JPH09124408A - Sustained release pheromone preparation - Google Patents

Abstract

(57) [Abstract] [Problem] Without adsorbing sex pheromones on soil,
Provided is a sustained-release pheromone preparation that efficiently diffuses into the atmosphere. The outer surface of a formulation containing a sex pheromone is coated with a water repellent. This sustained release pheromone formulation
It is preferable that the sex pheromone is dissolved, absorbed or adsorbed in the synthetic resin, and that the sex pheromone is supported by an inorganic substance. The water repellent is at least one selected from silicone water repellents, fluorine water repellents, and paraffin hydrocarbons, and among these, silicone water repellents are most preferable.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a sustained release pheromone preparation used for controlling the generation of harmful insects.

[0002]

2. Description of the Related Art There is a method of using a synthetic pheromone for controlling harmful insects that damage crops, flower fields, forests and the like. Among them, the communication disruption method is known as the most effective method. The communication disruption method releases a high concentration of sex pheromones into the atmosphere, disables communication between males and females of pests, reduces the chance of mating, and reduces the density of pests. The communication disruption method utilizes a sustained release pheromone formulation to release the sex pheromone into the atmosphere. There are various types of sustained release pheromone formulations.

In JP-A-62-223101, JP-A-2-96502, and JP-A-63-145201, there are those in which a synthetic pheromone is enclosed in a polymer container such as a thin tube or an ampoule. Have been described. JP 53
-34927, JP-A-59-25319,
Japanese Patent Laid-Open No. 7-192024 describes a synthetic resin carrying a synthetic pheromone. JP-A-59-139301 and JP-A-56-95101 describe solidification of an inorganic substance carrying a synthetic pheromone. These sustained-release pheromone preparations are required to have the ability to efficiently and efficiently disperse expensive synthetic pheromones.

[0004]

The sustained-release pheromone preparation is suspended or attached to a plant or sprayed from the ground or the air. However, most of the sex pheromones are taken up by the foliage and soil with which the pheromone preparation is in contact, and are often not effectively released into the atmosphere. In particular, when a pheromone preparation in which a sex pheromone is supported on a synthetic resin or an inorganic substance is sprayed, it is rare that the entire preparation adheres to the plant body. When the plant body is vegetables such as cabbage and radish, most of the formulation falls to the ground and the sex pheromone is absorbed into the soil.

The present invention has been made to solve the above problems, and an object of the present invention is to provide a sustained release pheromone preparation that efficiently diffuses sex pheromones into the atmosphere without absorbing them into the soil. .

[0006]

The sustained-release pheromone preparation of the present invention made to achieve the above object contains a sex pheromone, and its outer surface is coated with a water repellent. It has a feature. This sustained-release pheromone preparation is preferably one in which the sex pheromone is dissolved, absorbed or adsorbed in the synthetic resin, and one in which the sex pheromone is carried by an inorganic substance.

The sex pheromone has, for example, 10 to 2 carbon atoms.
4 higher aliphatic aldehyde compounds, acetate compounds,
Examples include propionate compounds and hydrocarbons. Specifically, hydrocarbon compounds such as Z9-tricosene, 14-methyl-1-octadecene, E5-decenyl acetate, E4-tridecenyl acetate, dodecyl acetate, Z7-dodecenyl acetate, Z8-do Acetate compounds such as decenyl acetate, E7Z9-dodecadienyl acetate, Z9-tetradecenyl acetate, Z11-tetradecenyl acetate, Z11-hexadecenyl acetate, E3Z13-octadecadienyl acetate, etc. Z9-Tetradecenal, Z9-
Hexadecenal, Z11 Z13-Hexadecadienal, Z13
-Aldehyde compounds such as octadecenal, ketone compounds such as Z13-icosen-10-one, epoxy compounds such as 7,8-epoxy-2-methyloctadecane, propionate compounds such as 8-methyl-2-decylpropionate and the like And mixtures containing these as the main components are exemplified. If necessary, various antioxidants, ultraviolet absorbers, etc. may be added and mixed.

As the synthetic resin, those having good compatibility with the above sex pheromone are suitable. For example, polyolefins such as ethylene, propylene and butylene, ethylene-vinyl acetate copolymer, ethylene-acrylic acid ester copolymer are suitable. Alternatively, an ethylene copolymer having a carboxyl group such as an ethylene-methacrylic acid ester copolymer, or a mixture of an ethylene copolymer having a carboxyl group and a polyolefin can be used.

Examples of the inorganic substance include silicic acid anhydride and various metal salts thereof, stearic acid and various metal salts thereof, talc, titanium oxide, kaolin, zinc oxide, magnesium carbonate, calcium carbonate and the like.

Examples of the water repellent agent include silicone type, fluorine type and paraffin type hydrocarbons. Among these, silicone water repellents are most preferable because of ease of coating treatment.

