JPS5913701A - Pheromone preparation - Google Patents

Abstract

PURPOSE:To provide the titled preparation capable of releasing the pheromone to the environment at a desired rate constantly for a long period, and consisting of a porous storage material containing the pheromone compound in the mutually interconnected pores. CONSTITUTION:The objective pheromone preparation is obtained by impregnating a pheromone compound or a pheromone-like compound in the pores of a porous storage material composed of a substrate nontrausmittible for UV-light, having low compatibility to the pheromone, and containing mutually connected pores through which the pheromone can be freely moved and diffused (e.g. cellulose, cellulose acetate, fluororesin, polyurethane, polysulfone, etc.). The rate of release can be controlled within the range of 1-50mug/day for pheromone having low rate of vaporization. When the releasing surface of the preparation is covered with a release-controlling membrane such as polyethylene film, the releasing rate can be controlled over a wider range (1-100mug/day) for pheromones having various rates of vaporization.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides long-term use of pheromones.
In which environment fl is released into the air at the discharge floor jW:
This invention relates to a formulation with 1ill + 1 function. More details C,? The invention comprises a vaporizable pheromone compound or a lactone-like compound, a porous storage body containing this compound in its pores, and
to cover at least a portion of this storage body, and to form a covering portion tCE.
and a control membrane that controls the permeation of the compound to the outside,
The pores of this porous reservoir are interconnected to allow free movement and diffusion of the compound within the reservoir.

Synthesize large amounts of pheromone compounds, which are attractant compounds secreted by insects for use in communication between the same species, or pheromone-like compounds that have a similar chemical structure to pheromones and have the same effects as pheromones, and release large amounts of these compound proboscises. These compounds can be used to control pests by interfering with the communication between insects of the same species, or by attracting insects to the willows where these compounds occur.6
Attempts are being made.

In order to utilize these compounds for insect control, the compounds must be continuously released at the desired effective rate throughout the pest season, depending on the control objective.

The first purpose of this preparation is to impregnate a rubber cap with a pheromone compound or directly seal it in a polyethylene cap or polyethylene tube.
It has already been put into practical use. These preparations, however,
Since the release rate of the pheromone compound decreases over time, it is difficult to maintain the medicinal effect of the pheromone compound over a long period of time.

In order to maintain a more stable release rate of the hepta-lomone compound from the preparation, a method is generally adopted in which the storage body containing the pheromone compound is encapsulated or laminated with a polymer membrane that can control the permeation of the hepta-lomone compound. It is being In these conventional methods, a polymeric material that is highly compatible with a pheromone compound is used as a storage medium.

Kone is making the pheromone compound 6th. It is difficult for the pheromone compound proboscis to diffuse smoothly through this polymeric material as a matrix, so its diffusion 41'[
In addition, the release of L-lomones (dissolved in the polymer material) decreases by 1 over time and the thermodynamic activity decreases, which significantly slows down the diffusion. Therefore, in the conventional pheromone preparation 1, the release rate of the pheromone compound cannot be maintained constant. Moreover, the pheromone compound dissolved in the polymer material.

Normally, about 40% remains in the storage body and is never released. Furthermore, in order to pre-contain the pheromone compound required to maintain pest control effects over a long period of time in the storage medium, it is difficult to use a t-rice preparation in which the solubility of the pheromone compound in the polymeric material is the limiting factor. It had no choice but to become something big.

Additionally, these preparations can be used outdoors in farmland, orchards, and forests, and the pheromone compounds contain chemically unstable compounds containing carbon-carbon double bonds and aldehyde groups during their chemical formation. Therefore, in practical use, pheromone compounds have a denaturing power due to ultraviolet rays (an indispensable force that prevents image formation).

One way to overcome these conventional drawbacks is (1) in the storage body (
7) maintaining the thermodynamic activity of the heptadromone compounds or pheromone compounds; (2) allowing free migration and diffusion of these compounds in the reservoir; and (3) ensuring that the reservoir These compounds inside $! I. Raise the value once, less (all three conditions are necessary. This invention +i
The present inventor's novel method that can simultaneously satisfy these three stripes fl+= by lining the groove with a porous 1M membrane fj with a base material having a low co-polymerization with the R storage body*pheromone compound or pheromone-like compound It was completed based on wisdom.

The object of the present invention is to be able to release a predetermined amount of heptaromone compound or pheromone-like compound necessary for controlling pests at a constant rate over a long period of time.

