JP2011046739A - Sustained release preparation containing two or more sex pheromone substances and controlling method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a sustained release preparation of sex pheromones enabling controlled simultaneous release of sex pheromones corresponding to developmental periods of two or more of insect pests, and a method for controlling the pests. <P>SOLUTION: The sustained release preparation for sex pheromones contains at least two sex pheromone substances comprising 10-20C aliphatic derivatives and is provided with a first chamber of a polymer material containing a part or total of sex pheromone substances having minimal carbon number excluding carbon number of functional groups among the aliphatic derivatives and a second chamber of a polymer material containing the remaining sex pheromone substances. There is further provided a controlling method to use the sustained release preparation of sex pheromones. <P>COPYRIGHT: (C)2011,JPO&amp;INPIT

Description

  TECHNICAL FIELD The present invention relates to a sustained release formulation and control method for sex pheromones to enable simultaneous release of a plurality of sex pheromone substances.

  Currently, the most effective use of pest pheromones is to disrupt a pest's mating behavior by causing a certain concentration of chemically synthesized sex pheromones to stay in the field, resulting in mating inhibition. The law has entered the practical stage. What is important at this time is the development of a controlled-release formulation (dispenser) for releasing the synthesized insect pheromone substance at a certain rate over a long period of time, and the setting of the period during which the target pest must be disrupted in communication. It is.

  Controlling the release of a single pest sex pheromone component at a constant rate over a period of time is often relatively easy because the sex pheromone substance is either a single type or a chemical structurally similar compound. However, some pests have sex pheromone substances that have completely different chemical structures, and it has been difficult to control the release by enclosing them in the same dispenser. For example, the sex pheromone substances of the pear which is a vegetable pest are (Z) -11-hexadecenal and (Z) -hexadecenyl acetate, and the sex pheromone substance of Shiroitomoyoto which is also a pest of vegetables is (Z, E) -9,12-tetradecadienyl acetate and (Z) -9-tetradecenol have different functional groups as sex pheromone substances. Moreover, the main component of the sex pheromone substance of the caterpillars which are pests of fruit trees and tea is (Z) -11-tetradecenyl acetate, but (Z) -9-dode which is a part of minor components. Cenyl acetate and 11-dodecenyl acetate have the same functional group in each compound but have compounds having different carbon numbers as sex pheromone substances. Even if they are enclosed in the same dispenser, the vapor pressure difference is large, so that both components cannot be controlled to be released. Furthermore, in general, there is rarely a single pest in a certain crop, especially in areas with complex pests such as Japan where multiple pests must be controlled simultaneously. Is almost.

When releasing chemical structurally different compounds at the same time, the difficulty in designing sustained release formulations is
(1) The boiling point difference (vapor pressure difference) varies greatly depending on the functional group, and the release cannot be controlled.
(2) Even with compounds having the same functional group, the difference in boiling point (vapor pressure difference) varies greatly due to the difference in the number of carbon atoms, and the release cannot be controlled.
(3) In a preparation supported on a porous carrier having no barrier property, a compound having a high vapor pressure is released quickly even if the evaporation area is constant.
Etc. Moreover, when protecting several pests simultaneously, it is mentioned as a design difficult point that the generation | occurrence | production period differs for every pest.

Microfilm of actual application No.61-88375 (No.62-198201) The microfilm of No. 63-149399 (No. 2-69902)

In this way, even when one kind of pest is mixed with sex pheromone substances that are chemically structurally different, or when multiple pesticide pheromone substances are mixed, it is difficult to release at the ratio of the composition filled inside the preparation. Not only was it more difficult to adapt to the pest outbreak period.
For example, in Japanese pears, Z-11-tetradecenyl acetate (Z-8-dodecenyl), which is mainly composed of Z-11-tetradecenyl acetate (carbon number 14 if the carbon of the ester group is not included) as a main component of the sex pheromone. Nashihimeshinki, Z-13-icosen-10-one (20 carbon atoms not including carbon of carbonyl group), which has acetate (carbon number not including ester group carbon as 12) as the main component of sex pheromone, It is indispensable to simultaneously control three kinds of pests of the peach sink moth as the main component. In particular, in pears, the pesticide sex pheromone Z-8-dodecenyl acetate of Nashihimeshinshin is important in autumn late cultivars even though its vapor pressure is higher than the other two species, and long-term release desired. At present, a sustained-release preparation satisfying this has not been developed. Acetate means acetate.