One of the silicone water repellents is, for example, a silicone compound represented by the following formula [1] R ¹ _a R ² _b SiO _{(4-ab) / 2} [1]. R ¹ and R ² are the same or different types of unsubstituted hydrocarbon groups or substituted hydrocarbon groups, hydrolyzable groups, and the same or different types of groups or atoms selected from —OH and —H. a and b are 0 ≦
The numbers are a <4, 0 ≦ b ≦ 4, and 0 <a + b ≦ 4.

R ¹ is, for example, an alkyl group having 1 to 15 carbon atoms such as methyl group, ethyl group, propyl group and decyl group, alkenyl group such as vinyl group and allyl group, aryl group such as phenyl group and tolyl group, A cycloalkyl group such as a cyclohexyl group, and a group such as a perfluoroalkyl group in which a part or all of hydrogen atoms bonded to carbon atoms of these groups are substituted with a halogen atom or a cyano group. R ² is, for example, an alkoxy group such as a methoxy group, an ethoxy group, an acyloxy group, a ketoxime group, an amino group, an aminoxy group, an amido group, an enoxy group, a hydrolyzable group such as an alkenyloxy group, a halogen atom such as chlorine, —OR ³ (R ³ is Na or K), —OH, —H and the like.

[0013] In this case, the silicone compound of the formula [1] specifically formula HO-Si (ONa) (CH 3) - [OSi (ONa) C
_{H 3] n -OH CH 3 -} [SiO (CH 3) 2] m - [SiO (H) (CH 3)] l
^{_{-Si (CH 3) 3 R 4}} - [SiO (CH 3) 2] k -Si (CH 3) 2 -R 4 CH 3 Si (OCH 3) 3, CF 3 CH 2 CH 2 Si (OCH
₃ ) Indicated by ₃ . Here, n is 0, 1 or 2, and l, m
Is an integer of 0 or more, k is an integer of 0 or more, and R ⁴
It is -OH, a -CH = CH ₂ or -OCH _3. Further, the silicone compound may be a partial hydrolyzate or a cohydrolyzate thereof.

As another embodiment of the silicone water repellent, a unit represented by the following formula [2] R ⁵ _c SiO _{(4-c) / 2} [2] and a unit represented by the following formula [3] R ⁶ _d are included in the molecule. Si (NR ⁷ ) _{(4-d) / 2 An} organopolysiloxazane polymer containing both units represented by [3], or an organopolysiloxane containing at least one unit represented by the formula [3] There is a siloxazane polymer. R ⁵ , R ⁶ and R ⁷ are hydrogen atoms, the same or different unsubstituted hydrocarbon groups or substituted hydrocarbon groups, c is a number selected from 1, 2, 3 and d is 1 or 2 is there.

R ⁵ , R ⁶ and R ⁷ are, for example, an alkyl group having 1 to 15 carbon atoms such as methyl group, ethyl group, propyl group and decyl group, alkenyl group such as vinyl group and allyl group, phenyl group and tolyl group. A group such as an aryl group such as a group, a cycloalkyl group such as a cyclohexyl group, or a perfluoroalkyl group in which a part or all of hydrogen atoms bonded to carbon atoms of these groups are substituted with a halogen atom or a cyano group.

Specific examples thereof include compounds whose structural units are represented by the following formula (CH ₃ ) ₃ Si (NH) _1.5 C _p F _{2p + 1} CH ₂ CH ₂ Si (NH) _1.5 . Here, P is a positive integer.

The sustained-release pheromone preparation is not limited in shape, material and the like. Specifically, molded and cut synthetic resin impregnated with sex pheromone, crushed resin pellets impregnated with sex pheromone, solidified inorganic substance supported and adsorbed by sex pheromone. There are things.

The sustained release pheromone preparation is produced, for example, by the following method. A sex pheromone is added to and mixed with a synthetic resin or an inorganic substance. In this mixture,
Add a binder such as hydroxypropyl cellulose and granulate. After dissolving the water repellent in a solvent such as toluene, n-hexane, ethanol, or acetone, the water repellent is sprayed on the surface of the elementary granules, or the elementary granules are dipped in the solvent and dried. After coating, a sustained release pheromone preparation is obtained. Before coating the elementary granules with the water repellent, the surface of the elementary granules may be coated with a coating agent such as hydroxypropylmethylcellulose.

[0019]

The sustained-release pheromone preparation of the present invention comes into contact with soil and the like, and the water repellent adheres to the outer surface thereof, so that the released sex pheromone can be prevented from adsorbing to the soil. Therefore, the sex pheromone is released into the atmosphere without waste. In particular, when the pheromone formulation to be sprayed has a large number per unit area or a large release surface area such as a synthetic resin or an inorganic substance, the loss of the sex pheromone can be surely suppressed.

[0020]

Embodiments of the present invention will be described below in detail.

(Preparation of sustained-release pheromone preparation) Light silicic anhydride (manufactured by Nippon Aerosil Co., Ltd .; trade name Aerosil) 30
By weight, 30 parts by weight of Z-9-tetradecenyl acetate (a sex pheromone component of Spodoptera litura) was mixed. Next, 2 parts by weight of hydroxypropyl cellulose (manufactured by Shin-Etsu Chemical Co., Ltd .; trade name HPC) as a binder was added, and 180 parts by weight of ethanol was added and kneaded. This mixture was granulated by an extrusion granulator to obtain spherical and cylindrical elementary granules having an average particle diameter of 1 mm.