The therapeutic effect of these compounds is maintained during the entire season when pests are active; it is important to obtain a pheromone preparation. Another object of the present invention is to provide a pheromone formulation with a release rate that is easily obtained.

The CC present invention will be explained below.

Generally, the pheromones of insects of the order Orinidae are long (0) non-Etetrahydric hydrocarbons, with a black acetate, aldehyde, or alcohol group at the end.

tui usual, 12.14.16 f from the solid carbon atom,
i! l, 1-2 (tAl) Many have a carbon-carbon double bond. It is used to contain pheromone compounds or pheromone-like compounds having 1,000,700
(combination (E'rFE), polytetrafluoroethylene (
It is made of at least one fluororesin such as P'rFE), and the pores are interconnected.The pore diameter is usually about 20μ.
The following can be selected. The pore size is determined depending on the model number of the compound to be stored in the storage body, and for example, a compound of about 60 or more is used. Such a preparation that can be swallowed by saliva is susceptible to the release of pheromones that have a slow vaporization rate, and in the preparation of the present invention containing a pheromone compound or a pheromone-like compound in the storage body 11,
The rate of release of the compound can be adjusted from about 1 μl/day to about 50/1jIZ day.

For pheromone compounds, the release rate of pheromone-like compounds can be adjusted over a wider range as desired.

As shown in FIG. 2, the compound release surface 11 of the storage body 1 can be covered with a compound release rate controlling film 2 made of polyethylene or the like. The storage body 1 is covered with the control membrane 2 f, (the part 10 is permeable to the compound fj
The polyethylene compound or pheromone-like compound that is backed with the backing film 3 is based on the density, elongation degree, and
The release rate can be arbitrarily controlled by varying the film thickness, film surface properties, etc. On the chemical groove layer of the sigma compound, for compounds with a high IW rate of permeation through this polyethylene film,
By using a dense and stretched polyethylene membrane, the release of the compound can be controlled. Furthermore, the release rate can be easily fine-tuned by changing the film thickness. The collateral film-attached preparation of the present invention obtained by straining in this way has a diameter of approximately 1 μm. It is possible to adjust the release rate from about 100 mp/day to about 100 mp/day. As the release rate control membrane 2, in addition to a polyethylene membrane, for example, an ethylene/vinyl acetate copolymer membrane can also be used. In this case, the release rate fW of the compound can be easily controlled by changing the vinyl acetate content. This ethylene/vinyl acetate copolymer generally has a higher compound permeability i than polyethylene, so polyethylene! To achieve a performance that is vaguely equivalent to that of a film, it is necessary to make the film thicker.

This is used to protect pheromone compounds or pheromone-like compounds from denaturation caused by UV rays and other harmful factors.

The storage body 1 is made of polysulfone or polyvinyl chloride. In addition, compound release full s published membrane 2
can be made of polyurethane. The relationship between the light wavelength and the transmittance is shown in Table 11 below for the base material (base material thickness 125μ).
I'm so happy. It can be seen that polysulfone, polyurethane, and polyvinyl chloride substrates all exhibit excellent opacity in the short wavelength ultraviolet region.

Table 1 Example 1 (Storage Formulation) A porous membrane with a thickness of 157.5μ, a porosity of 40%, and a pore size of 0.03μ was prepared from Z-7,
A pheromone preparation obtained by immersing 1 s-epoxy-2-methyloctadecane and accommodating the compound in the porous membrane G at a ratio of 511 Jl/c- (indicated by A in graph number 2)
and.

Same (Porous membrane made of P T F E with a thickness of 212.5μ, a porosity of 79cm, and a pore diameter of 1μ (the same Millipore RA)
A pheromone preparation obtained by accommodating the same compound at a rate of 5 my/c, - (indicated by B in the graph), and 25
The amount of pheromone compounds released from rose bushes was measured.

The results are shown in Figure 3. The release of pheromone compounds is 21 μl/cM per day in a storage body with a porosity of 40.
, and in a storage body with a porosity of 79 (11 days 28 μ
It can be seen that it continued at a constant speed for more than 30 days. The amount of pheromone released was determined from the weight loss of the formulation. The same applies to B in the following examples.

