JP2002068906A - Insect pest-repellent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a technique for repelling insect pests containing a hinokitiol compound capable of exhibiting excellent repelling effect on mosquitoes, cockroaches and acarids, and in its turn, exhibiting bactericidal effect, and further, having excellent bactericidal activities against various kinds of bacteria in a wide range. SOLUTION: An insect pest-repellent containing hinokitiol and/or a hinokitiol derivative.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a pest repellent. More specifically, the present invention relates to pest repellents containing hinokitiols, which exhibit an excellent repellent effect against mosquitoes, cockroaches, and mites, and also exhibit an insecticidal effect, and are also excellent in bactericidal activity against a wide variety of fungi.

[0002]

2. Description of the Related Art It has been described in literatures that hinokitiol has repellency against various pests. For example, JP-A-06-40833 discloses that hinokitiol is a tick,
It is described that it has repellent properties against cockroaches and the like, but no specific experimental example regarding repellent properties is shown. In addition, the publication only describes that a wood powder containing hinokitiol is used, and there is no specific description of the mode of hinokitiol existence for expressing a pest repellent effect, such as the concentration of hinokitiol, and hinokitiol is used as a pest. It is hard to say that the technology applied as a repellent has been sufficiently disclosed.

By the way, hinokitiol is unstable to light, and when exposed to light, it is denatured in a short time, losing its effect or causing discoloration. For this reason, light must not be applied during manufacturing, or light must be cut off when it is distributed as a product or when it is lined up in stores.In practice, it must be placed in a light-tight container. Did not. Despite the above-mentioned contrivance, the hinokitiol content may decrease when stored for a long period of time. In addition, since hinokitiol has sublimability, depending on the form of the preparation, there may be a problem that the insect repellent effect is reduced due to scattering.

[0004] In addition, since hinokitiol has the property of being easily colored by metals, particularly iron, when a compounding operation is carried out in a manufacturing apparatus mainly composed of iron, hinokitiol reacts with iron in the material and becomes colored. Sometimes. In this case, a situation sometimes arises in which the material must be changed to a material coated with a resin or the like, or to a material capable of reducing coloring so as not to cause a practical problem. Further, depending on the form of the preparation and the environment in which the preparation is used, coloring may be a problem when the product is used.

That is, hinokitiol has been used in mosquitoes,
Although it is said that it has a repellent effect on pests such as cockroaches and mites, its specific use mode and quantitative effect have not been shown, and therefore, the technology related to pest repellents, especially repellents against mosquitoes, is virtually impossible. Was not disclosed. Further, a technique for avoiding the sublimability of hinokitiol and the coloring property of metals, which sometimes become a problem when hinokitiol is applied as a pest repellent, has not been disclosed yet.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a technique for hinokitiol to quantitatively show the effect of hinokitiol on pests such as mosquitoes, cockroaches and ticks together with the mode of use and to use the hinokitiol as a pest repellent. I do. Further, it is another object of the present invention to provide a technique for avoiding sublimation and coloring by metal, which are sometimes problems in using hinokitiol as a pest repellent.

[0007]

Means for Solving the Problems As a result of diligent studies of the above-mentioned problems, the present inventors quantitatively proved the clear repellent effect of hinokitiol on mosquitoes, cockroaches and mites.
In addition, the inventors have found that the use of a hinokitiol derivative can effectively avoid sublimation, coloring by a metal, and the like, and completed the present invention.

That is, the present invention is as follows. (1) A pest repellent comprising hinokitiol and / or a hinokitiol derivative. (2) The pest repellent according to (1), wherein the pest is one or more selected from the group consisting of mosquitoes, cockroaches, and mites. (3) The pest repellent according to (1) or (2), wherein the hinokitiol derivative is an organic salt, a metal salt or a metal complex of hinokitiol. (4) The pest repellent according to (1) or (2), wherein the hinokitiol derivative is an acyl compound or glycoside of hinokitiol.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Hinokitiol (4-isopropyltropolone) in the present invention is a compound represented by the following formula (1).

