JPH07206615A - Insecticidal composition - Google Patents

Abstract

PURPOSE:To provide an insecticidal composition high in the insecticidal and insect-preventing effects, excellent in chemicai stability (insensitivity to metals) and safety, and used for clothing. CONSTITUTION:An insecticide composition comprises (A) empenthrin of formula I having a high insecticidal activity and volatility at the ordinary temperature and excellent in an eating damage-preventing effect against clothing insect pests at low doses, and (B) a silicone compound, preferably methylpolysiloxane of formula II (m is 1-50), methylphenylpolysiloxane of formula III (p is 0-50; q is 0-30; r is 0-20; but q and r are not 0 simultaneously; and p + q + r : 1-51), cyclopolysiloxane of formula IV (n is 3-20; R1 is methyl, phenyl; R2 is methyl, phenyl, vinyl), or methylhydrogenpolysiloxane of formula V (s is 1-100) in an A:B ratio of >=1.0. The combination of the empenthrin with the siloxane compound prevents the discoloration or denaturation of the empenthrin due to the affection of metals.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to improvement of insect repellents containing empentrin.

[0002]

BACKGROUND OF THE INVENTION Empentrin is particularly useful as an active ingredient of insect repellents for clothing because it has a high insecticidal activity, volatility at room temperature, and a low dose, which is excellent in terms of preventing food damage to clothing harmful insects. Is. However, empentryn has a drawback that it is susceptible to problems such as discoloration or deterioration under the influence of metals (particularly copper compounds), and a preventive measure against it has been earnestly desired.

As a countermeasure against this, for example, a method of using a certain triazole compound such as benzotriazole derivative and 2-mercaptobenzotriazole in empentrin is used in JP-A-61-30505, and a tetrazole compound is used. Attempts to compound them have been made in JP-A-63
Although it is disclosed in Japanese Patent Publication No. 126808, the effect of preventing discoloration and deterioration is not always sufficient.

[0004]

DISCLOSURE OF THE INVENTION The present invention aims to develop a useful insect repellent composition by searching for a compound that suppresses discoloration and deterioration of empentrin when used in combination with empentrin and can be used safely indoors. It was made.

[0005]

In order to achieve the above object, the present invention provides empentrin and a siloxane compound,
Preferably methylpolysiloxane, or methylphenylpolysiloxane, especially of formula I

[Chemical 5] (In the formula, m represents an integer of 1 to 50), or the formula II.

[Chemical 6] (In the formula, p, q, and r are 0 to 50, 0 to 30,
It represents an integer from 0 to 20. However, both q and r never become 0, and p + q + r is 1 to 51. ) Or a compound of formula III

[Chemical 7] (In the formula, n represents an integer of 3 to 20. In addition, R ₁ represents a methyl group or a phenyl group, and R ₂ represents a methyl group, a phenyl group or a vinyl group.), Formula IV

[Chemical 8] (In the formula, s represents an integer of 1 to 100.) A siloxane compound selected from methyl hydrogen polysiloxane represented by the formula: Pertain.

[0006]

The empentryn used in the present invention has the following formula V

[Chemical 9] It has a structure of 1 and has a high vapor pressure and shows a high insecticidal activity against clothing pests, and is therefore widely used for clothing insect repellents. The acid part and the alcohol part have optical isomers or geometrical isomers based on asymmetric carbons or double bonds, but each of these isomers or any mixture thereof is not included. Of course.

The present invention relates to empentryn together with a siloxane-based compound, preferably methylpolysiloxane, methylphenylpolysiloxane, cyclopolysiloxane,
The feature is that a compound selected from methylhydrogenpolysiloxane is blended. Siloxane-based compounds are used as silicone oils for cosmetics, conical treatments, etc., and their safety is extremely high. Therefore, the findings that prevent the discoloration and alteration action of empentrin are:
It is extremely useful because it can be safely used indoors. Although there are still many unclear points about the reason for its preventive effect, usually, one or more of these compounds may be blended in an amount of 1.0 times or more with respect to empentrin. Typical examples of the siloxane-based compound group are as follows,
The present invention is not limited to these. In addition, the compound called polysiloxane usually has various addition mole numbers, but it is exemplified here as the average mole number.

