JPH0224245B2 - - Google Patents

Description

[Detailed description of the invention]

INDUSTRIAL APPLICATION FIELD The present invention relates to a novel sublimable insect repellent composition. More specifically, the present invention relates to an inexpensive and practical sublimable insect repellent composition that is highly safe for the human body, has excellent antifeeding activity against textile pests, and has excellent sustainability of its effect. It is. Conventional technology Conventionally, naphthalene, sagebrush, p-dichlorobenzene, etc. have been used as insect repellents against clothing pests, and among them, p-dichlorobenzene is the most widely used because it has a strong insecticidal effect and is inexpensive. It is used. However, p-dichlorobenzene is a type of organic chlorine-based drug, and there is a risk that it may accumulate in living organisms and cause harm, so its use is becoming regulated. The use of organic chlorine agents aldrin and teldrin, which are used as insect repellents for textile processing, is already prohibited. Therefore, in recent years, extensive research has been conducted to develop insect repellents or repellents that are harmless to the human body in place of p-dichlorobenzene, and many new compounds and drug combinations have been proposed. For example, insect repellents for wool containing as active ingredients triisopropyl-s-trioxane or tri-tert-butyl-s-trioxane and combinations of linalool, anethole, menthol, cinnamaldehyde, thymol, eugenol, or derivatives thereof (JP-A-Show 50-24436), an insect repellent containing a cyclic compound having 10 carbon atoms and an ether bond as an active ingredient (Japanese Unexamined Patent Publication No. 110823/1982), adamantane, sublimable hydrocarbons, and sublimable or volatile (Japanese Patent Laid-Open No. 53-121936), an insect repellent containing a combination of naphthalene and thymol as an active ingredient (Japanese Patent Laid-Open No. 109938/1989), naphthalene and thymol; An insect repellent for clothing containing a combination of -isopropyl-5-methylphenol as an active ingredient (Japanese Patent Laid-Open No. 54-32620), an insect repellent for clothing containing acetoxime as the main ingredient (Japanese Patent Laid-Open No. 101425-1972) , an insect repellent containing as an active ingredient an aromatic compound having a substituent such as a carbon chain having a branch at the α-position
110321) and aromatic insect repellents containing l-carvone as an active ingredient (Japanese Unexamined Patent Application Publication No. 1982-19229). However, all of these insect repellents contain p-
Compared to dichlorobenzene, it has drawbacks such as being more expensive, its insect repellent effect being significantly inferior, its persistence being poor due to its high volatility, and its deterioration over time being significant. No, no. On the other hand, camphor is an insect repellent that has been used for a long time and is highly safe, and is in high demand especially as an insect repellent for Japanese clothing. There is a problem that it is lower than chlorobenzene etc. Therefore, various synergists for enhancing the insect repellent efficacy of camphor have been studied. Among these synergists, diphenyl (Japanese Patent No. 1262399)
and dihydroacetic acid (Japanese Patent No. 1247229),
Although it is an excellent synergistic insect repellent with a large synergistic insect repellent effect against camphor, the former has a large melting point drop with camphor, and if the two are mixed and left for a long time, it will liquefy even at room temperature, causing contamination. The latter has no problem in terms of liquefaction, but even the high-purity products currently available as industrial chemicals are colored pale yellow and contain α and β-
Due to the presence of unsaturated carbonyl groups, there is a problem of deterioration when stored for a long period of time. Problems to be Solved by the Invention Under these circumstances, the present invention provides a method that is highly safe for the human body, has excellent anti-feeding activity against textile pests, and does not deteriorate over a long period of time. The purpose of this invention is to provide an inexpensive and practical sublimable insect repellent composition with excellent long-lasting effects. Means for Solving the Problems As a result of extensive research in order to develop a practical insect repellent composition having the above-mentioned excellent properties, the present inventor found that camphor is an odorless, non-toxic crystal.
By combining dimethyl fumarate, which has a relatively high melting point and is excellent in suppressing feeding damage against textile pests, and adding cyclohexanone oxime, diphenylene oxide, and p-hydroxybenzoic acid ester as synergists, It was discovered that the insecticidal power was significantly enhanced and the objective could be achieved, and based on this knowledge, the present invention was completed. That is, the present invention uses a combination of (A) camphor, (B) dimethyl fumarate, and (C) at least one selected from cyclohexanone oxime, diphenylene oxide, and p-hydroxybenzoic acid ester as an active ingredient. The present invention provides a sublimable insect repellent composition. The present invention will be explained in detail below. In the composition of the present invention, dimethyl fumarate used as component (B) has a melting point of 102°C and a boiling point of 193°C/
It is a colorless crystalline solid of 760 mmHg, and has an acute oral toxicity LD ₅₀ value of 2240 mg/Kg for rats and a skin toxicity LD ₅₀ value of 1250 mg/Kg for rabbits, making it a highly safe and stable compound. This product can be easily produced, for example, by reacting fumaric acid and methyl alcohol in the presence of an esterification catalyst. This dimethyl fumarate has an excellent effect of suppressing feeding damage to textile pests, but has the disadvantage that its insecticidal power is somewhat weak. Therefore, in the composition of the present invention, in order to further enhance the insecticidal power in combination with camphor, component (C), namely cyclohexanone oxime, diphenylene oxide and p-hydroxybenzoic acid ester, is used as a synergist. At least one selected from among them is used. The cyclohexanone oxime has a melting point of 89-91°C,
It is a white crystal with a boiling point of 206-210°C and can be easily produced by converting cyclohexanone into an oxime. This substance is also a raw material for 6-nylon, and is a compound that can be obtained at an extremely low cost. This cyclohexanone oxime has virtually no insecticidal effect in its vapor, but when combined with the mixture of camphor and dimethyl fumarate, its insecticidal effect is significantly enhanced. On the other hand, diphenylene oxide has a melting point of 86℃ and a boiling point of
It is a colorless crystal at 287℃, and has no mutagenicity regardless of the presence or absence of metabolic activation, and the acute oral toxicity _LD50 value for rats is 10g/
Kg or more, it is a highly safe and stable compound. This product is a furan derivative and is present in tar, and can be obtained, for example, by decrystallizing, deacidifying, and desalting tar heavy oil, and then distilling it. The vapor of this diphenylene oxide has little insecticidal effect, but when combined with the mixture of camphor and dimethyl fumarate, its insecticidal effect is significantly enhanced. Furthermore, p-hydroxybenzoic acid ester is
It is a compound that has been conventionally used as a food preservative and anti-mold agent, and its safety has been confirmed. The esters are preferably methyl ester, ethyl ester, or n-propyl ester from the viewpoint of melting point and vapor pressure. Table 1 shows the melting points and toxicity of these lower esters.