An ethanol / water (8/2) 6 wt% solution of hydroxypropylmethyl cellulose phthalate (manufactured by Shin-Etsu Chemical Co., Ltd .; trade name HP-55) in a fluidizer was used to prepare 4
The elementary granules were spray-coated with air at 5 ° C. as a fluid medium. A sustained release pheromone preparation having a coating film of 30% by weight based on the elementary granules was obtained.

(Surface treatment of water repellent agent) The above pheromone preparation was treated with a methylsilane consisting of 18 mol% of [(CH ₃ ) ₂ SiO] units and 82 mol% of [CH ₃ Si (NH) _1.5 ] units as a water repellent agent. Dimethylsiloxazane polymer toluene /
Methylene chloride (5/5) type 5% by weight solution was added to a fluidizer 4
Spray coating was carried out using air at 5 ° C as a fluid medium. A pheromone preparation coated with 5% by weight of a water repellent was obtained, which was designated as Sample 1.

(Study of Sex Pheromone Emission) Soil collected from paddy fields in Kubiki village, Nakakubiki county, Niigata prefecture, was dried in the sun for 2 weeks, filtered through a 20 mesh sieve, and the soil that passed through the sieve was used in the following experiments. did.

Sample 1 was spread evenly so as not to overlap with the soil, and left under a constant condition of a temperature of 35 ° C. and a wind speed of 0.5 m / sec. A part of Sample 1 was collected every 5 days, and the amount of Z-9-tetrathecenyl acetate remaining in Sample 1 was quantified by a gas chromatogram to determine the pheromone residual rate.

For comparison, a pheromone preparation whose outer surface was not treated for water repellency was used as Sample 2, and the pheromone residual rate was measured in the same manner as in Sample 1. Sample 2 is not water-repellent treated, but other conditions are the same as those of sample 1. Table 1 shows the pheromone survival rates of Samples 1 and 2.

[0027]

[Table 1]

As shown in Table 1, Sample 1 uniformly diffused the sex pheromone over 30 days.

In order to examine the adsorption of the sex pheromone on the soil, the soil 20 on which the samples 1 and 2 were spread after 20 days
g was collected. Add 50 ml of acetone to the collected soil, stir for 20 minutes with a shaking stirrer, leave it for 10 minutes, then
Filtered. 100 ml of 2% saline and 100 ml of n-hexane were added to the filtrate, and the mixture was stirred for 15 minutes with a shaking stirrer, and then liquid separation operation was performed. The organic layer was dehydrated with Glauber's salt and then concentrated, and a gas chromatogram was measured.

From the soil where Sample 1 was spread, Z-9
-While tetradecenyl acetate was not detected, peaks of Z-9-tetradecenyl acetate and Z-9-tetradecenol were confirmed from the soil where Sample 2 was spread. Z-9-tetradecenol is produced by hydrolysis of Z-9-tetradecenyl acetate in soil. From this result, in sample 1,
It was confirmed that the sex pheromone has an action of suppressing the adsorption to the soil.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location // C08L 83/04 LRR C08L 83/04 LRR

Claims (6)

[Claims] 1. A sustained-release pheromone preparation containing a sex pheromone, wherein the outer surface is coated with a water repellent. 2. The sustained-release pheromone preparation according to claim 1, wherein the sex pheromone is dissolved, absorbed or adsorbed in a synthetic resin. 3. The sustained-release pheromone preparation according to claim 1, wherein the sex pheromone is supported on an inorganic substance. 4. The sustained-release pheromone preparation according to claim 1, wherein the water repellent is at least one selected from silicone water repellents, fluorine water repellents, and paraffin hydrocarbons. . 5. The silicone water repellent is represented by the following formula [1] R ¹ _a R ² _b SiO _{(4-ab) / 2} [1] (R ¹ and R ² are the same or different unsubstituted hydrocarbon groups. Or a substituted hydrocarbon group, a hydrolyzable group, the same or different group or atom selected from -OH, -H, a, b
Is a silicone compound represented by 0 ≦ a <4, 0 ≦ b ≦ 4, 0 <a + b ≦ 4), the sustained-release pheromone preparation according to claim 4. 6. The silicone water repellent in the molecule has the following formula [2] R ⁵ _c SiO _{(4-c) / 2} [2] (R ⁵ is a hydrogen atom, the same or different unsubstituted hydrocarbons). A group or a substituted hydrocarbon group, c is a unit selected from 1, 2, and 3) and a unit represented by the following formula [3] R ⁶ _d Si (NR ⁷ ) _{(4-d) / 2} [3] ( R ⁶ and R ⁷ are hydrogen atoms, the same or different unsubstituted hydrocarbon groups or substituted hydrocarbon groups, d is a unit represented by 1 or 2), and an organopolysiloxazane polymer containing both units, or a formula The sustained-release pheromone preparation according to claim 4, which is an organopolysiloxazane polymer containing at least one unit represented by [3].