Compound 1. Hexamethyldisiloxane

[Chemical 10] Compound 2. Decamethyltetrasiloxane

[Chemical 11] Compound 3. Hexamethylcyclotrisiloxane

[Chemical 12] Compound 4. Octamethylcyclotetrasiloxane

[Chemical 13] Compound 5. Decamethylcyclopentasiloxane

[Chemical 14] Compound 6.1,3,5,7-tetramethyltetravinylcyclotetrasiloxane

[Chemical 15] Compound 7.1,3,5,7,9-pentamethylpentavinylcyclopentasiloxane

[Chemical 16] Compound 8. Dimethyl polysiloxane (m = 25)

[Chemical 17] Compound 9. Octaphenylcyclotetrasiloxane

[Chemical 18] Compound 10.3,3-diphenylhexamethyltrisiloxane

[Chemical 19] Compound 11.1,3,5,7,9-pentamethylpentaphenylcyclopentasiloxane

[Chemical 20] Compound 12. Methylphenyl polysiloxane (p =
0, q = 3, r = 0)

[Chemical 21] Compound 13. Methylphenyl polysiloxane (p =
3, q = 0, r = 2)

[Chemical formula 22] Compound 14. Methylphenyl polysiloxane (p =
0, q = 10, r = 0)

[Chemical formula 23] Compound 15. Methylphenyl polysiloxane (p = 1
2, q = 1, r = 6)

[Chemical formula 24] Compound 16. Methylphenyl polysiloxane (p =
2, q = 4, r = 0)

[Chemical 25] Compound 17. Methylphenyl polysiloxane (p =
1, q = 5, r = 1)

[Chemical formula 26] Compound 18. Methyl hydrogen polysiloxane
(S = 30)

[Chemical 27] Compound 19. Methyl hydrogen polysiloxane
(S = 50)

[Chemical 28]

The siloxane-based compound used for the purpose of the present invention needs to be volatilized together with empentrin, and an appropriate number of added moles is appropriately selected. Generally, volatility and viscosity are correlated, and if expressed in terms of viscosity, 2
It is preferably 5 to 50 CS at 5 ° C. Usually, the viscosity of standard products is standardized. For example, methylphenylpolysiloxane SH-556 (Tore Silicone product name; 22.5CS), SF-557 (Torre silicone product name; 20CS). , Methylpolysiloxane SH-200 (trade name of Toray Silicone;
10CS, 20CS) and the like are examples of preferable siloxane compounds. These compounds are liquid at room temperature and are usually preferably suitable carriers together with empentrin.
It is prepared into a solid formulation such as a mat or a sheet using an excipient, and applied to the control of insect pests by a method according to each of these forms. As the mat or sheet carrier,
Examples thereof include mats made of pulp, paper, woven fabric, non-woven fabric, plastic molded products such as polyethylene, polypropylene, polyvinyl chloride, polyester, and ethylene vinyl acetate, and porous glass materials. The volatility can be adjusted by using a sublimable carrier such as adamantane, cyclododecane, or triisopropyl-trioxane, and can be prepared in a gel form by using a gelling agent such as polyvinyl alcohol, alginic acid, or carrageenan. You can also do it. The drug-containing carrier thus obtained is usually put into a plastic case, a non-woven fabric bag or the like for practical use.

The insect repellent composition of the present invention also contains N-octylbicycloheptenecarboximide (trade name: MGK).
-264), a mixture of N-octylbicycloheptenecarboximide and an aryl sulfonate (trade name: M
GK-5026), synepyrine 500, octachlorodipropyl ether, piperonyl butoxide and other synergists may be added. Furthermore, in the insect repellent composition of the present invention,
The addition of a phenol-based or amine-based antioxidant such as 2,6-ditertiary butyl-4 methylphenol (BHT), Yoshinox 425, 2,6-ditertiary butylphenol is effective for the insect repellent composition of the present invention. It is useful for improving stability over time.

Further, other insecticides such as fenitrothion, DDVP, organophosphorus agents such as diazinon, NAC,
By mixing a carbamate agent such as MTMC, BPMC, PHC, etc., a conventional pyrethroid insecticide such as pyrethrin, phtalthrin, phenothrin, permethrin or the like, an aromatic agent, a deodorant, a bactericide, etc., a highly effective multipurpose composition can be obtained. However, labor saving can be expected.

The thus obtained insect repellent composition of the present invention is applied to clothing storage furniture such as a chest of drawers and a clothing box, and exerts a high extermination effect against clothing pests such as squid, koga, scabbard beetle, and stag beetle. ,archive,
It is extremely useful as a measure against insects in exhibition rooms.

In order to further clarify that the insect repellent composition provided by the present invention is excellent, the test results of Examples and effects are shown below.

[0014]

Example 1 Empentrin 0.03 g, compound (1) 0.04 g, dibutylhydroxytoluene 0.0
A thick paper mat having a thickness of 2 mm, a length of 22 mm and a width of 35 mm was impregnated with a chemical solution containing 1 g, a slight amount of a fragrance and 0.02 g of kerosene, and the mat was stored in a non-woven fabric bag to obtain an insect repellent for clothing.

[0015]

Example 2 Using ethylene-vinyl acetate copolymer and chlorinated polyethylene as a controller, 0.6 g of empentrin and 2.0 g of compound (3) were added to 30 cm.
A 50 cm sheet was impregnated to obtain a sheet-like insect repellent for clothing.

