellent effect. Another object of the present invention is to provide a pest repellent method which is excellent in safety and high in pest repellent effect.

  As a result of intensive studies on pest repellents, the present inventors have found that hexyl 4-hydroxybenzoate (hexyl paraben) has a high repellent effect against pests such as slugs and ticks, and complete the present invention. It reached.

That is, the present invention provides a pest repellent containing hexyl 4-hydroxybenzoate represented by the formula (1).

  According to the pest repellent agent of the present invention, it is possible to obtain a high repellent effect against pests such as slugs and mites while being excellent in safety.

It is a photograph of the test area of Example 3, and a blank filter paper. It is a photograph of the test area of the comparative example 5, and a blank filter paper. It is a photograph of the test area of the comparative example 6, and a blank filter paper.

  The hexyl 4-hydroxybenzoate represented by the formula (1) used in the present invention may be a commercially available one, and for example, it is described in Japanese Patent Application No. 2016-240132 previously proposed by the applicant of the present invention. As obtained, one obtained by reacting 4-hydroxybenzoic acid with 1-hexanol in the presence of an acid catalyst may be used.

  The pest repellent agent of the present invention contains hexyl 4-hydroxybenzoate as an active ingredient. Hexyl 4-hydroxybenzoate is dissolved or dispersed in various solvents, mixed with or adsorbed on a solid carrier, and the aerosol agent, pump agent, liquid agent, coating agent, matting agent, sheet agent, tape agent It can be prepared into a dosage form such as powder, granule, gel, cream and the like, and used as a pest repellent.

  As the solvent, water, alcohols such as methyl alcohol and ethyl alcohol, ketones such as acetone and methyl ethyl ketone, ethers such as tetrahydrofuran and dioxane, aliphatic hydrocarbons such as hexane, kerosene and paraffin, benzene, toluene and the like One or more kinds of aromatic hydrocarbons and esters such as ethyl acetate and hexyl laurate can be used, and among these, water is preferable because it has less influence on the human body and the environment.

  When hexyl 4-hydroxybenzoate is dissolved or dispersed in a solvent to form the pest repellent of the present invention, the content of hexyl 4-hydroxybenzoate in the pest repellent is preferably relative to the mass of the pest repellent It is 0.1 to 50% by mass, more preferably 1 to 20% by mass.

  As a solid carrier, for example, mineral substances such as kaolin, talc, bentonite, clay, diatomaceous earth, calcium carbonate, silica, zeolite, etc. or mineral powders; Plant powders such as wood flour, soybean flour, flour, starch flour; Plastics such as polyamides, acrylics and polyesters; Synthetic fibers made of the plastics; Rubbers such as polybutadienes or powders thereof; Sublimable powders such as camphor, naphthalene, paradichlorobenzene, trioxane, cyclododecane and adamantane; Natural fibers such as linters and pulps Animal and vegetable fibers such as wool, cotton and silk; and regenerated fibers such as rayon. In addition, paper obtained from glass fiber, inorganic fiber such as asbestos, etc., non-woven fabric, etc. can be used as the solid carrier.

  When hexyl 4-hydroxybenzoate is mixed or adsorbed with a solid carrier to be the pest repellent of the present invention, the content of hexyl 4-hydroxybenzoate in the pest repellent is preferably relative to the mass of the pest repellent Is 0.1 to 50% by mass, more preferably 1 to 20% by mass.

  The pest repellent agent of the present invention is, if necessary, an optional component such as a film-forming agent, a surfactant, a wetting agent, a stabilizer, a propellant, a bactericidal agent, a fungicide, a fragrance, a water repellent and an oil repellent A may be contained. Examples of the film-forming agent include ethyl cellulose, hydroxypropyl cellulose, silicone, acrylic resin, chlorinated rubber, petroleum resin, methyl cellulose, vinyl acetate, polyvinyl alcohol, latex emulsion and the like. Examples of surfactants include aliphatic monocarboxylic acid salts, linear alkylbenzene sulfonic acid salts, alkyl sulfates, sorbitan fatty acid esters, polyoxyethylene alkyl ethers, polyethylene glycol fatty acid esters, fatty acid alkanolamides and the like. . As the wetting agent, for example, casein, gelatin, alginic acid, carboxymethylcellulose and the like can be mentioned. Examples of the propellant include stabilizers such as butylhydroxyanisole, dibutylhydroxytoluene, tocopherol and γ-oryzanol, liquefied petroleum gas, dimethyl ether, fluorocarbon, compressed gas and the like. Examples of bactericidal agents include parachlorometaxylate, and examples of flavoring agents include lemon-based, rose-based and green-based. Water repellent and oil repellent agents include waxes, fats and oils, metal soaps, and fluorine-based oil repellents. An oil agent etc. are mentioned.