  On the other hand, in order to simultaneously disrupt multiple pests, it is possible to create each dispenser and install and control it to match each pest occurrence period, but the cost of formulation increases, Installation of dispensers also requires a great deal of labor, which goes against labor saving in agriculture.

Thus, it has been desired to develop a sustained-release preparation that can successfully release a plurality of sex pheromones in a more labor-saving manner.
The object of the present invention is to enable simultaneous release control when a single type of insect pest is mixed with sex pheromone substances having different chemical structures or when a plurality of insect pests are mixed. It is an object of the present invention to provide a sustained release preparation of sex pheromone that can release sex pheromone adapted to the above and a method for controlling the same.

  The present inventors have solved these problems, can control the simultaneous release of a plurality of sex pheromone substances, and can release sex pheromones in accordance with the generation period of pests. As a result, a part or all of the sex pheromone substance having the smallest number of carbon atoms not including the carbon number of the functional group is encapsulated in one polymer material, and the remaining sex pheromone substance is encapsulated in the other polymer material. The present invention has been completed by finding that the above object can be achieved preferably by joining and integrating the two in parallel.

  Specifically, it is a sex pheromone sustained-release preparation containing at least two sex pheromone substances of aliphatic derivatives having 10 to 20 carbon atoms, and the sex pheromone having the shortest carbon number among the aliphatic derivatives. There is provided a sex pheromone sustained-release preparation comprising a first chamber of a polymer material containing a part or all of a substance and a second chamber of a polymer material containing a remaining sex pheromone substance. Moreover, the control method using this sex pheromone sustained release formulation is provided. As a reference example, a sex pheromone sustained-release preparation container containing at least two sex pheromone substances of an aliphatic derivative having 10 to 20 carbon atoms, the sex pheromone substance having the shortest carbon number among the aliphatic derivatives Provided is a sex pheromone sustained-release preparation container comprising a first chamber of a polymer material for housing part or all of the first chamber and a second chamber of a polymer material for housing the remaining sex pheromone substance. To do.

  According to the sustained-release preparation and the control method of the present invention, controlled simultaneous release is possible for a plurality of pests, and sex pheromones can be released in accordance with the generation period of the pests.

FIG. 1 shows the production process of the sustained-release preparation of the present invention. FIG. 1 (a) is a tube made of two polymer materials, FIG. 1 (b) is a joint provided, and FIG. FIG. 1 (d) shows a cross-sectional view of a sustained-release preparation, a sealing step using a heat seal device.

This will be described in detail below.
Examples of the pest pheromone of the present invention are the chemical structure of the component, the role of the target pest, the carbon number as an example, and the control of common Japanese pears and peaches as examples. Become. The vapor pressure was measured by a gas flow method at 25 ° C. in accordance with “OECD Chemicals Test Guideline Supplement Nos. 7-8” (adopted on July 27, 1995).

  When the above compound is wrapped in a tube tubule, capsule, laminate, etc. made of a polymer material membrane and this membrane is used as a barrier to control the release, the release control factor is as follows: (1) Vapor of enclosed sex pheromone substance Two points are important: pressure, (2) the affinity (solubility parameter) of the functional group of the sex pheromone substance and the polymer material.

  In the example of the above table, since the content of the trace component is small, paying attention to the main component, it is considered that the difference in affinity between each ester and the polymer material is extremely small, and the difference between the ester and ketone is also relatively small. Therefore, when a uniform solution in which all the compounds in the above table are mixed is sealed in a certain polymer material, the release rate of each component greatly depends on the vapor pressure. That is, the carbon number of the functional group such as ester having a high vapor pressure, 11-dodecenyl acetate, Z-8-dodecenyl acetate, Z-9-dodecenyl acetate, etc., not including carbon atoms is 12 The compound is preferentially released, and the release of Z-11-tetradecenyl acetate, Z-13-icosen-10-one and the like having a low vapor pressure is suppressed. In addition, a compound having a rapid release cannot achieve a uniform release, and as a result, the life (effective release period) as a sustained-release preparation is remarkably shortened.