[0010]

Embedded image

Hinokitiol is a natural substance contained in the essential oil of Taiwan Hinoki and Aomori Hiba, and is a very useful crystalline substance having excellent antibacterial properties against a wide variety of bacterial species. It is also known that hinokitiol is extremely resistant to resistant bacteria. Hinokitiol has also recently been produced by chemical synthesis and used for various applications. The hinokitiol derivative referred to in the present invention is not particularly limited as long as hinokitiol can be derived by general chemical transformation or the like. Or metal salt or metal complex, hinokitiol acyl, hinokitiol glycoside, hinokitiol cyclodextrin or clathrate of layered inorganic compound, hinokitiol organic wall or inorganic wall microcapsule, hinokitiol organic or inorganic particle impregnated. preferable. The raw material hinokitiol, which is the source of the derivative of hinokitiol, may be a natural extract or a chemically synthesized product.

The organic salt of hinokitiol referred to in the present invention is an organic amine salt such as triethanolamine. The metal salt or metal complex of hinokitiol in the present invention is represented by the following formula (2). Here, M represents a metal element, for example, Na,
Examples thereof include K, Mg, Ca, Zn, Ni, Cu, Al, and Ag. In the formula, n represents the valence of the metal.

[0013]

Embedded image

The method for producing the metal salt and metal complex of hinokitiol is not particularly limited, and may be synthesized by a known method. For example, by reacting hinokitiol with sodium hydroxide or potassium hydroxide, a sodium or potassium salt of hinokitiol can be synthesized, or hinokitiol alone or a sodium or potassium salt of hinokitiol can be converted to copper chloride, zinc chloride, calcium chloride. Inorganic salts, such as copper stearate, zinc stearate,
By reacting with an organic salt such as calcium stearate, a metal complex of hinokitiol can be synthesized. When producing a pest repellent, a metal salt or a metal complex of hinokitiol may be once synthesized and then compounded, or when producing a pest repellent, hinokitiol and Na, K, Mg, Ca,
Inorganic salts and organic salts of Zn, Ni, Cu, Al and Ag may be mixed together.

The term "acylated hinokitiol" as used in the present invention refers to an hinokitiol obtained by substituting a hydrogen atom of a hydroxyl group of an hinokitiol with an acyl group, and represented by the following formula (3) or (4):
It is represented by Here, R ₁ represents a substituted or unsubstituted alkyl group.

[0016]

Embedded image

[0017]

Embedded image

The conversion of hinokitiol into an acyl form may be carried out by a general method, for example, a method of reacting an acid chloride or ester of a carboxylic acid such as a fatty acid with hinokitiol, or a method of reacting a carboxylic acid such as a fatty acid with an enzyme. Examples thereof include a method of reacting (esterifying) an acid with hinokitiol. For example, butyric acid, valeric acid, caproic acid,
Octanoic acid, capric acid, lauric acid, myristic acid,
Method of reacting hinokitiol with acid chlorides such as unsaturated fatty acids such as palmitic acid and stearic acid, oleic acid and linoleic acid, and esterification of these acids with hinokitiol in the presence of enzymes such as lipase and esterase And the like.

The term "hinokitiol glycoside" as used in the present invention means a hydroxyl group of hinokitiol and a saccharide (R ₂ OH).
Is formed by dehydration-condensation of the hydroxyl group of the above to form an ether bond, and is represented by the following formula (5) or (6).

[0020]

Embedded image

[0021]

Embedded image

A saccharide (R ₂ O) bound to hinokitiol
H) is not particularly limited and general ones may be used, for example, glucose, fructose, mannose,
Monosaccharides such as hexoses such as galactose, pentoses such as xylose and arabinose, disaccharides such as primeverose, gentiobiose, rutinose, strophantobiose and cellobiose, and other polysaccharides and derivatives thereof can be used.