  When such an optional component A is blended, the blending amount is preferably 0.1 to 5% by mass, more preferably 0.2 to 4% by mass, based on the mass of the pest repellent Preferably it is 0.5-3 mass%. The above-mentioned optional component A can be blended in preparing the above-mentioned dosage form.

  The pest repellent agent of the present invention optionally contains, in addition to hexyl 4-hydroxybenzoate, optional component B such as an insecticide, other pest control agent or repellent agent in order to enhance the pest repellent action. You may Examples of the insecticide include pyrethroid insecticides, carbamate insecticides, organophosphorus insecticides, fluorine insecticides, insect growth regulators and the like, and examples of the repellent agent include N-diethyl-m- Tolu-amide, dimethyl phthalate and the like can be mentioned.

  When such an optional component B is blended, the blending amount is preferably 1 to 80% by mass, more preferably 5 to 70% by mass, based on the mass of hexyl 4-hydroxybenzoate, more preferably Is 8 to 65% by mass. The above-mentioned optional component B can be blended in preparing the above-mentioned dosage form.

  Pests to be repelled by the pest repellent agent of the present invention include: slugs, snails, snails, snails, mites, cockroaches, bees, flies, flies, flies, flies, flies, flies, flies, flies, bedbugs, bedbugs, flies, lice, parrots, ants, termites , One or more species selected from the group consisting of leafhoppers, whitefly, scorpion rickets, crayfish, dango worms and dwarf insects. Among them, one or more selected from the group consisting of slugs, mites and termites are suitably repelled, and slugs are more suitably repelled.

  By applying the pest repellent agent of the present invention to an application subject or a predetermined site thereof (hereinafter referred to simply as the application subject) or the periphery thereof, pests can be repelled from the application subject or the periphery thereof. In addition, the pest repellent agent may be carried on a carrier such as a non-woven fabric, a sheet, an inorganic carrier, etc., and they may be installed at a place where pests are desired to be repelled.

  The objects to be applied include, for example, a flowerpot and a planter, the bottom or the periphery of a nursery, the space between the bottom and the soil, the inside of a drain, the bottom of dead leaves, and the like. In addition, organisms themselves which can be a source of nourishing pests or the periphery of the organisms are also included in the application object in the present invention. For example, agricultural products themselves, fields in which they are grown, orchards, flower beds in which flowers are grown, etc. can be mentioned.

  Moreover, as an application place of a pest repellent agent indoors, kitchens, such as a general household or a cafeteria, a washroom, a veranda, storage, etc. are mentioned.

  Examples of the method for applying the pest repellent agent of the present invention to the application subject include spreading, spraying or application. The application amount of the pest repellent agent of the present invention can be appropriately determined according to the type of repellent agent, application method and application site.

  In the pest repellent agent of the present invention, the content of hexyl 4-hydroxybenzoate represented by the formula (1) can be appropriately determined according to the application form of the pest repellent agent, the application method, and the application site. For example, when used as a liquid such as a stock solution of aerosol agent or pump agent, it preferably contains 0.1 to 50% by mass, more preferably 1 to 20% by mass of hexyl 4-hydroxybenzoate in the pest repellent agent. It can be done. When used on a solid carrier such as non-woven fabric, preferably 0.1% by mass to 50% by mass, more preferably 1 to 30% by mass, and still more preferably hexyl 4-hydroxybenzoate in the pest repellent agent. 2 to 20% by mass can be contained. The solid support to be used can be optionally selected, for example, from the above-mentioned materials according to the application site and application method.

Reference Example 1 Preparation of hexyl paraben (hexyl 4-hydroxybenzoate) 91.2 g of 4-hydroxybenzoic acid in a 300 mL scale four-necked flask (reaction vessel) equipped with a stirrer, temperature sensor and Dean-Stark apparatus (0.66 mol), 101.1 g (0.99 mol) of 1-hexanol and 1.8 g of p-toluenesulfonic acid monohydrate as a catalyst are added, and the temperature is raised to 145 ° C. under a nitrogen stream of 38 mL / min The mixture was reacted at the same temperature for 6 hours to obtain a crude composition containing hexyl paraben. The mixture was neutralized with 48% sodium hydroxide and purified by distillation to obtain hexyl paraben (purity 99.8 wt%).

Tick Repellent Test [Example 1]
The culture medium (20 g) on which the test ticks were propagated was spread on a 14 × 17 × 2.5 hcm horo bat and placed in a 5 L plastic closed container. The inside of the container was adjusted to a humidity of 95 to 99% with washing water and stored at a temperature of about 27.0 ° C.

On 1.30 g of 10 × 10 cm black drawing paper, 1 ml of each test sample whose concentration is adjusted with acetone so as to be 0.026 mass% of hexylparaben (hexyl 4-hydroxybenzoate) is dropped and air-dried for 10 minutes After that, the black drawing paper was cut into 2.5 cm squares and used as a test area.
As in the case of the test sample, a section treated with only acetone was used as a blank.

