JPS6121442B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a sublimable pheromone agent, and more particularly to a sublimable pheromone agent prepared by blending a pheromone substance with a sublimable substance formed by mixing adamantane and other specific sublimable hydrocarbons.

Pheromones are already being investigated for their potential use in controlling pests in agricultural crops, and are being used on a trial basis to predict the emergence of pests. In this case, various methods for controlling the volatilization of the pheromone substance into the air have been studied, and it is currently considered that the best method is to allow the pheromone substance to be adsorbed onto a porous polymeric material, particularly a rubber material.

Regarding pheromone substances, various substances are known based mainly on research on insect sex pheromones, and sex pheromone is a mixture consisting of two components.

The present inventors have studied to develop an excellent method for controlling the volatilization of this pheromone substance, and found that it is possible to carry the pheromone substance on a sublimable substance made by mixing adamantane and other specific sublimable hydrocarbons. They discovered that it is effective and completed the present invention. According to the present invention, there is provided a sublimable pheromone agent that can convert a liquid pheromone substance into a solid state that is easy to handle, and can arbitrarily adjust the volatilization rate of the substance.

The sublimable material is a mixture of (A) adamantane and (B) other certain sublimable hydrocarbons. Here, (B) other specific sublimable hydrocarbons include endotrimethylenenorbornane (hereinafter abbreviated as TMN), cyclododecane (hereinafter abbreviated as CD), trimethylnorbornane, norbornane,
You can give things like Kung Huan.

Adamantane (hereinafter abbreviated as AD) is a non-toxic, odorless, water-insoluble, sublimable hydrocarbon compound with a high melting point (268°C). Therefore, even if other crystalline hydrocarbons are mixed, a sudden drop in melting point does not occur, so it can be easily mixed and molded with other sublimable hydrocarbons. In addition, it has good shape retention after molding, and when mixed with other sublimable hydrocarbons, the mechanical strength of the molded product can be increased.

Like AD, TMN is a non-toxic sublimable hydrocarbon and is a waxy crystal with caking properties at room temperature.
TMN has excellent moldability and mold release properties.

The specific sublimable hydrocarbon (B) used with adamantane may be one type, or two or more compounds may be used in an appropriate combination. Furthermore, it can also be used in combination with a sublimable polar compound described below. When combining adamantane and other specific sublimable hydrocarbons, it is preferable to use the sublimation rate required for the carrier as a guide to determine the amount to be blended in the composition. For example, when using AD and TMN in combination, AD1~
TMN is blended at a ratio of 99 to 75% by weight with respect to 25% by weight. If TMN is less than 75% by weight, it is undesirable because adamantane, which has a lower sublimation rate than TMN (1/8 of the sublimation rate of TMN), will be dusted on the surface of the composition, reducing the commercial value. On the other hand, if AD and CD are used together In this case, both can be mixed in any proportion.The reason is that the sublimation speed of CD is slower than that of AD (1/2 of the sublimation speed of AD).
Although CD remains on the surface of the composition, since CD has a low melting point (60°C), it forms a three-dimensionally continuous homogeneous phase and does not form powder. Usually AD5
It is preferable to mix CD in a ratio of 95 to 5% by weight to 95% by weight.

In the present invention, as the sublimable substance, a polar compound having sublimation property is used in addition to (A) and (B) above. As this polar compound, for example, 2,2-
Dimethyl-1,3-propanediol, 1,4-
Examples include crystalline alcohols such as cyclohexanediol and 1,6-hexanediol, dimethyl fumarate, ε-caprolactam, paradimethoxybenzene, benzoic acid, trioxymethylene, and coumarin.

A sublimable polar compound can be used alone or in combination with other sublimable substances, but when used in combination with a sublimable hydrocarbon, a compound that is almost incompatible with the hydrocarbon at room temperature should be used.

The sublimable polar compound should be a compound that is almost incompatible with adamantane and other specific sublimable hydrocarbons used together at room temperature. Further, the amount of the sublimable polar compound to be blended is appropriately determined by taking into consideration the properties of the sublimable hydrocarbon used together, the properties of the pheromone substance to be supported, etc. For example, ε-
When caprolactam is used, it is used in an amount of 0.1 to 10% by weight for AD-TMN compositions consisting of 1 to 25% by weight of AD and 99 to 75% by weight of TMN, and 0.5 to 20% by weight for AD-CD compositions. They may be mixed in proportion. When using dimethyl fumarate, AD
-Used in a proportion of 0.1 to 20% by weight based on the TMN composition.

