Sustained-release pheromone preparation

Abstract

To provide a sustained-release pheromone preparation which is easily installed and stably retained on an installation location.SOLUTION: A sustained-release pheromone preparation 10 is formed of at least one pheromone substance 3-containing polymer tube with both ends 2 sealed or pheromone substance 3-containing polymer rod, wherein (a) a circular space 7 closed at a crossover point and one or more spaces 71 closed at two crossover points and an opening portion 6 are formed in a front view by bending in an arc and making the polymer tube or polymer rod cross itself, and the sustained-release pheromone preparation 10 is not crossed in a side view; (b) a circular curvature radius R is 6-15 mm; (c) a linear distance D from a top point 8 of a circularly formed arc to a crossover point 5 that is closest to the top point is 10-50 mm; and (d) a repelling force when opening the crossover point 5 that is closest to the arc to establish a clearance G of 20 mm in the front view is 1.0 N or larger.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a sustained-release pheromone formulation. [Background technology]

[0002] As one method for controlling pests, a mating disruption method has been put into practical use, in which the sex pheromone substances of pests are released to inhibit the mating behavior of the pests, thereby suppressing the density of the pests in the next generation. In control by mating disruption, a technically important practical issue is to provide a sustained-release pheromone formulation that can stably and long-term release the sex pheromone substances of pests in a predetermined location where the sex pheromone substances should be effective, and that can release the sex pheromone substances very gradually and continuously. In response to the above-mentioned issues, a tubular sustained-release pheromone formulation has been proposed, in which a sex pheromone substance is filled into a polymeric thin tube and both ends are sealed. Although it has been shown that tubular sustained-release pheromone formulations can stably release sex pheromones over a long period of time, there has been a problem in how to maintain them in a stable location for a long period of time. As methods for solving this problem, the following have been reported: a sustained-release pheromone preparation in which a sex pheromone substance is stored inside a thin polymeric tube joined (attached) to (an axial direction of) this thin polymeric tube (Patent Document 1); a sustained-release pheromone preparation in which two thin polymeric tubes are joined to form a ring, so that it can be hung from fruit trees or other trees without the need for a metal wire (Patent Document 2); a sustained-release pheromone preparation in which two thin polymeric tubes are twisted together and joined at both ends, thereby utilizing the restoration and repulsive force of the thin polymeric tube to further improve the gripping strength (Patent Document 3); and a sustained-release pheromone preparation in which a thin polymeric tube is bent and rotated to form a ring (Patent Document 4). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 57-156403 [Patent Document 2] Japanese Patent Application Publication No. 11-225646 [Patent Document 3] Japanese Patent Application Laid-Open No. 2013-188159 [Patent Document 4] Japanese Utility Model Application Publication No. 62-122801 Summary of the Invention [Problem to be solved by the invention]

[0004] The sustained-release pheromone formulation in Patent Document 1 has a structure in which a metal wire is attached, and the shapeability of the metal wire allows for easy installation and stable retention. However, it has drawbacks such as increased manufacturing costs and costs for filling the sex pheromone substance due to the use of metal wire, the fact that installation takes some time because the metal wire is twisted to secure it, the hassle of removing it from the installation location after use, and the metal wire damaging pruning blades when pruning fruit trees and other shrubs. Furthermore, although the sustained-release pheromone formulations of Patent Documents 2 and 3 solve the problem of metal wires remaining in orchards and the like, installation requires passing the branches of the fruit trees or other trees through a ring, which requires the use of both hands or a special tool, and therefore does not reduce the effort required for installation. Furthermore, in the sustained-release pheromone formulation of Patent Document 4, the intersections of the capillaries are fused or glued, or are in contact or have a gap of up to three times the diameter of the capillaries, but in the case of fusion or glue, the loops formed must be passed through the branches of the fruit tree or other tree, which limits the locations where they can be installed. Also, in the case of contact or with a small gap, although they can be hung from the branches of the fruit tree or other tree through this gap, there is a problem that they can fall due to natural wind or wind pressure from pesticide spraying machines, etc. In view of the above circumstances, there has been a demand for the development of a sustained-release pheromone formulation that is suitable for controlling the release of sex pheromones over a long period of time, is easy to install, can be stably maintained in place, and does not require high manufacturing costs. [Means for solving the problem]

[0005] As a result of extensive research to achieve the above object, the present inventors discovered that by molding a polymeric thin tube or rod into a predetermined shape, it is possible to obtain a sustained-release pheromone preparation that is easy to install and can be stably retained at the installation location, and this discovery led to the completion of the present invention. According to one aspect of the present invention, A sustained-release pheromone preparation comprising a polymeric thin tube or rod having an outer diameter of 1.5 to 6 mm and having each end sealed, the polymeric thin tube or rod containing at least one pheromone substance, wherein the polymeric material constituting the polymeric thin tube or rod is polybutylene succinate or a mixture of polybutylene succinate and polybutylene succinate adipate; (a) A sustained-release pheromone preparation in which the polymeric thin tubes or rods are bent in an arc and crossed to form a circular space closed at one crossing point, one or more spaces closed at two crossing points, and one opening when viewed from the front, and which does not cross when viewed from the side, (b) the radius of curvature of the circular shape is 6 to 15 mm; (c) the straight-line distance from the apex of the circular arc to the intersection closest to the apex is 10 to 50 mm; (d) When viewed from the front, the repulsive force is 1.0 N or more when the distance between the intersection closest to the arc is 20 mm. A sustained release pheromone formulation is provided. [Effects of the Invention]

[0006] The present invention provides a sustained-release pheromone formulation that can be easily installed on fruit trees and other trees while maintaining its release control capability, and that can be stably maintained in place without falling even when exposed to strong winds that occur in nature or wind pressure and vibrations from pesticide sprayers, etc., and that can provide reliable sustained release over a long period of time. [Brief explanation of the drawings]