  After 30 minutes of juxtaposing the test zone and the blank one by one, the number of ticks crawling on black drawing paper was observed, and the repellent rate was calculated.

Comparative Example 1
The tick repelling test was carried out in the same manner as in Example 1 except that hexyl paraben (hexyl 4-hydroxybenzoate) was changed to butyl paraben (butyl 4-hydroxybenzoate). The results are shown in Table 1.

Comparative Example 2
The tick repelling test was carried out in the same manner as Example 1 except that hexyl paraben (hexyl 4-hydroxybenzoate) was changed to 2-ethylhexyl paraben (2-ethylhexyl 4-hydroxybenzoate). The results are shown in Table 1.

Comparative Example 3
The tick repelling test was carried out in the same manner as in Example 1 except that hexyl paraben (hexyl 4-hydroxybenzoate) was changed to benzyl paraben (benzyl 4-hydroxybenzoate). The results are shown in Table 1.

<Tick used in the test>
Tick 1: The burnt house dust mite Tick 2: the diamondback mite tick

Slug evasion test [Example 2]
86 g of water was added to an Erlenmeyer flask, and 4 g of agar was added thereto with heating to 100 ° C. with stirring. Heating was stopped and an additional 10 g of hexyl paraben (hexyl 4-hydroxybenzoate) was added with stirring. Stirring was stopped, and poured into a 0.5 L vat cooled with ice, followed by cooling for 1 hour to obtain an agar containing 10% by mass of hexyl paraben.

  The obtained agar containing 10% by mass of hexyl paraben was spread on a half of a 140 mm long × 175 mm wide × 14 mm high tray (treated area), and food (cat food) was placed at the center of the tray. In the remaining portion (non-treated area) of the agar-free tray, 10 rats were placed, and the tray was wrapped in a small holed wrap and stored in the dark. The number of slugs in the untreated area and the treated area after 6 hours and 24 hours was observed. Similar tests were performed using agar without hexyl paraben as a blank. The results are shown in Table 2.

Comparative Example 4
46 g of water was added to an Erlenmeyer flask, and 4 g of agar was added thereto with heating to 100 ° C. with stirring. Heating was stopped and an additional 50 g of propyl paraben (propyl 4-hydroxybenzoate) was added with stirring. Stirring was stopped, and after flowing in an ice-cooled 0.5 L vat, it was cooled as it is for 1 hour to obtain agar containing 10% by mass of propylparaben.
Thereafter, the test was performed under the same conditions as in Example 2. The results are shown in Table 2

Termite Repellent Test [Example 3]
A bellows-shaped aluminum foil was placed in a draft, and a 55 mm diameter qualitative filter paper (ADVANTEC) was placed on the aluminum foil. 0.4 mL of hexyl paraben (hexyl 4-hydroxy benzoate) acetone solution previously adjusted to 1.8% w / v was dripped uniformly on the whole single side | surface of filter paper (processing amount 10% w / w). Air-dried in a draft for 3 hours (Hexyl paraben-treated filter paper). As a blank, a filter paper (blank filter paper) in which only acetone was dropped by the same method and dried was prepared.

  In each of two corners (on a diagonal line) of a stainless steel bat (24 cm × 20 cm × height 3 cm), one sheet of each of the hexyl paraben-treated filter paper and the blank filter paper was placed, and 1 mL of tap water was dropped on both filters. In the center of the bat, 30 pestle termites were released, covered with a plastic bag for moisturizing, and left for a further 6 days at 25 ° C. covered with a black plastic bag for light shielding from above. The mass of hexyl paraben-treated filter paper and blank filter paper was measured and the mass loss was calculated. The results are shown in Table 3. The greater the mass loss of the filter paper, the more the filter paper is fed by the termites.

Comparative Example 5
The test was performed in the same manner as in Example 3 except that hexylparaben was changed to butylparaben. The results are shown in Table 3.

Comparative Example 6
The test was performed in the same manner as in Example 3 except that hexylparaben was changed to 4-hydroxybenzoic acid docosyl ester (C22). The results are shown in Table 3.

Claims (5)

Formula (1)
The pest repellent agent containing 4-hydroxyhexyl benzoate represented by these.   Pests include: slugs, snails, sweetfish, mites, cockroaches, bees, flies, fly larvae, mosquitoes, flies, fleas, centipedes, bedbugs, bedbugs, flybacks, moths, agaricus, termites, leafhoppers, whiteflys, scum bees, The pest repellent agent according to claim 1, which is at least one member selected from the group consisting of dango worms and red flour beetles.   The pest repellent agent according to claim 1, wherein the pest is one or more selected from the group consisting of slugs, mites and termites.   A pest repellent method comprising applying the pest repellent agent according to any one of claims 1 to 3 to an application subject or its periphery.   The pest repellent method according to claim 4, wherein the application to the object of application is performed by spreading, spraying or application.