  Therefore, as a result of various studies, the present inventors have found that when one kind of pest is mixed with sex pheromone substances having different chemical structures, or when a plurality of pest sex pheromone substances are mixed, the plurality of sex pests are mixed. Among the pheromone substances, the sex pheromone substance having the smallest number of carbon atoms not including the carbon number of the functional group and having a high vapor pressure (in the table, Z-8-dodecenyl acetate, Z-8-dodecen-1-ol) All or a part of the mixture is sealed in a first chamber of an independent polymer material, and the remaining sex pheromone substance is sealed in a second chamber of the polymer material, preferably joined in parallel and integrated. By using this formulation, it is possible to simultaneously control the long-lasting pesticide pheromone and peach moth pheromone, including the highest vapor pressure pesticide pheromone component, without suppressing the release of other components. It found that can be released, and have completed the present invention.

The sex pheromone substance used in the present invention is an aliphatic derivative having 10 to 20 carbon atoms, preferably a lepidopteran aliphatic linear alcohol, an ester thereof, and a ketone, and two or more kinds thereof are simultaneously released. Is the case. The aliphatic derivative is preferably a group consisting of an aliphatic linear alcohol having 10 to 18 carbon atoms, an aliphatic linear acetate having 12 to 20 carbon atoms and an aliphatic linear ketone having 10 to 20 carbon atoms. Chosen from. In addition, since the carbon number of the functional group of the aliphatic linear acetate and the aliphatic linear ketone is 2 and 1, respectively, the carbon number not including the carbon number of the functional group is the aliphatic linear acetate. 10 to 18, and 9 to 19 for aliphatic linear ketones.
Two or more kinds of aliphatic derivatives may be two or more kinds of sex pheromone substances belonging to the same class, or two or more kinds of sex pheromone substances belonging to different classes. In addition, a stabilizer such as an antioxidant and an ultraviolet absorber and a colorant can be mixed with these substances as long as they are 10% by weight or less.

For example, in the case of a communication disrupter for a plurality of types of pests targeting Japanese pears and peaches, three types of pests are targeted as shown in Table 2.
Nashihime Shinkai has a sex pheromone containing Z-8-dodecenyl acetate as a main component and Z-8-dodecen-1-ol as a minor component, and its generation period is from late April to late September. The caterpillars are mainly composed of Z-11-tetradecenyl acetate, Z-9-tetradecenyl acetate, Z-9-dodecenyl acetate, 11-dodecenyl acetate and 10-methyl- It has a sex pheromone containing dodecyl acetate and Z-11-tetradecen-1-ol as trace components, and the generation period is from mid-May to early September. Peach squid has a sex pheromone whose component is Z-13-icosen-10-one, and the generation period is from late May to mid-September.
In addition, a main component means the thing with most content among the structural components of the sex pheromone of each pest. The fine component refers to a component other than the main component among the components of the sex pheromone of each pest.

Among them, as a main component, all or a part of the shortest carbon number pesticide pheromone substance is enclosed in the first chamber of an independent polymer material, and other peach sinker moths and leafworm sex pheromones are contained in the polymer material. Enclose in the second chamber. At this time, the second chamber contains a trace component with the same carbon number as the main component of Nashihimeshinkui, but the biological component of the trace component may not be fully elucidated, so it is the same as the main component. It is desirable to release from the same polymeric material portion by mixing it with the polymeric material portion.
The amount of the sex pheromone substance stored in each chamber varies depending on the release period of the sustained-release preparation, the volatility of the sex pheromone substance, the affinity with the polymer material of the container, and the like. 150 mg, preferably 100 mg, 200-300 mg, preferably 230 mg for the second chamber.

