WO2002049431A1

WO2002049431A1 - Insect repellent compositions

Info

Publication number: WO2002049431A1
Application number: PCT/JP2001/010556
Authority: WO
Inventors: Mitsuyasu Makita; Keisuke Watanabe
Original assignee: Sumitomo Chemical Company, Limited
Priority date: 2000-12-18
Filing date: 2001-12-03
Publication date: 2002-06-27
Also published as: AU2002218528A1; JP2002187802A

Abstract

Insect repellent compositions containing, as the active ingredients, calan-3,4-diol and alkylene glycol mono ether compounds represented by the following general formula (1) which show an excellent insect repellent effect: R-O-(A-O-)nH (1) wherein R represents C3-8 alkyl, phenyl, etc.; A represents CH2CH2-, etc.; and n is an integer of 1 to 3.

Description

Description Pest repellent composition Technical field

The present invention relates to a pest repellent composition. Background art

It is disclosed in US Pat. No. 5,130,136 that insect repellents containing certain monoterpene diol compounds have excellent repellency against blood-sucking and sanitary pests. The U.S. Pat. Specification mentions carane-1,3,4-diol as an example of such a monoterpene diol compound.

However, although the composition containing carane-1,3-diol has an excellent repellent effect as described above, it is not always perfect. In practical control of blood-sucking pests such as mosquitoes, in particular, even if a repellent effect of 900/0 or more is obtained, it is not sufficient if there is any biting as a result. There is a need for an effect, and a better repellent effect has been desired.

On the other hand, Japanese Patent Application Laid-Open No. 61-289002 discloses that glycol ethers such as ethylene glycol monophenyl ether (2-phenoxyethanol) and jeti-lendaricol monobutyl ether are used to repel arthropods, molluscs and the like. Although described in the gazette, the effect is not sufficient. Disclosure of the invention

ADVANTAGE OF THE INVENTION According to this invention, the composition containing a carane-1,3,4-diol and a specific alkylene glycol monoether compound as an active ingredient exhibits not only a synergistic repellent effect but also a very excellent repellent effect. Is to bring.

That is, the present invention relates to curane-3,4-diol and a compound of the formula (1)

R-0- (A-0-) H (1) (Wherein, R represents a C3-C8 alkyl group, a phenyl group or a C7-C8 phenylalkyl group, and A represents a formula —CH ₂ CH ₂ —, —CH (CH ₃ ) CH ₂ — or —CH ₂ CH (CH ₃ ) —, where n represents an integer of 1 to 3.)

And a pest repellent composition containing an alkylene glycol monoether compound represented by the formula:

Karan-1,3,4-diol, one of the pest repellent active ingredients of the present invention, can be produced, for example, by the method described in US Pat. No. 5,130,136. In the present invention, any active carane-1,4-diol isomer or a mixture thereof can be used. In particular, an effective amount of 1S, 3R, 4R, 6R-force isomer is used as a power 3,4-diol. In the case of using a 1,3,4-diol-containing karan-1,3,4-diol, a mixture of the karan-1,3,4-diol and the alkylene glycol monoether compound represented by the formula (1) is more preferably used. Provides excellent synergistic effects.

The content of carane-1,3,4-diol in the pest repellent composition of the present invention is usually 0.1 to 50% by weight, and preferably 0.2 to 40% by weight ⁰ / o.

Examples of the alkylene glycol monoether compound represented by the formula (1) include 2-phenoxyethanol (ethylene glycol monophenyl ether), 2-benzyloxethanol (ethylene glycol monobenzyl ether), and ethylene glycol monoether compound. 2-ethylhexyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, diethylene glycol mono 2-ethylhexyl ether, dimethylene glycol monophenyl ether, triethylene glycol monobutyl ether, propylene glycol monophenyl ether, dipropylene glycol mono Butyl ether, dipropylene glycol monophenyl ether, etc., which may be used alone or as a mixture of two or more. It is possible to have. Among them, 2-phenoxyethanol, ethylene glycol monobutyl ether, diethylene glycol monohexyl ether, ethylene glycol mono-2-ethylhexyl ether and triethylene glycol monobutyl ether are preferred.

The content of the alkylene glycol monoether compound represented by the formula (1) in the pest repellent composition of the present invention is usually 0.2 to 90% by weight, preferably 0.2 to 60% by weight, more preferably 0 to 60% by weight. 3-50% by weight. Also, the mixing ratio of the carane-1,3,4-diol and the alkylene glycol monoether compound represented by the formula (1) in the pest repellent composition of the present invention is determined. In this case, the weight ratio is usually from 1: 0.01 to 1: 5, preferably from 1: 0,2 to 1: 2.5.