In the present invention, hinokitiol or a derivative thereof is an essential component, but it is preferable to use a hinokitiol derivative in terms of excellent light stability and reduced sublimability. Examples of hinokitiol derivatives include organic or metal salts or metal complexes of hinokitiol, acyl forms of hinokitiol, glycosides of hinokitiol, clathrates of cyclodextrins and layered inorganic compounds of hinokitiol, organic or inorganic wall microcapsules of hinokitiol, Organic or inorganic particles impregnated with hinokitiol may be mentioned.

The raw material hinokitiol from which the hinokitiol derivative is derived may be a natural extract or a chemically synthesized product. Among the hinokitiol derivatives, an organic salt, a metal salt or a metal complex of hinokitiol can be easily synthesized from inexpensive raw materials, and is preferable as the hinokitiol derivative of the present invention. In the present invention, the compounding amount of hinokitiol and / or hinokitiol derivative is 0.00 depending on the use and form (microcapsule, organic or inorganic substance support, etc.).
It can be set arbitrarily in the range of 01 to 100 wt%. The pest repellent of the present invention is particularly effective against mosquitoes, cockroaches and mites, but has been found to be especially effective against mosquitoes.

In the pest repellent of the present invention, hinokitiol or a derivative thereof is an essential component, but one or more selected from the following components may be co-blended as appropriate. Isopenpinerine, bergapten, zantoxin, coxagine, dihydrocoxagine, diethyltoluamide (De
et), dimethyl terephthalate, diethyl terephthalate, dibutyl phthalate, benzyl benzoate, M
GK11, MGK326, Dabtrex, Indalone, 2-ethyl-1,3-hexanediol, 2-butyl-2-ethyl-1,3-propanediol, dimethyl carbate, propylmandelate, propyl N, N-
Diethylsuccinate, benzamide, 0-chloro-
General-purpose pest repellents such as N, N-diethylbenzamide, isobornyl thiocyanoacetate, phenyl salicylate, benzyl salicylate, dibutyl sebacate, paradichlorobenzene;

Pyrethrin, cinerin, jasmolin, allethrin, phthalthrin, resmethrin, flammethrin, phenothrin, permethrin, imibrotrine, cyphenothrin, tralomethrin, etofenprox, praletrin, cyfluthrin, silafluofen,
Pyrethroids such as bifenthrin, flumethrin, fluvalinate, deltamethrin; natural ingredients such as α-pinene, geraniol, citronellal, camphor, linalool, casinole;

Pine, cypress, camphor, hiba, citronella, rose, geranium, cedarwood, lavender, anise, spearmint, nutmeg, peppermint,
Cinnamon, clove, eucalyptus, garlic, marjoram, palmarosa, cumin, coriander, origanum, peppermint, lemon peel, rosemary and other plant essential oils;

The pest repellent of the present invention can be prepared in a solvent (e.g., ethanol, acetone, water, toluene, xylene, acetate, etc.) suitable for the intended use in a concentration suitable for the intended use (0.001 to 95).
%) Can be applied to a target article by a method such as spraying or dipping. For example, the solution is woven, knitted, non-woven, leather made of natural or synthetic material,
By spraying or impregnating a sheet-like material such as felt or paper, a pest repellent sheet can be obtained, which can be used for repelling pests in kitchens, clothes dancing, and the like.

The pest repellent of the present invention can be used in various forms such as fibers, leather, wood, building materials, paints / adhesives, plastic films, daily necessities, electric products, paper / pulp, oils, foods, etc. It can be put to practical use. The following is an example. In the form of microcapsules containing melamine, urethane, gelatin, silica or the like as an encapsulating agent, silica gel, a form supported on an inorganic substance such as zeolite, a form encapsulated in cyclodextrin or a layered inorganic compound, or in the form of a solution The pest repellent of the present invention is polyester, polyamide, polyurethane, polyvinylidene chloride, polyvinyl chloride, rayon, cupra, cotton,
It can be attached to fibers such as hemp and silk to obtain a pest repellent fiber product. For example, when applied to pantyhose, lower limbs can be effectively prevented from being bitten by mosquitoes. It is also effective when applied to mosquito nets.