When a sublimable hydrocarbon and a sublimable polar compound as described above are used in combination, the former mainly functions to adjust the sublimation rate of the entire composition, while the latter retains the pheromone substance, which is an active ingredient, and also controls the sublimation property. It acts to reduce the distribution ratio of active ingredients to hydrocarbons and prevent a drop in the melting point of sublimable hydrocarbons. Therefore, the mechanical strength of the composition does not decrease due to the addition of the active ingredient.

There are no particular restrictions on the pheromone substance that can be used in the present invention, and any suitable substance can be used depending on the purpose. Generally, sex pheromones are used, and any of the sex pheromones of various insects that have been studied so far can be used. For example, cis-9, trans-11-tetradecadienyl acetate (component A), cis-9, trans-12-
There are sex pheromones such as tetradecadienyl, acetate (component B), and other sex pheromones such as cypress pheromones, apple pomegranates, white snail moth, snail moth, and honey snail moth.

The amount of the pheromone substance added is not particularly limited and varies depending on factors such as the purpose of use and the type of pheromone substance, and cannot be determined unambiguously, but it is generally in the range of 0.01 to 15 parts by weight per 100 parts by weight of the sublimable substance. It is. Further, an antioxidant or a small amount of volatile substance can be added as necessary. The former is effective to prevent oxidation of the pheromone material, and the latter can aid in the volatility of the pheromone material.

In an example of manufacturing the sublimable pheromone agent of the present invention, for example, a sublimable substance is heated and melted, then the pheromone substance is added, and the mixture is cooled and solidified. If necessary, operations such as crushing and molding can be performed. In addition, when adding an antioxidant or a volatile substance, these substances may be added after heating and melting the sublimable substance and before cooling and solidifying the sublimable substance.

Since the sublimable pheromone agent obtained in this way uses a sublimable substance as a carrier, the period of use of this preparation can be arbitrarily set, and the end point of the effective period of use can be clarified. This is because the volatilization of the added pheromone substance can be controlled by appropriately selecting a sublimable carrier, and this is a major feature of the present invention.
Another feature is that the necessary mechanical strength, shape, etc. can be set according to the purpose of use, place of use, etc. of this preparation.

Therefore, the sublimable pheromone agent of the present invention can be expected to be effectively used for predicting the occurrence of, controlling, etc. pests in agricultural crops.

Next, the present invention will be explained in detail with reference to examples.

Example 1 0.1 part by weight of cis-9,trans-11-tetradecadienyl acetate and cis-
After adding 0.01 part by weight of 9, trans-12-tetradecadienyl acetate and 0.01 part by weight of hydroquinone as an antioxidant, the mixture was immediately cooled and solidified.

This solidified material is powdered and compressed into a diameter
The tablets were 1.29 mm and 0.37 mm thick.

This tablet was suspended in the middle of a cylindrical container (inner diameter 90 mm) having a ventilation hole at the bottom, air was blown from the bottom of the container at a linear velocity of 40 cm/min, and the tablet was sublimed at a temperature of 20°C. The wind direction was parallel to the circular plane of the tablet. In this way, the sublimation properties of the tablets were determined. The results are shown in Figure 1. The total concentration of pheromone substances in the figure shows the relative concentration when the initial concentration in the composition after molding is set to 1. Note that the volatilization rates of the two types of pheromone substances were almost equal.

Example 2 0.4 parts by weight of cis-9, trans-11-tetradecadienyl acetate and 0.4 parts by weight of cis-9, trans-12-tetradecadienyl were added to the melt obtained by heating and mixing 20 parts by weight of AD and 80 parts by weight of CD. After adding 0.04 parts by weight of acetate, an experiment was conducted in exactly the same manner as in Example 1.

The results are shown in Figure 2.

[Brief explanation of the drawing]

FIGS. 1 and 2 are graphs showing the volatilization characteristics of the sublimable pheromone agent of the present invention.

Claims (1)

[Claims] 1. Sublimation consisting of (A) adamantane and (B) one or more sublimable hydrocarbons selected from the group consisting of endotrimethylenenorbornane, cyclododecane, tritylnorbornane, norbornane, and camphuan. A sublimable phemolone agent made by combining a pheromone substance with a sex substance. 2. The sublimable pheromone agent according to claim 1, which contains an antioxidant as an auxiliary component. 3. The sublimable pheromone agent according to claim 1, wherein the amount of the pheromone substance blended is 0.01 to 15 parts by weight per 100 parts by weight of the sublimable substance.