The pest repellent composition of the present invention usually contains a solvent which is a liquid carrier, in addition to the carane-1,3,4-diol and the alkylene glycol monoether compound represented by the formula (1). Examples of such a solvent include alcohols such as ethanol, various types of denatured ethanol, isopropyl alcohol, phenethyl alcohol, and cinnamon alcohol; polyalkylene glycols such as diethylene glycol, triethylene glycol, dipropylene glycol, and tripropylene glycol; IP-1620; Hydrocarbons such as isoparaffin such as IP-2028 and IP-2835 (trade names of Idemitsu Petrochemical Co., Ltd.) and normal paraffin such as Norpar 15 (trade name of Exxon Chemical Co., Ltd.), squalane, turpentine, Animal and vegetable oils such as terbineol, olive oil, soybean oil, rapeseed oil, castor oil, corn oil, linseed oil, coconut oil, palm oil, jojoba oil, safflower oil, isopropyl myristate, and monoglycol ethylene glycol , Ethylene glycol monocabronate Monoesters such as propylene glycol monopropylate, esters such as dibasic acid ester such as diisopropyl adipate and diisobutyl adipate, ketones such as anisylacetone, perhydrohydrofuran, dioxane, perfluoro Ethers such as polyethers, methylpolysiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, methylphenylpolysiloxane, poly (oxyalkylene) methylpolysiloxane copolymer, methylhydrogenpolysiloxane, etc. And the like.

When the pest repellent composition of the present invention contains the solvent, the content of the solvent is usually 5-99% by weight.

The pest repellent composition of the present invention may further comprise lipidronyl butoxide (PBO), N- (2-ethylhexyl) bicyclo [2.2.1] hepta-5-en-2,3-dicarboxy. Synergists such as amide (MGK264) and octachlorodipropyl ether (S421); phenols such as dibutylhydroxytoluene (BHT); antioxidants such as tocophenol (vitamin E); UV absorbers such as 2-ethoxyxetyl acid) and oxybenzone (2-hydroxy-14-methoxybenzophenone); humectants such as glycerin, urea and lactate; varnish oil, basil oil, citronella oil, etc. Fragrances, coloring agents such as Red No. 2 and Blue No. 2, Diet, p-menthane-1,8-diol, hyssop oil, 2- (2-hydroxyethyl) -1-piperidi It may contain other pest repellent components such as carboxylic acid 1-methylpropyl ester.

In addition, for facilitating uniform spread on the skin to which the pest repellent composition of the present invention has been applied, and facilitating formation of a coating film, for example, triethanolamine hydroprillate, triethanolamine power Organic acid amine salts such as ethanolamine, pyrrolidone triethanolamine pyrrolidone carboxylate, N-coconut oil fatty acid acyl-glutamic acid and ethanolamine may be contained in the pest repellent composition of the present invention. .

The pest repellent composition of the present invention comprises a curan-1,4-diol, an alkylene glycol monoether compound represented by the formula (1), a solvent, and other components, if necessary, which are uniformly dispersed at a temperature of usually from room temperature to about 50 ° C. It can be manufactured by mixing and stirring until it becomes.

Examples of pests that can be repelled by the pest repellent composition of the present invention include arthropods such as various pests and harmful daini. In particular, the pest repellent composition of the present invention is particularly useful for mosquito nets such as Acaesica and Kogatakaie, Aedes spp. Powers Anopkeles spp.), Numuka Mansonis spp.), Musca (Chironomidae), Houseflies (Muscidae) such as house flies, flies, flies and flies, Calliphoridae, and flies

(Sarcophagidae), Drosophila Psychodidae), Tabes (Tabanidae), Bhu (Simuliidae), Sashi, Stomoxylidae, Fleas / Phase (Phoridae), Nukaka

(Ceratopogonidae) and other suitable insect repellents such as dipteran insect pests.

When using the pest repellent composition of the present invention, usually, an effective amount of carane-1,3,4-diol and an alkylene glycol monoether compound represented by the formula (1) are applied to a site where the pest has entered.