  The polymer material used in the present invention is polyolefin, polyacryl, polyester, polyamide, polymethacryl, polyolefin-vinyl alcohol ester copolymer, etc., and if the film is used as a barrier, general extrusion Tubes processed into a tube by a molding method, capsules, bags, laminates and the like can be mentioned, and plasticizers, lubricants, stabilizers, colorants and the like can be appropriately mixed in the processing. In the present invention, the two encapsulated polymeric materials can be the same or different from each other as long as they can be connected in some form, preferably integrated.

The storage chamber made of a polymer material used in the present invention is not particularly limited as long as it can store a sex pheromone substance. For example, it is wrapped with a tube capillary, a capsule, a laminate, etc. made of a polymer material film. Release can be controlled using a membrane as a barrier.
The dimensions of the polymer film used can be appropriately selected depending on the physical properties of the sex pheromone substance to be enclosed, and the wall thickness and inner / outer diameter are the same in the first chamber and the second chamber of the two polymer materials, It may be different. In particular, the wall thickness is greatly affected by the evaporation rate of the sex pheromone component, so that a suitable thickness can be selected according to the required release period, the vapor pressure of the sex pheromone component, and the dissolution parameters. If there is an extreme difference in wall thickness between the two chambers, it will be difficult to carry out sealing processing at the time of encapsulation in practice, so care must be taken in selecting a practical range.

  In the present invention, the structure of the first chamber and the second chamber of the polymer material is not particularly limited, but preferably can be chemically connected using a heat seal or an adhesive. Moreover, you may connect physically using a tape, a wire, etc. At that time, the tubes 1 and 2 that become the first chamber and the second chamber of the polymer material are independent as shown in FIG. 1A, but are joined by the joint portion 3 as shown in FIG. You may integrate in parallel. Moreover, as shown in FIG.1 (c), by connecting the front-end | tip of a tube chemically or physically using the heat-seal apparatus 4, it will finally show in sectional drawing of FIG.1 (d). Alternatively, a sustained-release preparation having sex pheromones A1 and A2 may be used. It becomes a figure. However, the shape is not limited to this.

EXAMPLES Hereinafter, although an Example, a reference example, and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example.
[Example 1]
Three kinds of compound sustained-release preparations of Nashihimeshin-imo-imo-sigaiga-caterpillars The following tubes (A) and (B) are prepared in parallel as shown in FIG. Was installed on May 9 as shown in FIG. As a result, until the mid-October harvest, no damage was observed on the fruit beetles, peach moth, and pear moth. Table 3 shows the residual ratio of the pheromone component for each insect after the formulation is installed.
(A) The following components are enclosed in a high-density polyethylene tube having an inner diameter of 1.4 mm and an outer diameter of 2.5 mm (thickness of 0.55 mm).
Z-11-tetradecenyl acetate 88mg
Z-9-tetradecenyl acetate 17mg
10-methyl-dodecyl acetate 2mg
Z-9-dodecenyl acetate 5mg
11-dodecenyl acetate 2mg
Z-11-tetradecen-1-ol 1mg
(Peach squid component)
Z-13-Icosen-10-one 80mg
(Nashihime Shinkui component)
Z-8-dodecenyl acetate 34mg
Z-8-dodesen-1-ol 0.3mg
(B) The following components are sealed in a high-density polyethylene tube with an inner diameter of 0.90 mm and an outer diameter of 2.30 mm (wall thickness: 0.70 mm).
Z-8-dodecenyl acetate 95mg
Z-8-dodesen-1-ol 1mg

[Comparative Example 1]
The sex pheromone component used in the examples in a 20 cm high-density polyethylene tube with an inner diameter of 1.5 mm and an outer diameter of 2.6 mm (thickness 0.55 mm) joined with an aluminum wire to give formability An encapsulated solution in which all were uniformly mixed was prepared, and a part of this preparation was placed in the same pear garden as in the above example, and the change over time in the amount of residual pheromone due to its release was measured.
The results are shown in Table 4 below.

  From this result, it is considered that the life of Nashihime Shinkui is about 90 days.