In the fiber spinning step, the pest repellent of the present invention can be added to the fiber to obtain a pest repellent fiber product. For example, the pest repellent of the present invention is kneaded in the process of spinning synthetic fibers such as polyester or polyamide, or the pest repellent of the present invention is mixed with a spinning solution in dry spinning such as polyurethane, rayon, or cupra. It is possible. Nonwoven fabric, wrapping the pest repellent of the present invention with a breathable material such as paper, and function as a pest repellent such as mites if placed in clothes dance or closet,
In the kitchen etc., it can be used as a cockroach repellent. In addition, if the pest repellent of the present invention is applied to a tatami mat, a tick repelling effect on the tatami mat can be obtained. Moreover, in these cases, the excellent antibacterial properties inherent to hinokitiol are also exhibited, the occurrence of fungi such as mold is suppressed, and a sanitary environment is ensured for both pests and fungi.

If the pest repellent of the present invention is applied to a vacuum cleaner dust bag, it is possible to eliminate mites contained in the inhaled dust in the bag. If the pest repellent of the present invention is applied to the paint, not only can the pest repellency be imparted to the coating film,
The excellent antibacterial property inherent to hinokitiol can also be imparted at the same time. When applied to films and resins such as polyethylene, polypropylene, polyvinyl chloride, polyvinylidene chloride, cellophane, polyester, and polyamide, the insect repellent effect and the antibacterial property can be imparted to them.

If the pest repellent of the present invention or a substance impregnated in a gel-like material is installed in a living room, bathroom, toilet, or the like, a pest repellent and antibacterial atmosphere can be obtained.
The use and form of use of the pest repellent of the present invention are not limited to the above examples, and there are various other uses and forms of use. Next, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto. In addition, all parts and% in the compounding amount and the like are based on mass.

[0033]

Examples 1 and 2 and Comparative Example 1 A mouse was placed in a stainless steel fixed wire mesh (6 × 12.5 cm = 150 cm ² ).
The chemical solution was sprayed on both sides so as to be 1.5 ml / 150 cm ² . After air-drying for 1 hour, this was
pipiens pallens) was hung on the ceiling of a cage in which about 25 test insects (animals anesthetized with diethyl ether or carbonic acid and only female adults were selected in advance) were released, and after 2, 4, 6, 8, and 24 hours The number of blood sucked is counted, and the blood sucking rate (= tested insect / blood-tested insect × 100)
I asked. An untreated section was provided as a control section. The test was performed twice and the average was taken. The results are shown in Table 1.

The sprayed hinokitiol solution showed a clear mosquito repellent effect as compared with the control. Particularly, those sprayed with a high-concentration (20%) hinokitiol solution maintain an excellent mosquito repellent effect.

[0035]

Examples 3 to 12, Comparative Examples 2 to 11 Veneer plates (external dimensions:
3.5 × 15cm, inner surface: 3 × 15cm)
A cockroach shelter with a triangular pole (hiding place)
Used as Hinokitiol was diluted with ethanol so that the amount of the active ingredient was 1 g / 50 ml and 10 g / 50 ml. This diluted solution is treated at a processing volume of 50 ml / m.
After evenly dropping the inner surface of the shelter so as to be ² , the shelter was air-dried all day and night (sample shelter). On the other hand, another shelter was similarly treated with ethanol to obtain a control shelter.

In order to prevent cockroaches from escaping, a plastic container (30 × 65 × 20Hc) coated with butter inside
m), water and a bait (solid feed: solid MF manufactured by Oriental Yeast Co., Ltd.) are installed in the center of the m), and a predetermined number of test insects (Blattula germanica, Blattellellamanica)
15 male and female adults) were released. In the juxtaposition test, the sample shelter and the control shelter were placed in the above-mentioned plastic container so as to face each other with water and food therebetween. In the single test, only the sample shelter was placed. After 24 hours,
The latent number of the test insects inside the shelter was counted. In addition, the number of knockdowns (upturned) or deceased individuals were recorded at each observation. The number of cockroaches outside the shelter was also recorded.