[Table] The blending ratio of each of the above components in the composition of the present invention may be such that it increases the insecticidal efficacy of camphor and dimethyl fumarate and provides long-term insecticidal and feeding damage prevention effects. , there is no particular limit, but usually Kamphua 50-95
% by weight, dimethyl fumarate from 1 to 20% by weight and the synergist from 1 to 30% by weight. If it deviates from this range, the effects of the present invention will not be sufficiently exhibited, which is not preferable. In addition to these essential components, the composition of the present invention can also contain a moisture-proofing agent such as silica gel or calcium chloride. Further, the composition may be used in a state in which each component is homogeneously mixed, or it may be used after being molded into a desired shape by a tabletting method, melt-solidification method, etc., if necessary. . Effects of the Invention The sublimable insect repellent composition of the present invention contains as an active ingredient a combination of camphor and dimethyl fumarate with cyclohexanone oxime, diphenylene oxide, and p-hydroxybenzoic acid ester as synergists. It is an inexpensive practical drug that is highly safe for the human body, has excellent feeding inhibiting properties against textile pests, does not deteriorate over a long period of time, and has excellent long-lasting effects. This composition has excellent insect repellent and insecticidal effects against textile pests, so it is effective for repelling and killing textile products such as clothing and carpets, silk, and wool.It also has a fungicidal effect. Therefore, its sublimation property can be used to treat objects and places that are not suitable for direct treatment with chemicals such as surface treatment and internal treatment, such as food packaging materials, pharmaceutical packaging materials, textile products such as clothing, leather raw materials, and It is also useful for preventing mold on products, agricultural products, etc., indoors in cupboards, drawers, closets, bathrooms, furniture, clothing cases, etc., and outdoors in warehouses, greenhouses such as vinyl houses, etc. Examples Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples in any way. Example 1 200 mg of a mixture of 5 parts by weight of cyclohexanone oxime, 5 parts by weight of dimethyl fumarate, and 90 parts by weight of camphor was placed at the bottom of a 0.5 mm wide-mouth bottle, and 10 burr (Tinea Pellionella L.) larvae and wool standard test were placed above it. The basket containing the cloth was fixed. Next, seal the bottle and place it in a constant temperature and humidity chamber at a temperature of 30℃ and humidity of 65% for 5 minutes.
After leaving it for a day, the number of dead insects was counted. In addition, a mixture of cyclohexanone oxime and dimethyl fumarate, which was conducted in parallel for comparison,
The measurement results for a mixture of camphor and dimethyl fumarate, dimethyl fumarate alone, and camphor alone are also shown in Table 2. The values in the table are average values obtained by conducting the test three times.

【table】

[Table] Example 2 Anthrenus
verbasci L.) larvae were tested in the same manner as in the example. The results are shown in Table 3.

【table】

[Table] Example 3 Place 400 mg of a mixture of 10 parts by weight of cyclohexanone oxime, 5 parts by weight of dimethyl fumarate, and 85 parts by weight of camphor at the bottom of the wide-mouthed bottle in Example 3 1, and above it place 10 Japanese cutworms with an average weight of 90 mg per head. A cage containing 10 (Attagenus Piceus Oliv.) larvae and a wool standard test cloth was fixed. Next, the bottles were sealed and left in a constant temperature and humidity chamber at 25°C and 65% humidity for 20 days, after which the number of dead insects was counted and the amount of damage to the fabric was measured. For comparison, dimethyl fumarate alone,
Camphor alone and a mixture of dimethyl fumarate and camphor were simultaneously tested. The test was conducted three times, and the average values are shown in Table 4.

【table】

Claims (1)

[Claims] 1. A sublimation insect repellent containing as an active ingredient a combination of (A) camphor, (B) dimethyl fumarate, and (C) at least one selected from cyclohexanone oxime, diphenylene oxide, and p-hydroxybenzoic acid ester. agent composition.