In particular, when used to protect animals such as humans, livestock, and pets from blood-sucking pests, the pest repellent composition of the present invention is usually used as it is on the skin such as arms, legs, and face, and on clothing that covers the skin. It is used by coating and spray coating. The pest repellent composition of the present invention can be used as a pest repellent by enclosing it in a pressure-resistant container together with a propellant to form an aerosol, and spray-coating the aerosol in the same manner. When the pest repellent composition of the present invention is applied to the skin, the application amount is usually 1,3-diol of carane and an alkylene represented by the formula (1). 5 m _g from 0. 02 mg per 1 cm ² in the total amount of the glycol monoether compound is a 2 mg of preferably 0. 1 mg. Example

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

Example 1

0.5 g of 1 S, 3R, 4R, 6R-calane-3,4-diol and 0.5 g of 2-phenoxyethanol (ΡΟΕ) were weighed in a 10-mL volumetric flask. Ethanol was added to dissolve uniformly, and the total amount was further adjusted to 10 m with ethanol to obtain Composition 1 of the present invention.

Example 2

This composition 2 was obtained in the same manner as in Example 1, except that diethylene glycol monobutyl ether (BDG) was used instead of POE.

Example 3

This composition 3 was obtained in the same manner as in Example 2 except that the amount of BDG was changed to 1.0 Og.

Example 4

This composition 4 was obtained in the same manner as in Example 1, except that diethylene glycol monohexyl ether (HDG) was used instead of POE.

Example 5

This composition 5 was obtained in the same manner as in Example 4, except that the amount of HDG was changed to 1.0 Og.

Example 6

This composition 6 was obtained in the same manner as in Example 1, except that diethylene glycol mono 2-ethylhexyl ether (EHDG) was used instead of POE.

Example 7

This composition 7 was obtained in the same manner as in Example 6, except that the amount of EHDG was changed to 1.0 Og.

Comparative Example 1

0.5 g of 1S, 3R, 4R, 6R-forced 3,4-diol was weighed into a 10-mL volumetric flask. Ethanol was added thereto, uniformly dissolved, and the total amount was further adjusted to 1 OmL with ethanol to obtain Comparative Composition 1.

Comparative Example 2 Comparative composition 2 was obtained in the same manner as in Comparative example 1 except that the amount of 1 S, 3R, 4R, 6R—force 3,4-diol was changed to 1.0 Og.

Comparative Example 3

0.5 g of POE was weighed into a 10-mL volumetric flask. Ethanol was added to dissolve uniformly, and the total amount was further adjusted to 10 mL with ethanol to obtain Comparative Composition 3.

Comparative Example 4

Comparative composition 4 was obtained in the same manner as in Comparative example 3 except that BDG was used instead of POE. Comparative Example 5

Comparative composition 5 was obtained in the same manner as in Comparative example 3 except that HDG was used instead of PO. Comparative Example 6

Comparative composition 6 was obtained in the same manner as in Comparative Example 3, except that EHDG was used instead of POE. Comparative Example 7

Comparative composition 7 was obtained in the same manner as in Comparative example 6, except that the amount of EHDG was changed to 1.0 Og.

Example 8

The composition 8 was obtained in the same manner as in Example 1 except that diethylene glycol monophenyl ether was used instead of PO.

Example 9

This composition 9 was obtained in the same manner as in Example 1, except that propylene glycol monophenyl ether was used instead of POE.

Example 10

In a 10 ml_ volumetric flask were weighed 0.5 g of the present compound, 0.3 g of POE, and 0.3 g of IP-2028 (Idemitsu stone; isoparaffin, manufactured by I-Danigaku Co., Ltd.). Ethanol was added to dissolve uniformly, and then the total amount was adjusted to 10 ml_ with ethanol to obtain 10 of the present composition.

Example 1 1

In a 10-mL volumetric flask, 0.5 g of the present compound, 9 g of BDGO. And 0.1 g of silicone KF-54 (methylphenylpolysiloxane manufactured by Shin-Etsu Chemical Co., Ltd.) were weighed. Ethanol was added to dissolve uniformly, and the total amount was further adjusted to 10 mL with ethanol to obtain the present composition 11. Example 1 2

This composition 12 was obtained in the same manner as in Example 3, except that triethylene glycol monobutyl ether was used instead of BDG. Test example 1

About 500 adults of Aedes agipti were released in cages (48 cm 48 cm X 48 cm) covered with 80 mesh nylon net. Cut a part of the elbow cover so that a polyethylene (5cm x 10cm) opening is formed in the upper arm of the disposable elbow cover made of polyethylene when a person wears it on the arm. Affix a double-sided adhesive tape about 1 cm wide along the inside of the elbow cover along this rectangular opening.

The disposable elbow cover with the double-sided adhesive tape is attached to the upper arm, and the disposable elbow cover is attached to the upper arm with the double-sided adhesive tape so that only the rectangular opening is exposed. Attach styrofoam tape (thickness: 3 mm, width: 1 cm) to the boundary around the rectangular opening.