[0007] [Figure 1] FIG. 1A is a partial cross-sectional front view showing an embodiment of the present invention consisting of a single capillary tube, and FIG. 1B is an enlarged partial view thereof. [Figure 2] FIG. 2 is a perspective view showing a method for placing the formulation of FIG. 1 on a tree branch. [Figure 3] FIG. 3A is a partial cross-sectional front view showing an embodiment of the present invention which comprises a single capillary tube formed by bending the sections from both sealed ends to the intersection nearest to the ends, and FIG. 3B is a partially enlarged view thereof. [Figure 4] Fig. 4A is a front view showing an example of an R-pin shape, Fig. 4B is a front view showing an example of a hexagonal shape, Fig. 4C is a front view showing an example of a star shape, and Fig. 4D is a front view showing an example with four intersections. [Figure 5] 5A and 5B are front views showing details of an embodiment of the present invention, in which FIG. 5A shows the radius of curvature, FIG. 5B shows the angle of the arc, and FIG. 5C shows the linear distance from the apex of the arc to the intersection point. [Figure 6] 6A and 6B are perspective views showing a method for measuring a repulsive force, in which FIG. 6A shows a preparation state and FIG. 6B shows a state in which an external force is applied. [Figure 7] 1 is a diagram showing the relationship between repulsion force and drop rate. [Figure 8] 8A is a perspective view showing two parallel capillaries, FIG. 8B is a perspective view showing three parallel capillaries, FIG. 8C is a triplet capillary, FIG. 8D is a capillary with a thin rod attached, FIG. 8E is a capillary with two parallel capillaries attached, and FIG. 8F is a perspective view showing two twisted capillaries. [Figure 9] 9A and 9B are perspective views showing examples of thin rods having different cross sections, where FIG. 9A is a cylindrical thin rod, FIG. 9B is a star-shaped thin rod, and FIG. 9C is a semi-tubular thin rod. [Figure 10] 10A and 10B are perspective views showing capillaries having different cross sections, and FIGS. 10C and 10D are perspective views showing square capillaries. [Figure 11] FIG. 11A is a schematic diagram showing a bending jig, and FIG. 11B is a schematic diagram showing the processing steps. [Figure 12] FIG. 2 is an external view showing a bending jig used in Example 1. [Figure 13] FIG. 1 is an external view showing the sustained-release pheromone formulation obtained in Example 1. [Figure 14] FIG. 2 is a cross-sectional view showing the state of extrusion molding of a polymeric thin tube. DETAILED DESCRIPTION OF THE INVENTION

[0008] First, the shape of the sustained-release pheromone preparation, which is a feature of the present invention, will be described.

[0009] The sustained-release pheromone preparation is formed by bending at least one polymeric thin tube or rod containing a pheromone substance into an arc and crossing it to form two or more closed spaces (closed spaces 7 and 71 in Figure 1) and an opening 6 when viewed from the front, as shown in Figure 1. The shape of the closed space is not limited as long as it satisfies the radius of curvature, linear distance, and repulsive force described below. For example, the space 7 closed at the intersection 5 shown in Figure 1 is circular, and the space 71 closed at the intersections 5 and 51 is elliptical; the space 7 closed at the intersection 5 shown in Figure 4A is elliptical, and the space 71 closed at the intersections 5 and 51 is semicircular; the space 7 closed at the intersection 5 shown in Figure 4B is hexagonal, and the space 71 closed between the intersections 5 and 51 is semicircular; and the space 7 closed at the intersection 5 shown in Figure 4C is star-shaped, and the space 71 closed between the intersections 5 and 51 is semicircular. Furthermore, the number of closed spaces may be more than two. For example, as shown in Figure 4D, the closed space 7 at intersection 5 is circular, the closed space 71 at intersections 5 and 51 is elliptical, and two additional elliptical closed spaces 72 and 73 are provided at intersections 52 and 53. However, in the case of the shape of Figure 4D, if the cross section ends at intersection 52 without intersection 53, the capillaries will overlap when pushing the opening 6 between the two sealed ends 2 into the branch, making it impossible for the branch to enter. Therefore, when considering preventing dropping by increasing the number of intersections in this way, it is important that the number of intersections is always an even number. As shown in Figure 1, the opening 6 may have a shape in which the thin tube or thin rod portion between the intersection 51 and both sealed ends 2 is not processed. However, if the opening 6 is bent so that a semicircle is formed between the intersection 51 and both sealed ends 2 as shown in Figure 3, the thin tube or thin rod portion is less likely to escape sideways when the opening 6 between both sealed ends 2 is pressed against the branch, thereby further improving attachment ease.

[0010] The sustained-release pheromone formulation is a sustained-release pheromone formulation that does not cross in side view. As shown in Figure 2, the sustained-release pheromone formulation passes through closed space 71 by pressing branch 9 or the like against opening 6, and is then suspended from the branch or the like in closed space 7. The sustained-release pheromone formulation suspended from the branch is prevented from falling by closed space 71 formed between intersections 5 and 51. The polymeric thin tubes or rods may be in contact with each other in side view, or may have a slight gap in side view that does not affect the drop. If intersections 5 and 51 are crossed, fused, or glued, the workability of installation and retrieval is reduced. By not allowing the sustained-release pheromone formulation to cross in side view, it is possible to easily install and retrieve it with one hand, for example, and this contributes to improved work efficiency.

[0011] The radius of curvature of the polymeric thin tubes or thin rods bent into an arc and crossed is 4 to 15 mm, preferably 6 to 12 mm, and more preferably 6 to 10 mm. If the radius of curvature is less than 4 mm, the bending process of the thin tubes or thin rods may exceed the elastic deformation range, causing the thin tubes or thin rods to break, which is not appropriate. On the other hand, if the radius of curvature exceeds 15 mm, the repulsive force decreases and is not practical. Here, the radius of curvature refers to the radius R of the arc formed by bending into an arc shape, as shown in FIG. 5A.

[0012] The linear distance D from the apex 8 of the arc formed by bending a polymeric thin tube or rod into an arc to the intersection 5 closest to the apex is 10 to 50 mm, preferably 15 to 45 mm, and more preferably 20 to 40 mm. If the linear distance is less than 10 mm, the total length of the thin tube or rod will be 50 mm or less, which is uneconomical. If the linear distance is more than 70 mm, even if a thin tube or rod with a certain degree of rigidity is used, the repulsive force of the intersection 5 will not be sufficient, resulting in a lack of installation stability. Here, the straight-line distance refers to the distance D from the inside of the vertex 8 of the curved arc to the center of the intersection 5 closest to the vertex, as shown in FIG. 5C.

[0013] Next, the repulsive force of the sustained-release pheromone preparation will be explained. In this invention, assuming that the formulation will actually be placed on and retrieved from branches, etc., the repulsive force was evaluated when the distance between the two is 20 mm when viewed from the front and the intersection is open. In actual use, the sustained-release pheromone formulation is placed outdoors on plants or supports in a field for an extended period of time, from just before the emergence of target pests until the end of the emergence. During this time, the sustained-release pheromone formulation must not fall due to natural phenomena such as rain and wind, or agricultural work using machinery such as pesticide spraying, fruit thinning, and pruning. To achieve this, the repulsive force is 1.0 N or more, preferably 1.2 N or more, more preferably 2.5 N or more, and even more preferably 3.5 N or more. The method for measuring the repulsive force will be described below. As shown in Figure 6, the repulsive force used as an index was measured by fixing one curved end of the sustained-release pheromone formulation horizontally with a metal chuck 31, and using a force gauge (Imada Co., Ltd.: DST-20N) 32, hook 33 of the attachment was placed on the other curved end, and pulled downward until the distance G at the intersection was 20 mm when viewed from the side, so that the polymer thin tube or rod would not separate. The peak value at this time was measured as the repulsive force.