Using the following equation, the number of latencies to each shelter was calculated, and the repellent rate against German cockroaches was calculated. Latency (%) = (number of cockroaches in the sample shelter) / (total number of cockroaches tested) x 100 Repellency (%) = 100-latency (%) Note that the juxtaposition test was performed three times and the single test was performed four times. Repeated. The results are shown in Tables 2 to 4.

Hinokitiol was found to have a clear cockroach repellent effect. Particularly when the hinokitiol concentration is high (10 g / m ² ), 99
% Or more of the cockroach repellent effect was recognized.

[0039]

Examples 13 to 15 and Comparative Example 12 1 ml of a solution of hinokitiol in acetone was applied to 5 cm black paper, air-dried at room temperature for 2 hours, and then cut into 2.5 cm squares (drug-treated paper).
On the other hand, black paper cut into 3 cm squares is used for Dermatophagoides farinae (De
rmatophagoides farinaeHug
Hes) was placed on a growth medium, the above-mentioned drug-treated paper was placed thereon, the number of Dermatophagoides farinae crawling was counted, and the repellency index was determined by the following equation. However, if the repulsion index is obtained as a negative value, it is set to 0. Repellent index = {(CT) / C} × 100 (C is the number of mites crawling in the control group, T is the number of mites crawling in the treated group) The results are shown in Table 5. Hinokitiol had a clear mite repellent effect.

[0040]

Examples 16 and 17 and Comparative Example 13 A filter paper was cut into a 10 cm square, an acetone solution of hinokitiol was applied, and air-dried at room temperature for 2 hours. Then cut into 5 × 10 cm, 2
It was folded and made into a bag shape with clips on both sides. Test mite (Dermatophagoid, Dermatophagoid)
es farinae Hughes) was collected with a small brush, placed in the above-described filter paper bag, and capped with an eyeball clip to prevent mites from escaping. About 20 ticks were introduced.

The filter paper bag containing the test mites was placed at a temperature of 25 ° C.
The sample was stored under conditions of a relative humidity of 75 to 85%, and after 24 hours and 48 hours, the number of dead mites in the filter paper was examined. The mortality was determined from the total number of mortality and the number of test specimens after 24 hours and 48 hours, and the corrected mortality was determined by the following equation. However,
If the corrected lethality is negative, it is set to 0. Corrected lethal rate (%) = (CT) / C｝ × 100 (C is lethal rate in control plot, T is lethal rate in treated plot) The results are shown in Table 6. Hinokitiol had a clear acaricidal effect. This test clearly shows that hinokitiol has an acaricidal effect in addition to the mite repellent effect,
High practical value was shown.

[0042]

Example 18 A mosquito repellent effect was examined in the same manner as in Example 1 except that a hinokitiol copper complex was used instead of hinokitiol. As a result, no blood sucking was observed even after 48 hours. In this example, since a hinokitiol derivative (metal complex) is used, it is considered that the sublimability of hinokitiol is suppressed, and the durability of the effect is improved.

[0043]

Example 19 As a result of examining the mosquito repellent effect in the same manner as in Example 1 except that an acyl form of hinokitiol (hinokitiol n-octanoate) was used instead of hinokitiol, no blood sucking was observed even after 48 hours. Was.
In this example, since a hinokitiol derivative (acyl compound) is used, it is considered that the sublimability of hinokitiol is suppressed, and the sustainability of the effect is improved.

[0044]

Example 20 The mosquito repellent effect was examined in the same manner as in Example 1 except that hinokitiol glycoside (glucose glycoside) was used instead of hinokitiol. As a result, blood sucking was observed even after 48 hours. I couldn't. In this example, since a hinokitiol derivative (glycoside) was used, it is considered that the sublimability of hinokitiol was suppressed, and the sustainability of the effect was improved.