Example 2 (Preparation with Control Membrane) Z-7-dodecynyl acetate 2omp was made into a porous membrane made of cellulose acetate and cellulose nitrate and having a diameter of 1.7α, a thickness of 150μ, a pore size of 82cm, and a pore size of 2tt. A container (trade name: Millipore RA) manufactured by Millipore Corporation of the United States was housed therein. The obtained pheromone storage body was encapsulated in a 25μ thick high-density stretched polyethylene membrane and a 200μ thick aluminum sheet to prepare a desired formulation. The outer diameter of this ridge side is 3
．． 0 cm, seal width 0.5 m, emission area 3.1 cr
It was A. Figure 1 shows the release of pheromone compounds from this skin preparation using a high-strength oriented polyethylene membrane exposed to 25°C. Compound release was sustained over 100 days at a constant rate of 30 microns per day. By increasing the thickness of this polyethylene film to 125μ, the compound release rate can be increased to 60μ per day! (This was successfully controlled. As a control formulation, a formulation obtained by enclosing 1 μ of a low-density polyethylene capped pheromone compound was used. In this control formulation, no release control function was observed. Control Formulation 1
1 is a storage body obtained by decomposing a pheromone compound into a polyvinyl chloride polymer material.

A preparation obtained by encapsulating with a release control membrane made of cellulose acetate and cellulose nitrate was used. This pair (I6 formulation is also 20
It is possible that the release rate after the first day will decrease over time without any limitation.

Example 3 (preparation with control film) Z-7,8-epoxy-2-methyloctadecane F3t
np was prepared using cellulose acetate and cellulose nitrate to prepare a porous η membrane (trade name: Mi 11 Bore 1 (trade name: Mi 11 Bore 1) (trade name: Mi 11 Bore 1) (trade name: 50μ of the obtained f' pheromone compound storage body
11 liters of the formulation of the present invention was encapsulated in a thick low-density polyethylene membrane and a 200 μm thick aluminum sheet.

This preparation (outer diameter 2. OL: rn, seal width 0.5
1 piece in cm.

The release of pheromone compounds from this formulation at 25°C through a low density polyethylene membrane is shown in 151d. Release of pheromone compounds was sustained for 200 days at a constant FW of 15 μl per day. This emission, ffl[, is
By changing the thickness of the polyethylene film to 25μ, -
Easy to control with 30 μl per day.

Example 4 (UV-opaque formulation) Z, I! , 1.25 mp of -9,12-tetradecachenyl acetate was placed in a 1.7 Crn porous membrane. The porous membrane has four storage bodies: a storage body made of [1'j-acid cellulose and cellulose nitrate, a storage body made of P'I'FE, a storage body made of polysulfone, and a storage body made of polyvinyl chloride. It is also used. The film thickness, porosity B and pore diameter of each are shown in Table 21 below. Each pheromone compound storage body is made of a polyurethane film (thickness 125μ) that is opaque to UV rays and has a release control function, and has a thickness of σ2.
It was enclosed in a 00μ aluminum sheet. The obtained preparation had an outer diameter of 3. Ocrn, seal width fJ, 5σ is 1.

The release of pheromone compounds from these drugs at 25°C is shown in Figure 6. Preparations obtained using UV-impermeable porous membranes such as polysulfone and polyvinyl chloride as storage bases. The pheromone release rate is 7.5μp/
cM and lasted for 50 days. on the other hand.

The release rate of agent A σ) compound, which is made of cellulose 2 and a substrate that transmits ultraviolet rays such as P'l'FE, was extremely unstable.

Table 2 z l E-711t -he* as a pheromone compound
5 ml of Satecadienyl acetate) was used. This was placed in a storage body of polysulfone porous membrane (same as in Example 4) with a diameter of 1.4 crn, and a preparation was prepared using a 100 μm thick polyurethane membrane as a release control membrane. The release of pheromone compounds from this formulation at 25°C is shown in Figure 7. The F31tl daily release rate was sustained over 200 days.

Example 6 (UV-opaque formulation) l+”-7+11-hexadecachenyl acetate and Z,Z-7,11-hexadecachenyl T-fl
f-gkk mixture 5 was used as a grape pheromone compound, and a storage body made of the same base material and i of the same type material as in Example 5 was used.
A formulation consisting of a +t control membrane was prepared. The resulting formulation had an outer diameter of 2.6 cm and a seal width of 0.5 cm.

Figure 48 shows the release of pheromone compounds at 25°C from this arbor.
It maintains the release rate of 1 day.

Example 7 (Ultraviolet radiation! 4 agents) E, E-8,10-dodecageno/l/20 mJl was housed in a polysulfate reservoir with a diameter of 1.7α, and this reservoir was placed in a body with a thickness of 20 (Jμ). Enclose with a polyurethane film and prepare the preparation. The prescribed preparation is in an outer sachet 3. Ocm
, which lasted for more than a day.