[0014] The angle of the arc formed by bending the polymer thin tube or rod into an arc is preferably 20 to 120 degrees, more preferably 20 to 90 degrees, and even more preferably 20 to 80 degrees, from the viewpoint of maintaining a good repulsive force. The smaller the arc angle, the stronger the repulsive force of the polymer, making it more difficult for the ends to open, and therefore, better prevention of dropping can be expected. Here, the angle of the arc refers to the intersection angle θ of the tangents at both end points of the arc formed by bending in an arc shape as shown in FIG. 5B.

[0015] Next, the polymer thin tube or polymer thin rod will be described. The polymeric capillary is filled with a pheromone substance and has both ends sealed. The inner diameter of the polymeric capillary varies depending on the amount of pheromone substance required per preparation, but is preferably 0.2 to 3 mm, more preferably 0.3 to 2.0 mm, from the viewpoint of formability of the preparation or filling the tube with the sex pheromone. The wall thickness of the capillary is preferably 0.15 to 1.5 mm, more preferably 0.3 to 0.8 mm, from the viewpoint of ease of processing and maintaining a good repulsive force. The outer diameter of the capillary, which is determined by the inner diameter and wall thickness of the capillary, is preferably 1.5 to 6 mm, from the viewpoint of ease of processing and maintaining a good repulsive force.

[0016] The polymer thin rod may be, for example, a polymer material described below into which a pheromone substance or an inorganic filler carrying a pheromone substance has been kneaded, or the polymer material may be impregnated with the pheromone substance. From the viewpoint of ease of processing and maintaining a good repulsive force, the diameter of the thin rod is preferably the same as the outer diameter of the polymer thin tube, and is preferably 1.5 to 6.0 mm.

[0017] When a pheromone substance is injected into a polymeric capillary tube, the amount of the pheromone substance supported in the polymeric capillary tube is preferably 50 to 600 mg, and more preferably 80 to 500 mg, for the most common effective length L of 200 mm. If the amount supported is less than 50 mg, the amount of pheromone liquid released during the installation period may be insufficient, and the pest control effect due to mating disruption may decrease. On the other hand, if the amount supported is more than 600 mg, the volume may be excessive, and the pheromone may remain even after the pest emergence period and be wasted. Note that even when the pheromone substance is diluted with a solvent before use to control the release amount, the amount of the pheromone substance supported is preferably within the above range. When a pheromone liquid is kneaded into a thin polymer rod, the content of the pheromone substance in the thin polymer rod is preferably 50 to 600 mg, and more preferably 80 to 500 mg, when the effective length L is 200 mm. The content of the pheromone substance in the thin polymer rod is preferably 2 to 60 mass %, and more preferably 2 to 40 mass %, based on the total mass of the thin polymer rod including the pheromone substance. A content of less than 2 mass % may not ensure a sufficient release rate, while a content of more than 60 mass % may not provide sufficient release control. The pheromone substance may be a natural pheromone substance extracted and separated from a pest insect, but synthetic pheromone substances are preferred from the standpoint of cost and ease of obtaining large quantities.

[0018] The cross section of the polymer thin tube and polymer thin rod is not particularly limited and can have various shapes. Examples of polymeric capillaries include the circular shape shown in FIG. 8, the elliptical shape shown in FIGS. 10A and 10B, and the rectangular shape shown in FIGS. 10C and 10D. In particular, the elliptical and rectangular shapes with thick side walls are advantageous in that they can increase the repulsive force during processing. As for the thin polymer rod, for example, a circle as shown in FIG. 9A, a star shape as shown in FIG. 9B, and a hollow circle as shown in FIG. 9C can be mentioned.

[0019] The length of the polymeric thin tubes and rods must be at least 100 mm to form a closed space such as a circle, semicircle, ellipse, hexagon, or star shape, and is preferably 100 to 400 mm, more preferably 150 to 300 mm, from the viewpoints of installation stability and ease of installation and retrieval. Processing a thin tube or rod-like object longer than 400 mm is not preferred because the linear distance from the apex of the arc to the intersection becomes too long, making installation time-consuming and preventing the required repulsive force from being obtained.

[0020] The polymeric materials constituting the polymeric thin tubes and polymeric thin rods used in the sustained-release pheromone formulations are preferably polycaprolactone, polybutylene succinate, polyethylene succinate, polybutylene adipate, polyglycolic acid, polylactic acid, polyhydroxyalkanoate, etc., or copolymers thereof. These polymeric materials may be used alone or in combination of two or more. When polymeric thin tubes and rods, which have a relatively small outer diameter and are molded into a long shape, require a resilient force to be able to be suspended from a fruit tree or other tree. Formulations made by bending thermoplastic resins such as polyethylene, ethylene-vinyl acetate copolymer, and polyvinyl chloride into an arc exhibit plastic deformation rather than elastic deformation, and therefore, when the intersections are opened to suspend them from a tree or other tree, they do not return to their original shape but remain open, making them unsuitable. The polymeric materials listed above are suitable for the elastic deformability of the molded product. Among these, polybutylene succinate, polybutylene adipate, and polybutylene succinate adipate are particularly preferred from the viewpoint of ease of processing.

[0021] Although at least one polymeric capillary tube or rod is required to constitute the sustained-release pheromone formulation, two or three polymeric capillary tubes 1 arranged in parallel may be used, as shown in FIGS. 8A and 8B. Alternatively, three polymeric capillary tubes 1 may be stacked as shown in FIG. 8C. Furthermore, as shown in FIGS. 8D and 8E, a polymeric capillary tube 1 and a polymeric rod 11 may be arranged side by side. In the embodiment shown in FIGS. 8D and 8E, where a polymeric capillary tube 1 and a polymeric rod 11 are arranged side by side, a polymeric rod not containing a pheromone substance may be arranged side by side with the polymeric capillary tube. Depending on the type of pheromone substance and the type of target pest, multiple polymeric capillaries or rods with different materials and dimensions such as inner and outer diameters may be required. In such cases, multiple polymeric capillaries 1 may be twisted together as shown in FIG. 8F.