Apply 50 μl of the composition shown in Tables 1 and 2 uniformly to the rectangular opening of the upper arm, and after 15 minutes of application, insert the upper arm into the cage and guide it to the rectangular opening exposed for 120 seconds. Bow I Count the number of insects left on the mosquito. After a lapse of 120 seconds, the upper arm is taken out of the cage, and the number of bites (mosquito bites) is counted.

The same test was performed 30 minutes and 1 hour after application of the composition. The results are shown in Tables 1 and 2. Glycol Kalage-Monoether Glyco after a predetermined time from application

Lumonoate

Le

(Concentration 15 minutes 30 minutes 1 hour w / v%)

This composition 1 ΡΟΕ 5/5 0/0 0/0 0Z0 This composition 2 BDG 5/5 0/0 0/0 1 1 This composition 3 BDG 5/1 0 0/0 0/0 0/0 Composition 4 HDG 5/5 0/0 0/0 0 0 Composition 5 HDG 5/1 0 0/0 0/0 0 0 Composition 6 EHDG 5/5 0/0 0/0 0/0 Composition 7 EHDG 5/1 0 0 0 0/0 1/1

Gluco Calangi-Lumonoel Glyco after a predetermined time has passed since application

Mosquito Attraction Number Mosquito Stimulation Number

Lumonoete

One ter

(Concentration 15 minutes 30 minutes 1 hour w / v%) Comparative composition 1 ― 5/0 11/3 Discontinued Discontinued Comparative composition 2 10/0 7/2 Discontinued Discontinued Comparative composition 3 POE 0/5 14/4 Discontinued Discontinued Comparative composition 4 BDG 0/5 1/0 21 / 5 Discontinued Comparative composition 5 HDG 0/5 5/1 Discontinued Discontinued Comparative composition 6 EHDG 0/5 12/3 Discontinued Discontinued Comparative composition 7 EHDG 0Z10 10X2 Discontinued Discontinued Industrial availability

ADVANTAGE OF THE INVENTION According to this invention, the pest repellent effect of carane-1,3,4-diol is further enhanced, and almost complete pest repellent can be achieved.

Claims

The scope of the claims

1. Carane-1,3-diol and formula (1)

R-0- (A-0-) _n H (1)

(In the formula, R represents a C3-C8 alkyl group, a phenyl group or a C7-C8 phenylalkyl group, and A represents a formula —CH ₂ CH ₂ —, one CH (CH ₃ ) CH ₂ — or one CH ₂ CH (CH ₃ ) —, where n represents an integer of 1 to 3.)

A pest repellent composition comprising an alkylene glycol monoether compound represented by the formula (1) as an active ingredient.

2. The pest repellent composition according to claim 1, wherein the carane-1,3,4-diol is 1S, 3R, 4R, 6R-carane-1,3,4-diol.

3. When the alkylene glycol monoether compound represented by the formula (1) is 2-phenoxyethanol, 2-benzyloxyethanol, ethylene glycol mono 2-ethylhexyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, diethylene glycol monoether. Claims are at least one selected from 2-ethylhexyl ether, diethylene glycol monophenyl ether, triethylene glycol monobutyl ether, propylene glycol monophenyl ether, dipropylene glycol monobutyl ether, and dipropylene glycol monophenyl: renyl ether. The pest repellent composition described in 1.

4. The alkylene glycol monoether compound represented by the formula (1) is at least selected from 2-phenoxyethanol, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, diethylene glycol mono 2-ethylhexyl ether and triethylene glycol monobutyl ether. 2. The pest repellent composition according to claim 1, which is one kind.

5. The pest repellent composition according to claim 1 or 2, wherein the content of 1,3,4-diol of karan is 0.1 to 40% by weight.

6. The pest repellent composition according to claim 1, 3 or 4, wherein the content of the alkylene glycol monoether compound represented by the formula (1) is 0.2 to 60% by weight.

7. The pest repellent composition according to claim 1, comprising curan-3,4-diol, an alkylene glycol monoether compound represented by the formula (1), and one or more solvents.

8. The ratio of the contents of the carane-3,4-diol to the alkylene glycol monoether compound represented by the formula (1) in a weight ratio of 1: 0. 01 to 1: 5. 2. The pest repellent composition according to item 1.

9. Claim that the ratio of the contents of the carane-1,3-diol to the alkylene glycol monoether compound represented by the formula (1) is in the range of 1: 0.2 to 1: 2.5 by weight. Item 2. The pest repellent composition according to Item 1.