Example 8 (Ultraviolet opaque preparation) Z-11-hexadecanol LOnll with 1α diameter 1.7
The sample was housed in a polysulfone storage body of 1.5 cm in diameter, and this was sealed with a 100 μm piece of polyurethane film. The obtained tl, f preparation has an outer diameter of 3. Ocm S and seal width 0.5 vice.

The release of the compound at 25° C. is shown in 41 oat.

25 μp/day of one pair of release series 1 (is 120 [:I t
Hold it for a long time and get one light.

'碍1iihaWIJ9(3g external radiation opaque-M IE-
11~Tetradecenal 157n/ was contained in a polysulfone storage body with a diameter of 1.4 cm, and fl, 37571
Enclose it in thick polyurethane. The obtained preparation had an outer diameter of 26 - seal width U, and had a diameter of 5 cn+. The release of the compound at 25°C is expressed as r, i', 111Δ
Shown below. Release of 45 μl/day] East time or 150 days 1
I have one child and one child.

[Brief explanation of the drawing]

No. 11A is a side 1 vertical view showing an example of the preparation of the present invention comprising a compound and a storage body, No. 21.4 +-! Kihatsu 111J uses a release rate control membrane to horizontally release the pheromone storage body.
Figure 42 fa+ shows the formulation, and the side surface curve Ld of one example thereof.
. Figure 2 (bl is the side force of another example), Figure 3 is the compound release arrester IK of the pheromone storage body at 75
Figures 4 and 5 are graphs showing the compound release rates of stool preparations formed by encapsulating a pheromone storage body with a release rate α811 T41 membrane, respectively. +z Figures 6 to i11
The figures are graphs showing the release rate of compounds of UV-opaque formulations. 1. Storage body, 2. Release rate controlling membrane, 3.
Linking film, 11- Compound release surface of storage body ○ and below
-1'P Riju Yamaki Hide Sakuyoshi 1 Kasumi A2 figure (O) (b) Poetry Itl (Japanese) Yoshi 5 figure left 6 figure 0 10 20 30 40 50B now Ifl (Japanese) Sho 7 figure Yoshi 8 figure time direction (Japanese) Yoshi 9 figure Yoshi figure 10 figure a4 Tfl (cup 711 figure time m (Japanese) Procedural amendment (self-motivated) Akira [J5 Tsukuda f) October 13 Commissioner of the Patent Office Tono 1, Display of case 1982 Patent Application No. 122537 2
, Title of the invention: Pheromone '1ul13, Representative of the person making the amendment: Hijikata 3, Department 4, Agent: 530 Address: No. 17, 2-47 Tenjinbashi, Kita-ku, Osaka-shi, Osaka Prefecture Ci, 2 of the invention increased by the 5th amendment 〇Figure 2 (CI) V'' (b) 03

Claims (1)

[Claims] 1. It has a pheromone compound or a pheromone-like compound and a porous storage body that accommodates the compound in its pores, and nucleation is performed so that the compound can freely move and diffuse within the storage body. A pheromone preparation that communicates with each other. 2. The preparation according to claim 1, wherein the storage body is a base material with low compatibility with a pheromone compound or a pheromone-like compound. 3. +ffl nQ The preparation according to claim 2, wherein the R storage body is at least one selected from the group consisting of cellulose, cellulose acetate, cellulose nitrate, and fluororesin. 4. The storage body is an ultraviolet opaque base material,
Samurai rFii? The formulation according to Item 2 of the Scope of Claims J. 5. Pre-grip claim 4, wherein the storage body is polyurethane, polysulfone or polyvinyl chloride.
Self-contained formulation. 6. a pheromone compound (proboscis or) dilomone-like compound; a porous storage body containing the compound in the pores; and a control membrane for controlling permeation into the porous reservoir, wherein the pores of the porous reservoir are in communication with each other so that the compound can freely move and diffuse within the reservoir. 7. The preparation according to claim 6, wherein the storage body is a group I having low compatibility with a pheromone compound or a pheromone-like compound. 8. The storage medium is cellulose or cellulose acetate. Selective formula i from the group consisting of cellulose nitrate and fluororesin
1. The formulation according to claim @ 7, which is at least one type of. 9. The formulation according to claim 7, wherein the storage body is a UV-impermeable base material. 10. The formulation according to claim 9, wherein the reservoir is polyurethane, polysulfone or polyvinyl chloride. 11, +jjJ control membrane made of polyethylene 11
12, "iJ 1 [1 Thin film or ultraviolet opaque substrate f,
13. The formulation as set forth in claim 6.13. formulation.