[0022] The pheromone substance may be a pheromone substance that is liquid at 25°C, a carrier containing a pheromone liquid, or a solid pheromone substance. Specific examples of the pheromone substances used in the present invention include Z,Z-7,11-hexadecadienyl acetate and Z,E-7,11-hexadecadienyl acetate, which are the sex pheromone substances of the pink bollworm (pink bollworm), Z-8-dodecenyl acetate, which is the sex pheromone substance of the oriental fruit moth (oriental fruit moth), E-5-decenyl acetate, which is the sex pheromone substance of the peach twig borer (oriental fruit moth), and Z-9-dodecenyl acetate, which is the sex pheromone substance of the grapeberry moth (oriental fruit moth). E,Z-7,9-dodecadienyl acetate, the sex pheromone of the European grapevine moth (Grapevine vine moth), E-11-tetradecenyl acetate, the sex pheromone of the light brown apple moth (Apple vine moth), E,E-8,10-dodecadienol, the sex pheromone of the codling moth (Codling moth), Z-11-tetradecenyl acetate, the sex pheromone of the leaf roller (Tortricidae), and the sex pheromone of the peach tree borer (Peach tree moth). The sex pheromone compounds are Z,Z-3,13-octadecadienyl acetate and E,Z-3,13-octadecenyl acetate, Z-11-hexadecenal, the sex pheromone compound of the American bollworm (Helicoverpa armigera), Z-9-hexadecenal, the sex pheromone compound of the Oriental tobacco budworm (Helicoverpa gracilis), E,E-8,10-dodecadienyl acetate, the sex pheromone compound of the soybean pod borer (Helicoverpa chinensis moth), and Z-11-hexadecenal, the sex pheromone compound of the diamondback moth (Plutella xylostella). Z-11-hexadecenyl acetate and Z-11-hexadecenal, Z-11-hexadecenol and n-hexadecyl acetate, which are sex pheromones of the cabbage armyworm (Mamus brassicae), Z,E-9,12-tetradecadienyl acetate and Z-9-tetradecenol, which are sex pheromones of the beet armyworm (Spodoptera exiguai), and Z,E-9,11-tetradecadienyl acetate and Z,E-9, which are sex pheromones of the common cutworm (Spodoptera litura).12-Tetradecadienyl acetate, Z-9-tetradecenyl acetate, the sex pheromone substance of the fall armyworm, E-4-tridecenyl acetate, the sex pheromone substance of the tomato pinworm, Z-11-hexadecenal and Z-13-octadecenal, the sex pheromone substances of the rice stem borer (chilo suppressalis), 5,9-dimethylpentadecane and 5,9-dimethylhexadecane, the sex pheromone substances of the coffee leafminer, and the sex pheromone substance of the peach leafminer (peach leafminer). 14-methyl-1-octadecene, Z-7-icosen-11-one, the sex pheromone of the peach fruit moth (Peach fruit moth), 7,8-epoxy-2-methyloctadecane, the sex pheromone of the gypsy moth (Lymantria dispar), Z-13-hexadecen-11-ynyl acetate, the sex pheromone of the pine processional moth, 2-butanol, the sex pheromone of the woolly scarab beetle, and Z-7,15-hexadecane, the sex pheromone of the yellow-wish elongated chafer (Long-legged chafer). Sadecadien-4-olide, n-dodecyl acetate, the sex pheromone of the sugarcane wireworm (Okinawa sugarcane wireworm), E-9,11-dodecadienyl butyrate and E-9,11-dodecadienyl hexanate, the sex pheromone of the sugarcane wireworm (Sakishima sugarcane wireworm), (R)-Z-5-(oct-1-enyl)-oxacyclopentan-2-one, the sex pheromone of the cuprea chafer (Diamondback beetle), and the rice leaf bug (Akahigehisomiridae). Hexyl hexanoate, E-2-hexenyl hexanoate, and octyl butyrate are sex pheromones of the Japanese white sorghum bug (Mistyes sieboldii), hexyl butyrate, E-2-hexenyl butyrate, and E-4-oxo-2-hexenal are sex pheromones of the sorghum plant bug (Red-striped Mistyes), and 6R-Z-3,9-dimethyl-6-isopropenyl-3,9-decadienyl propionate and 6R-Z-3,9-dimethyl-6-isopropenyl-3,9-decadienyl propionate are sex pheromones of the white peach scale (Mulberry scale).Examples include 9-decadienol, S-5-methyl-2-(1-propen-2-yl)-4-hexenyl 3-methyl-2-butenoate, the sex pheromone of the vine mealybug, Z-9-tricosene, the sex pheromone of the house fly, gentisylquinone isovalerate, the sex pheromone of the German cockroach, and olean, the sex pheromone of the olive fly.

[0023] Other examples of the pheromone substances that can be used in the present invention include spiroacetals, linear aliphatic aldehydes, linear aliphatic acetates that are saturated or have one or more double bonds, linear aliphatic alcohols, linear aliphatic ketones, aliphatic hydrocarbons, and carboxylic acids.

[0024] Specific examples of spiroacetals include 1,6-dioxaspiro[4.5]decane, 2-ethyl-1,6-dioxaspiro[4.4]nonane, 3-hydroxy-1,7-dioxaspiro[5.5]undecane, 4-hydroxy-1,7-dioxaspiro[5.5]undecane, 7-methyl-1,6-dioxaspiro[4.5]decane, 2-methyl-1,6-dioxaspiro[4.5]decane, 1,7-dioxaspiro[5.5]undecane, and 2,7-dimethyl-1,6-dioxaspiro[4.4] Nonane, 2,4,8-trimethyl-1,7-dioxaspiro[5.5]undecane, 2-methyl-1,7-dioxaspiro[5.5]undecane, 1,7-dioxaspiro[5.6]dodecane, 2,8-dimethyl-1,7-dioxaspiro[5.5]undecane, 2,2,8-trimethyl-1,7-dioxaspiro[5.5]undecane, 2-ethyl-1,7-dioxaspiro[5.5]undecane, 2-methyl-1,7-dioxaspiro[5.6]dodecane, 2-ethyl-7-methyl-1,6- Dioxaspiro[5.6]decane, 7-ethyl-2-methyl-1,6-dioxaspiro[5.6]decane, 2,7-diethyl-1,6-dioxaspiro[4.4]nonane, 2,7-dimethyl-1,6-dioxaspiro[4.6]undecane, 2-methyl-7-propyl-1,6-dioxaspiro[4.4]nonane, 3-hydroxy-2,8-dimethyl-1,7-dioxaspiro[5.5]undecane, 2-propyl-1,7-dioxaspiro[5.5]undecane, 2-ethyl-8-methyl-1 ,7-dioxaspiro[5.5]undecane, 8-ethyl-2-methyl-1,7-dioxaspiro[5.5]undecane, 2,7-diethyl-1,6-dioxaspiro[4.5]decane, 2,7-dipropyl-1,6-dioxaspiro[4.4]nonane, 7-butyl-2-methyl-1,6-dioxaspiro[4.5]decane, 8-methyl-2-propyl-1,7-dioxaspiro[5.5]undecane, 2-propyl-8-methyl-1,7-dioxaspiro[5.5]undecane, and the like.

[0025] The aliphatic linear aldehyde preferably has a carbon number of 10 to 18. Specific examples of the aliphatic linear aldehyde having a carbon number of 10 to 18 include Z-5-decenal, 10-undecenal, n-dodecanal, Z-9-dodecenal, E5Z10-dodecadienal, E8E10-dodecadienal, n-tetradecanal, Z7-tetradecenal, Z9-tetradecenal, Z11-tetradecenal, Z9E11-tetradecadienal, Z9Z11-tetradecadienal, Z9E12-tetradecadienal, Z9E11,13-tetradecatrienol, and Z10-pentadecenal. E9Z11-pentadecadienal, n-hexadecanal, Z7-hexadecenal, E6Z11-hexadecadienal, E4Z6-hexadecadienal, E4E6Z11-hexadecatrienal, E10E12E14-hexadecatrienal, n-octadecanal, Z9-octadecenal, E14-octadecenal, E2Z13-octadecadienal, Z3Z13-octadecadienal, Z9Z12-octadecadienal, Z9Z12Z15-octadecatrienal, and the like.