[Reference Example 2]
As a sex pheromone formulation of Peach Twig Borer (Anarsia lineatella), a pest of overseas fruit trees, a 20 cm tube-form formulation in which the following (A) and (B) tubes are integrated in parallel as shown in FIG. Release was confirmed in a constant temperature bath at 25 ° C. and 0.3 m / s. Table 5 shows the change in the residual rate of each sex pheromone component with respect to the number of days elapsed.
(A) A high density polyethylene tube having an inner diameter of 1.07 mm and an outer diameter of 2.07 mm (wall thickness of 0.50 mm) sealed with 140 mg of E-5-dodecenyl acetate.
(B) A high-density polyethylene tube having an inner diameter of 0.70 mm and an outer diameter of 1.10 mm (wall thickness of 0.20 mm) sealed with 60 mg of E-5-dodecenol.

[Comparative Example 2]
The sex pheromone used in Reference Example 2 with a 20 cm high-density polyethylene tube with an inner diameter of 1.28 mm and an outer diameter of 2.48 mm (thickness 0.60 mm) joined with aluminum wire to give formability. An encapsulated solution in which all the components were uniformly mixed was prepared, and the change over time of the residual ratio of each sex pheromone component was measured for this preparation under the same conditions as in Reference Example 2 above. The results are shown in Table 6.

The claims at the time of filing of the original application of the present application are as follows.
[Claim 1]
A sex pheromone sustained-release preparation containing at least two sex pheromone substances of aliphatic derivatives having 10 to 20 carbon atoms, wherein the aliphatic derivatives have the smallest number of carbon atoms not including the carbon number of the functional group A sex pheromone sustained-release preparation comprising a first chamber of a polymer material containing a part or all of the sex pheromone substance and a second chamber of a polymer material containing the remaining sex pheromone substance.
[Claim 2]
The aliphatic derivative is selected from the group consisting of an aliphatic linear alcohol having 10 to 18 carbon atoms, an aliphatic linear acetate having 12 to 20 carbon atoms, and an aliphatic linear ketone having 10 to 20 carbon atoms. The sex pheromone sustained-release preparation according to claim 1.
[Claim 3]
The sex pheromone sustained release preparation according to claim 1 or 2, wherein the sex pheromone sustained release preparation targets a plurality of types of pests.
[Claim 4]
The control method using the sex pheromone sustained release formulation in any one of Claims 1-3.
[Claim 5]
Polymer for containing a part or all of a sex pheromone substance containing at least two sex pheromone substances and having a minimum number of carbon atoms not including the functional group carbon number. A sex pheromone sustained-release preparation container comprising at least one first chamber of material and at least one second chamber of polymeric material for housing the remaining sex pheromone substance.

DESCRIPTION OF SYMBOLS 1 Tube 2 Tube 3 Joint part 4 Heat seal apparatus A1 Sex pheromone substance A2 Sex pheromone substance

Claims (5)

  A sex pheromone containing a mixture of sex pheromones having different chemical structures of one kind of pest or a mixture of sex pheromone substances of a plurality of pests, containing at least two sex pheromone substances of aliphatic derivatives having 10 to 20 carbon atoms A sustained-release preparation, wherein the aliphatic derivative comprises an aliphatic linear alcohol having 10 to 18 carbon atoms, an aliphatic linear acetate having 12 to 20 carbon atoms, and an aliphatic linear chain having 10 to 20 carbon atoms. A first chamber of a polymer material selected from the group consisting of a ketone and containing a part or all of a sex pheromone substance having a minimum number of carbon atoms not including the carbon number of the functional group among the aliphatic derivatives; A second chamber of a polymer material containing the remaining sex pheromone substance is provided, and the sex pheromone substance having the smallest number of carbon atoms not including the functional group carbon number has 10 to 12 carbon atoms not including the functional group carbon number. Aliphatic linear Sex pheromone sustained-release formulation is Seteto.   The sex pheromone sustained release preparation according to claim 1, wherein the sex pheromone sustained release preparation targets a plurality of types of pests.   The sex pheromone sustained-release preparation according to claim 1 or 2, wherein the polymer materials in the first chamber and the second chamber are homogeneous.   The sex pheromone sustained-release preparation according to any one of claims 1 to 3, wherein the thickness of the first chamber is thicker than the thickness of the second chamber.   The control method using the sex pheromone sustained release formulation in any one of Claims 1-4.

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