[0016]

[Test Example 1] Insecticidal test by transpiration and stability test against metal 2.2 cm × 3.5 cm containing a mixture of empentrin and each compound in a petri dish having a diameter of 9 cm and a height of 2.1 cm.
A pulp mat was included. Similarly, the diameter is 9 cm and the height is 2.
Ten koigami larvae were released on a 1 cm petri dish, sandwiched with a 16-mesh wire net, and placed on the petri dish containing the drug. That is, the koga larvae were exposed to only the chemical vapor and left for 24 hours to observe the knockdown state of the test insects. Furthermore, after the exposure, the test insects were transferred to another container, and the mortality rate after 24 hours was examined. The results are shown in Table 1. Also, instead of the larvae of Koga, 1 cm
A piece of copper of 2 cm was put therein, and similarly, a 16-mesh wire net was sandwiched between the pieces, and the piece was left in a thermostatic chamber at 50 ° C. Table 1 also shows the results of examining the surface portion of each copper plate after 3 days and examining the effect of vapor on the metal. In addition, as a comparison, the test was performed also in the case where one mat was impregnated with empentrin or each compound alone.

[0017]

[Table 1]

As a result of the test, the insect repellent composition snout of the present invention was 2
The knockdown rate and lethality rate to carp after 4 hours were excellent, and the insecticidal efficacy was almost the same as that of empentrin alone (Comparative Example 1). Further, almost no insecticidal effect was observed with the siloxane-based compound alone (Comparative Examples 2 to 4). Further, while the effect of empentrin alone on the metal was remarkably observed, the insect repellent composition of the present invention showed almost no abnormality, and it was confirmed that the siloxane compound suppresses the effect of empentrin on the metal.
The effect of preventing discoloration and deterioration of these compounds is 1.0 to 10 times as much as that of empentrin, and even if it exceeds it, the special effect is not enhanced. It was insufficient (Comparative Example 5).

[0019]

[Test Example 2] Practical test using transpiration Insect repellent for clothing prepared according to Example 1 (6 cm x 8 c
m) was suspended in a chest of 600 l. Immediately after and 6 months after the start of the test, glass rings (both sides covered with a wool cloth) having a diameter of 4 cm and a width of 2 cm in which 10 first-instar larvae of squid were released were placed in the closet, and after 1 day, 2 days, and 7 days. The mortality of insects was observed. Further, when the clothes with brass buttons which had been put in the closet from the start of the test were also observed, it was as shown in Table 2.

[0020]

[Table 2]

As a result of the test, the insect repellent composition of the present invention in which empentrin and the siloxane compound are mixed is more effective against the larvae of squid than the conventional product containing only empentrin.
The insecticidal and insecticidal effects were almost the same over a long period of time. Himekatsu of Simushi, Himemaru Cut of Shimushi, Koiga,
It was similarly effective against other clothing pests such as Juutanga. Furthermore, in the insect repellent composition of the present invention, the effect of empentrin on the metal was suppressed by the action of the siloxane-based compound to such an extent that there was no problem, and it was confirmed that it is extremely useful in practice. Therefore, the insect repellent composition of the present invention can be applied not only to drawers, drawers, etc., but also to various scenes such as machine equipment and exhibition rooms.

[0022]

INDUSTRIAL APPLICABILITY The present invention provides a mosquito repellent composition excellent in high insecticidal and insect repellent effects, safety, and chemical stability (not easily affected by metal) by using empentryn and a siloxane compound in combination. I will provide a.

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Claims (6)

[Claims] 1. An insect repellent composition comprising empentrin and a siloxane-based compound in an amount of 1.0 times or more the amount of empentrin. 2. The insect repellent composition according to claim 1, wherein the siloxane compound is methylpolysiloxane or methylphenylpolysiloxane. 3. A methylpolysiloxane having the formula I (In the formula, m represents an integer of 1 to 50.) The insect repellent composition according to claim 1 or 2, wherein 4. Methylphenyl polysiloxane has the formula II (In the formula, p, q, and r are 0 to 50, 0 to 30,
It represents an integer from 0 to 20. However, both q and r never become 0, and p + q + r is 1 to 51. The insect repellent composition according to claim 1 or 2, which is represented by the formula (1). 5. A siloxane-based compound kiss is of formula III (In the formula, n represents an integer of 3 to 20. In addition, R ₁ represents a methyl group or a phenyl group, and R ₂ represents a methyl group, a phenyl group or a vinyl group.). The insect repellent composition according to claim 1, wherein the insect repellent composition is present. 6. A siloxane-based compound is represented by the formula IV: (In the formula, s represents an integer from 1 to 100.) A methylhydrogenpolysiloxane represented by the formula, wherein the insect repellent composition according to claim 1.