[0026] The saturated or aliphatic linear acetate having one or more double bonds preferably has 12 to 20 carbon atoms. Specific examples of the saturated or C12-C20 aliphatic linear acetate having one double bond include decyl acetate, Z3-decenyl acetate, Z4-decenyl acetate, undecyl acetate, Z7-undecenyl acetate, Z8-undecenyl acetate, E9-undecenyl acetate, dodecyl acetate, E7-dodecenyl acetate, Z7-dodecenyl acetate, and E8-dodecenyl acetate. E9-dodecenyl acetate, 11-dodecenyl acetate, 10-methyldodecenyl acetate, tridecyl acetate, Z4-tridecenyl acetate, E6-tridecenyl acetate, E8-tridecenyl acetate, Z8-tridecenyl acetate, tetradecyl acetate, Z7-tetradecenyl acetate, E8-tetradecenyl acetate, Z8-tetradecenyl acetate, E9-tetradecenyl Acetate, Z9-Tetradecenyl acetate, E10-Tetradecenyl acetate, Z10-Tetradecenyl acetate, E12-Tetradecenyl acetate, Z12-Tetradecenyl acetate, 12-Methyltetradecenyl acetate, Pentadecyl acetate, Z8-Pentadecenyl acetate, E9-Pentadecenyl acetate, Hexadecyl acetate, Z3-Hexadecenyl acetate, Z5-Hexadecenyl acetate Heptadecenyl acetate, E6-hexadecenyl acetate, Z7-hexadecenyl acetate, Z9-hexadecenyl acetate, Z10-hexadecenyl acetate, Z12-hexadecenyl acetate, heptadecenyl acetate, Z11-heptadecenyl acetate, octadecyl acetate, E2-octadecenyl acetate, Z11-octadecenyl acetate, E13-octadecenyl acetate, and the like.

[0027] As the aliphatic linear acetate having 12 to 20 carbon atoms and two or more double bonds, specifically, for example, a conjugated diene and / or 1,4-pentadiene acetate compound is preferred. Specifically, Z3E5-decadienyl acetate, Z3E5-dodecadienyl acetate, E3Z5-dodecadienyl acetate, Z5E7-dodecadienyl acetate, E5Z7-dodecadienyl acetate, Z9Z9-dodecadienyl acetate, Z8Z10-dodecadienyl acetate, 9,11-dodecadienyl acetate, E4Z7-tridecadienyl acetate, 11-methyl-Z9,12-tridecadienyl acetate, E3E5-tetradecadienyl acetate, E8E10-tetradecadienyl acetate, Z10Z12-tetradecadienyl acetate, Z10E1 Examples include 2-tetradecadienyl acetate, E10Z12-tetradecadienyl acetate, E10E12-tetradecadienyl acetate, E11,13-tetradecadienyl acetate, Z8Z10-pentadecadienyl acetate, Z8E10-pentadecadienyl acetate, Z8Z10-hexadecadienyl acetate, Z10E12-hexadecadienyl acetate, Z11Z13-hexadecadienyl acetate, Z11E13-hexadecadienyl acetate, E11Z13-hexadecadienyl acetate and Z11E14-hexadecadienyl acetate.

[0028] The linear aliphatic alcohol preferably has 7 to 20 carbon atoms. Specific examples of the linear aliphatic alcohol having 7 to 20 carbon atoms include saturated linear aliphatic alcohols and linear aliphatic alcohols having one or more double bonds. Specific examples include n-heptanol, Z4-heptenol, Z6-nonenol, Z6,8-nonadienol, E6,8-nonadienol, n-decanol, Z5-decenol, E5-decenol, n-undecanol, undecenol, 11-chloro-E8E10-undecadienol, n-dodecanol, Z5-dodecenol, Z7-dodecenol, and E7- Dodecenol, Z8-dodecenol, E8-dodecenol, Z9-dodecenol, E9-dodecenol, E10-dodecenol, 11-dodecenol, Z5E7-dodecadienol, E5Z7-dodecadienol, E5E7-dodecadienol, Z7Z9-dodecadienol, Z7E9-dodecadienol, E7Z9-dodecadienol, 8,9-difluoro -E8E10-dodecadienol, 10,11-difuro-E8E10-dodecadienol, 8,9,10,11-tetrafluoro-E8E10-dodecadienol, Z9,11-dodecadienol, E9,11-dodecadienol, n-tridecanol, n-tetradecanol, Z5-tetradecenol, E5-tetradecenol, Z7-tetradecenol, Z8-tetradecenol, Z11-tetradecenol, E11-tetradecenol, Z9Z11-tetradecadienol, Z9E11-tetradecadienol, Z9Z12-tetradecadienol, Z9E12-tetradecadienol, Z10Z12-tetradecadienol, E10E12-tetradecadienol, n-pentadecanol, 6,10,14-Trimethyl-2-pentadecanol, n-hexadecanol, Z9-hexadecenol, Z11-hexadecenol, E11-hexadecenol, Z7Z11-hexadecadienol, Z7E11-hexadecadienol, E10Z12-hexadecadienol, E10E12-hexadecadienol, Z11Z13-hexadecadienol, Z11E13-hexadecadienol, E11Z13- Examples include hexadecadienol, E11Z13-hexadecadienol, Z13-hexadecen-11-en-ol, E4Z6Z10-hexadecatrienol, E4E6Z10-hexadecatrienol, n-octadecanol, Z13-octadecenol, E2Z13-octadecadienol, Z3Z13-octadecadienol, E3Z13-octadecadienol, and n-eicosanol.

[0029] The aliphatic linear ketone preferably has a carbon number of 10 to 20. Specific examples of the aliphatic linear ketone having a carbon number of 10 to 20 include heptadecan-2-one, Z12-nonadecen-9-one, Z6Z9-nonadecadien-3-one, Z7-nonadecen-11-one, Z7-eicosen-11-one, Z6-heneicosen-11-one, Z6-heneicosen-9-one, Z6E8-heneicosadien-11-one, Z6E9-heneicosadien-11-one, Z6Z9-heneicosadien-11-one, and Z7-tricosen-11-one.