[0045]

Example 21 The same method as in Example 6 except that the test was carried out after using a copper complex of hinokitiol in place of hinokitiol, dripping the inside of the shelter, air-drying all day and night, and leaving it to stand at 40 ° C. for 1 month. Performed a cockroach repellent test. The cockroach repellency was 92.3%. In this example, since the hinokitiol derivative (copper complex) is used, it is considered that the cockroach repellent effect is maintained despite being left at 40 ° C. for one month.

[0046]

Example 22 An acyl form of hinokitiol (hinokitiol n-octanoate) was used in place of hinokitiol, and the inside of the shelter was dropped and air-dried for 24 hours.
A cockroach repellent test was carried out in the same manner as in Example 6, except that the test was carried out after standing at 40 ° C. for one month. The cockroach repellency was 93.5%. In this embodiment, since a hinokitiol derivative (acyl form) is used,
Therefore, it is considered that the cockroach repellent effect is maintained despite being left for one month.

[0047]

Example 23 A glycoside of hinokitiol (glucose glycoside) was used in place of hinokitiol, the inside surface of the shelter was dropped, air-dried all day and night, and then left at 40 ° C. for one month before conducting the test. A cockroach repellent test was performed in the same manner as in Example 6. Cockroach repellent rate is 91.
7%. In this example, since a hinokitiol derivative (glycoside) was used, it is considered that the cockroach repellent effect was sustained despite being left at 40 ° C. for one month.

[0048]

Example 24 A mite repellent test was carried out in the same manner as in Example 15 except that the test was carried out after leaving the drug-treated paper at 40 ° C. for one month using a copper complex of hinokitiol instead of hinokitiol. Tick repellent rate is 8 in 24 hours
7.5%. In this example, since a hinokitiol derivative (copper complex) is used, it is considered that the mite repellent effect is maintained despite being left at 40 ° C. for one month.

[0049]

Example 25 A mite was treated in the same manner as in Example 15 except that the test was carried out after leaving the drug-treated paper at 40 ° C. for one month and using the acyl form of hinokitiol (hinokitiol n-octanoate) instead of hinokitiol. A repellency test was performed. The tick repellency was 83.3% at 24 hours. In this example, a hinokitiol derivative (acyl form)
It is considered that the mite repellent effect is maintained even though the mite repellent is left at 40 ° C. for one month.

[0050]

Example 26 The same method as in Example 15 was carried out except that a test was carried out after leaving the drug-treated paper at 40 ° C. for one month using a hinokitiol glycoside (glucose glycoside) instead of hinokitiol. A mite repellent test was performed. The tick repellency was 84.2% at 24 hours. In this embodiment,
Since a hinokitiol derivative (glycoside) is used, 4
It is considered that the mite repellent effect is maintained despite being left at 0 ° C. for one month.

[0051]

[Table 1]

[0052]

[Table 2]

[0053]

[Table 3]

[0054]

[Table 4]

[0055]

[Table 5]

[0056]

[Table 6]

[0057]

According to the present invention, it is possible to provide a technique for using hinokitiol as a pest repellent against harmful insects such as mosquitoes, cockroaches and mites. Furthermore, it is also possible to provide a technique for avoiding sublimation and coloring by metal, which are sometimes problems when using hinokitiol as a pest repellent.

Claims (4)

[Claims] 1. A pest repellent comprising hinokitiol and / or a hinokitiol derivative. 2. The pest repellent according to claim 1, wherein the pest is at least one member selected from the group consisting of mosquitoes, cockroaches, and mites. 3. The pest repellent according to claim 1, wherein the hinokitiol derivative is an organic salt, a metal salt, or a metal complex of hinokitiol. 4. The insect repellent according to claim 1, wherein the hinokitiol derivative is an acyl compound or glycoside of hinokitiol.