[0030] The aliphatic hydrocarbon preferably has a carbon number of 10 to 20. Specific examples of the aliphatic hydrocarbon having a carbon number of 10 to 20 include 1E11-pentadecadiene, 1Z11-pentadecadiene, 5,9-dimethylpentadecane, 2-methylhexadecane, 3,13-dimethylhexadecane, 5,9-dimethylhexadecane, n-heptadecane, 2-methylheptadecane, 2,5-dimethylheptadecane, 5-methylheptadecane, 5,11-dimethylheptadecane, and 7-methylheptadecane. , 7,11-dimethylheptadecane, Z3Z6Z9-heptadecatriene, Z6Z9-heptadecadiene, Z7-octadecene, 10,14-dimethyl-1-octadecene, 5,9-diethyloctadecane, 2-methyloctadecane, 14-methyloctadecane, Z3Z6Z9-octadecatriene, n-nonadecane, 2-methylnonadecane, 9-methylnonadecane, Z3Z6Z9Z11-nonadecatetraene, 1E3Z6 Z9-nonadecatetraene, Z3Z6Z9-nonadecatriene, Z6Z9-nonadecadiene, Z9-nonadecene, n-eicosane, Z9-eicosene, Z3Z6-eicosadiene, Z3Z6Z9-eicosatriene, 1Z3Z6Z9-eicosatetraene, 1Z3Z6Z9-heneicosatetraene, n-heneicosane, Z3Z6-heneicosadiene, Z6Z9-heneicosadiene, Z6Z9,20-heneicosatriene, Z Examples thereof include 3Z6Z9-heneicosatriene, Z6-13-methylheneicosene, Z9-heneicosene, n-docosaene, Z3Z6Z9-docosatriene, Z6Z9-docosadiene, n-tricosene, Z3Z6Z9-tricosatriene, Z6Z9-tricosadiene, n-tetracosane, n-pentacosane, Z3Z6Z9-pentacosatriene, n-hexacosane, n-heptacosane, n-octacosane, and n-nonacosane.

[0031] The carboxylic acid is not particularly limited as long as it is a compound having a carboxyl group, but preferably has 10 to 20 carbon atoms. Specific examples of carboxylic acids having 10 to 20 carbon atoms include those having multiple methyl groups in the carbon skeleton and those having a double bond. Specific examples include 3,5-dimethyldodecanoic acid, Z-5-undecenoic acid, E-5-undecenoic acid, and (E,Z)-3,5-tetradecadienoic acid.

[0032] If necessary, additives such as antioxidants and ultraviolet absorbers may be added to the pheromone substance. Examples of antioxidants include 2,6-di-tert-butyl-4-methylphenol (BHT), butylhydroxytoluene, butylhydroxyanisole, hydroquinone, 2,2'-methylenebis(4-methyl-6-t-butylphenol), vitamin E, and the like. Examples of ultraviolet absorbers include 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole (HBMCBT), 2-hydroxy-4-octoxybenzophenone, 2-(3,5-di-t-butyl-2-hydroxyphenyl)-5-chlorobenzotriazole, and 2,5-di-t-butylhydroquinone.

[0033] Next, a method for producing the sustained-release pheromone formulation of the present invention will be described. First, a polymeric capillary tube containing a pheromone substance or a polymeric rod containing a pheromone substance is prepared. The polymeric capillary tube is obtained by extruding a polymeric material into a tubular shape and simultaneously injecting the pheromone substance to encapsulate the pheromone substance. For example, as shown in Figure 14, an infinitely long polymeric capillary tube filled with pheromone liquid A is continuously extruded. Molten polymer material B in feeder 83 is extruded into a tubular shape through die 84 to form polymeric capillary tube 85. At this time, synthetic pheromone liquid is continuously injected into polymeric capillary tube 85 through core hole 82 in mandrel 81 of the die, filling it, and the polymeric rod is then wound on a reel. Alternatively, a polymeric rod can be obtained by mixing and stirring the polymeric material with pheromone liquid or a carrier such as an inert substance containing pheromone liquid, followed by extrusion molding into a rod shape. For example, a pheromone liquid or a carrier containing a pheromone liquid is dispersed in a molten polymer material, which is extruded through a die into a rod-like polymeric thin rod material, and then wound up on a reel.

[0034] The carrier may be any polymeric material or inorganic or organic filler that has the property of forming a solution or suspension with the pheromone at a temperature equal to or higher than the melting point of the polymeric material used, without any particular limitation. Examples of polymeric materials used for the support include poly-ε-caprolactone, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, polyvinyl chloride, polyvinyl acetate, polymethacrylic acid ester, cellulose derivatives such as cellulose acetate butyrate, polystyrene, polyethylene, polypropylene, polybutadiene, and polyisoprene. The filler used in the carrier may be any inorganic or organic material, without particular limitation. Examples include inorganic fillers such as iron powder and other metal powders, silicic acid, silicates, alumina, calcium carbonate, barium sulfate, gypsum, slate powder, mica, kaolin, clay, talc, asbestos, graphite, carbon black, and cement, and organic fillers such as linter and wood flour. Because the pheromone retention capacity of these fillers varies depending on the type, particle size, and shape, fillers with an oil absorption capacity of 15 ml or more, and more preferably 30 ml or more, are used. The higher the oil absorption, the greater the pheromone retention capacity, making it easier to mix and disperse the pheromone. The oil absorption, based on the test method specified in JIS K5105-1965, is the amount of oil that can be mixed with 100 g of filler.

[0035] Such supports can be used in an amount of preferably 2 to 50% by weight, more preferably 5 to 40% by weight, assuming the total amount of the pheromone substance and support to be 100% by weight. Amounts less than 2% by weight may be insufficient to retain the pheromone, while amounts greater than 50% by weight may make it impossible to control the release of the pheromone and ensure long-term release. These supports may be used alone or in combination. Furthermore, for ease of production, it is more desirable to use a mixture of polymeric and filler-based supports.

[0036] Next, a method for processing a polymer thin tube or a polymer thin rod into a predetermined shape will be described. The processing method is not particularly limited. For example, a fixing jig 23 shown in FIG. 11A is used to fix polymeric tubules or rods with both ends already sealed, with multiple protrusions provided at appropriate locations on a plate. As shown in the schematic diagram of FIG. 11B, this fixing jig 23 is continuously transported on a belt conveyor 26, passing through a hot water bath 24 for a certain period of time, and then through a cooling water bath 25 for a certain period of time. After that, the polymeric tubules or rods are removed from the fixing jig and air-dried in an air-drying device 27, enabling mass production. The temperature of the water in the hot water bath 24 is preferably 70 to 90°C, depending on the polymeric material used. The temperature of the water in the cooling water bath 25 is preferably 5 to 25°C, depending on the polymeric material used. As another processing method, there is a method using a thermocouple, a heat gun or a heat box. For example, in the case of thin tubes or rods made of polybutylene succinate or polybutylene succinate adipate, the thin tubes or rods can be shaped by sealing both ends, bending them into the desired shape, heating them to 80°C (melting point is 110°C), and cooling them while maintaining the shape. [Example]

[0037] EXAMPLES The present invention will be specifically explained below with reference to examples and comparative examples, but the present invention is not limited to the following examples.

[0038] [Example 1] Using an extrusion molding machine (die temperature 130°C), two parallel-arranged long thin tubes made of polybutylene succinate (Mitsubishi Chemical: BioPBS FZ91PB) were produced, each with an inner diameter of 1.40 mm, a wall thickness of 0.40 mm, and an outer diameter of 2.20 mm. This long thin tube was cut to a length of 20 m, and one end of the long thin tube was immersed in a solution of (Z)-8-dodecenyl acetate, the sex pheromone of the Oriental Fruit Moth, to which 1% by mass of 2,6-di-tert-butyl-4-methylphenol (antioxidant) and 1% by mass of 2-(5-chloro-2-hydroxy-3-tert-butyl-5-methylphenyl)-p-cresol (ultraviolet absorber) had been added. The sex pheromone solution was then filled into the thin tube by suction from the other end using a pump. A 20m long thin tube filled with sex pheromone was ultrasonically sealed (amplitude 28μm, pressure 117.6kPa, sealing time 1.2 seconds) at 200mm intervals, and then the sealed portions were cut with a cutter to produce 1000 sustained-release pheromone formulations made from polymer thin tubes with a total length of 200mm. This sustained-release pheromone formulation was fixed to a plate by bending the polymeric capillaries with rollers of 8 mm, 12 mm, and 8 mm diameter (see Figure 12). The plate was then immersed in 80°C hot water for 15 seconds, and then placed in a water bath at 20°C, yielding the sustained-release pheromone formulation shown in Figure 13. The resulting sustained-release pheromone formulation had two closed spaces when viewed from the front and did not intersect when viewed from the side. The radius of curvature of the arc of the closed portion of the resulting sustained-release pheromone formulation was 8 mm, the angle of the arc was 80°, and the linear distance from the apex of the arc to the closest intersection point to the apex was 22 mm. The repulsive force of this sustained-release pheromone formulation was measured using the method shown in Figure 6, and was found to be 2.8 N. This sustained-release pheromone formulation can be bent into an arc shape and then simply grasped with the fingers and place a tree branch on the opening between the two sealed ends. The branch will then fit into the arc shape (closed space 7), and once the tree branch is in the closed space 7, the projection-like shapes underneath the circle overlap, preventing it from coming off the tree branch.

[0039] [Example 2] Using an extrusion molding machine (die temperature 130°C), two parallel-arranged long thin tubes of polybutylene succinate (Mitsubishi Chemical: BioPBS FZ91PB) and polybutylene succinate adipate (Mitsubishi Chemical: BioPBS FD92PB) were produced in an 80:20 mass ratio. Each tube had an inner diameter of 1.07 mm, a wall thickness of 0.40 mm, and an outer diameter of 1.87 mm. This long thin tube was cut into a length of 100 m, and one end of the long thin tube was immersed in a solution of (E,Z)-7,9-dodecadieaacetate, the sex pheromone of the European grapevine moth, to which 2% by mass of 2,6-di-tert-butyl-4-methylphenol (antioxidant) and 2% by mass of 2-(5-chloro-2-hydroxy-3-tert-butyl-5-methylphenyl)-p-cresol (ultraviolet absorber) had been added. The sex pheromone solution was then filled into the thin tube by suction from the other end using a pump. A 100m long thin tube filled with sex pheromone was ultrasonically sealed (amplitude 28μm, pressure 117.6kPa, sealing time 1.0 seconds) at 200mm intervals, and then the sealed portions were cut with a cutter to produce 5,000 sustained-release pheromone formulations made from polymer thin tubes with a total length of 200mm. The resulting sustained-release pheromone formulation had two closed spaces when viewed from the front and did not intersect when viewed from the side. The radius of curvature of the arc of the closed portion of the resulting sustained-release pheromone formulation was 8 mm, the angle of the arc was 80°, and the linear distance from the apex of the arc to the intersection closest to the apex was 22 mm. The repulsive force of this sustained-release pheromone formulation was measured using the method shown in Figure 6 and was found to be 3.1 N. This sustained-release pheromone formulation was obtained in the same manner as in Example 1. Simply gripping the arc portion formed by bending this sustained-release pheromone formulation with your fingers and placing a tree branch against the opening between the two sealed ends allowed the branch to enter the arc portion (closed space 7) formed by bending it into the curved arc. Furthermore, once the tree branch entered the closed space 7, the projection-like shapes below the circle overlapped, preventing it from coming off the tree branch.

[0040] [Comparative Example 1] Using an extrusion molding machine (die temperature 130°C), two parallel-arranged long thin tubes of polybutylene succinate (Mitsubishi Chemical: BioPBS FZ91PB) and polybutylene succinate adipate (Mitsubishi Chemical: BioPBS FD92PB) were produced in a mass ratio of 80:20. Each tube had an inner diameter of 0.58 mm, a wall thickness of 0.30 mm, and an outer diameter of 1.18 mm. This long thin tube was cut into a length of 100 m, and one end of the long thin tube was immersed in a solution of (E,Z)-7,9-dodecadieaacetate, the sex pheromone of the European grapevine moth, to which 2% by mass of 2,6-di-tert-butyl-4-methylphenol (antioxidant) and 2% by mass of 2-(5-chloro-2-hydroxy-3-tert-butyl-5-methylphenyl)-p-cresol (ultraviolet absorber) had been added. The sex pheromone solution was then filled into the thin tube by suction from the other end using a pump. A 100 m long thin tube filled with sex pheromone was ultrasonically sealed (amplitude 28 μm, pressure 98.0 kPa, sealing time 0.8 seconds) at 200 mm intervals, and then the sealed portion was cut with a cutter to produce 5,000 sustained-release pheromone formulations made from polymer thin tubes with a total length of 20 cm. This sustained-release pheromone formulation was obtained in the same manner as in Example 1. The resulting shape was similar to that of Example 2, but the repulsive force was measured using the method shown in Figure 6 and was found to be 0.8 N. When this sustained-release pheromone formulation was bent into an arc, the arc portion was grasped with the fingers, and a tree branch was placed against the opening between the two sealed ends, and the branch entered the arc portion (closed space 7), but the repulsive force of the curved portion was small, causing it to come off the branch and fall due to wind pressure and branch vibration.

[0041] <Working hours> [Example 3] To examine the ease of installation of the sustained-release pheromone formulation obtained in Example 1, installation work was carried out in an apple orchard. In a 10-are apple orchard where apple trees were planted at 6 m intervals, work was carried out to install three bottles of the sustained-release pheromone formulation per apple tree (installation of 99 bottles / 10 ares). Installation was possible with one hand, and it took one person 45 minutes to install 99 bottles, which was a shorter work time than in Comparative Example 2.

[0042] Comparative Example 2 Using an extrusion molding machine (die temperature 130°C), two parallel-arranged long thin tubes made of polybutylene succinate (Mitsubishi Chemical: BioPBS FZ91PB) were produced, each with an inner diameter of 1.40 mm, a wall thickness of 0.40 mm, and an outer diameter of 2.20 mm. This long thin tube was cut to a length of 20 m, and one end of the long thin tube was immersed in a solution of (Z)-8-dodecenyl acetate, the sex pheromone of the Oriental Fruit Moth, to which 1% by mass of 2,6-di-tert-butyl-4-methylphenol (antioxidant) and 1% by mass of 2-(5-chloro-2-hydroxy-3-tert-butyl-5-methylphenyl)-p-cresol (ultraviolet absorber) had been added, and the sex pheromone solution was filled into the thin tube by suction from the other end using a pump. A 20m long thin tube filled with sex pheromone was ultrasonically sealed (amplitude 28μm, pressure 117.6kPa, sealing time 1.2 seconds) at 200mm intervals, and then the sealed portions were cut with a cutter to produce 1000 sustained-release pheromone formulations made from polymer thin tubes with a total length of 200mm. The sustained-release pheromone formulation obtained above was placed in a 10-are apple orchard where apple trees were planted at 6 m intervals, with three bottles placed per apple tree (99 bottles / 10 ares) in the same manner as in Example 3. The formulation required the work of spreading the ring-shaped formulation and threading it through the branches, and it took one person 70 minutes to place 99 bottles.

[0043] <Fall rate measurement> First, 97 parts by mass of polybutylene succinate adipate (Mitsubishi Chemical: BioPBS FD92PB) pellets and 3 parts by mass of a solution containing (Z)-8-dodecenyl acetate, the sex pheromone of the oriental fruit moth, to which 1% by mass of 2,6-di-tert-butyl-4-methylphenol (antioxidant) and 1% by mass of 2-(5-chloro-2-hydroxy-3-tert-butyl-5-methylphenyl)-p-cresol (ultraviolet absorber) had been added were mixed in a V-type mixer until the pellets no longer blocked (the phenomenon in which pellets stick together and form clumps). The polymer was then extruded through a die with a circular hole of 4.1 mm diameter (die temperature: 130°C) and passed through water baths (first water bath: 2 m long, temperature: 60°C; second water bath: 5 m long, temperature: 15°C) to cool and solidify the pellets and form cylindrical rods. By winding up this thin rod at a constant speed, we produced long, polymeric rods impregnated with sex pheromones. By maintaining a constant winding speed and adjusting the extrusion screw speed of the extruder, we were able to freely vary the diameter (outer diameter) of the cylinders. When the winding speed was kept constant at 60 m / min and the extruder was equipped with a 50 mm diameter screw and rotating at 12.8 RPM, we obtained long, pheromone-containing rods with an outer diameter of 1.0 mm. Similarly, when the screw speed was increased to 26.8 RPM at 60 m / min, the outer diameter was 1.5 mm. At 47.4 RPM, the outer diameter was 2.0 mm. Furthermore, by changing the diameter of the circular die hole to 6 mm, and extruding at 40 m / min and a screw speed of 52.2 RPM, we obtained rod-shaped extrusions with an outer diameter of 2.5 mm. Further molding was performed with a die hole diameter of Φ6, a winding speed of 30 m / min, and a screw rotation speed of 54.0 RPM to obtain rod-shaped molded products with an outer diameter of 3.0 mm.Further molding was performed with a die hole diameter of Φ6, a winding speed of 18 m / min, and a screw rotation speed of 57.5 RPM to obtain rod-shaped molded products with an outer diameter of 5.0 mm. Next, using an extrusion molding machine (die temperature 130°C), long thin rods and long thin tubes of polymeric thin tubes (single tube) and polymeric thin tubes (two parallel tubes) listed in Table 1 were produced from polybutylene succinate adipate (Mitsubishi Chemical: BioPBS FD92PB). These long tubules were each cut to a length of 20 m, and one end of a single polymer tubule, or one end of each of two parallel polymer tubules, was inserted into a solution of (Z)-8-dodecenyl acetate, the sex pheromone of the Oriental fruit moth, to which 1% by mass of 2,6-di-tert-butyl-4-methylphenol (an antioxidant) and 1% by mass of 2-(5-chloro-2-hydroxy-3-tert-butyl-5-methylphenyl)-p-cresol (an ultraviolet absorber) had been added, and the sex pheromone solution was filled into the tubules by sucking from the opposite end with a pump. A 20m long thin tube filled with sex pheromone was ultrasonically sealed (amplitude 28μm, pressure 117.6kPa, sealing time 1.2 seconds) at 20cm intervals, and then the sealed portion was cut with a cutter to produce 100 sustained-release pheromone formulations each in the form of a polymer thin tube with a total length of 200mm. The resulting polymeric rod and polymeric tubule sustained-release pheromone formulations were each molded in the same manner as in Example 1. The molded sustained-release pheromone formulation had two closed spaces when viewed from the front and did not intersect when viewed from the side. The radius of curvature of the arc of the closed portion of the resulting sustained-release pheromone formulation was 8.0 mm, the angle of the arc was 80°, and the linear distance from the apex of the arc to the intersection closest to the apex was 22 mm. The repulsive force of the sustained-release pheromone formulation, measured by the method shown in Figure 6, is shown in Table 1. Next, five of these molded sustained-release pheromone formulations were placed between the protrusions on a fixed 400mm long, 15mm diameter wooden piece with 2mm thick, 15mm long protrusions spaced 5cm apart. The suspended sustained-release pheromone formulations were exposed to a wind speed of 25m / s for 60 seconds, and the number of sustained-release pheromone formulations that fell was counted and used as the fall rate. The results are shown in Table 1 and Figure 7. These results indicate that sustained-release pheromone formulations with a repulsive force of 1.0N or more, measured using the measurement method described above, had a fall rate of 0.4 or less (1-2 out of 5 formulations fell, or none fell), demonstrating excellent installation stability.

[0044] [Table 1] [Explanation of symbols]

[0045] 1. Polymer thin tube 2 Sealed end 3. Pheromone substances 5, 51 intersection 6 Opening 7, 71 space 8 Vertex of the Arc 9 branches 10. Sustained-release pheromone preparations 11 Polymer thin rod 23 Fixture 24 Hot water tank 25 Cooling water tank 26 Conveyor Belt 27 Air drying equipment 31 Metal chuck 32 Force Gauge 33 Small hook attachment 81 Mandrel 82 Cored hole 83 Feeder 84 Die 85 Polymer capillary material A. Pheromone liquid B Polymer material

Claims

[Claim 1] A sustained-release pheromone preparation comprising a polymeric thin tube or rod having an outer diameter of 1.5 to 6 mm and having each end sealed, the polymeric thin tube or rod containing at least one pheromone substance, wherein the polymeric material constituting the polymeric thin tube or rod is polybutylene succinate or a mixture of polybutylene succinate and polybutylene succinate adipate; (a) A sustained-release pheromone preparation in which the polymeric thin tubes or rods are bent in an arc and crossed to form a circular space closed at one crossing point, one or more spaces closed at two crossing points, and one opening in a front view, and which do not cross in a side view, (b) the radius of curvature of the circular shape is 6 to 15 mm; (c) the straight-line distance from the apex of the circular arc to the intersection point closest to the apex is 10 to 50 mm; (d) When viewed from the front, the repulsive force is 1.0 N or more when the distance between the intersection closest to the arc is 20 mm. A sustained-release pheromone formulation.

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