JP2796629B2 - Pheromone-containing polymer membrane - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a pheromone-containing polymer film in which pheromone is stabilized.

BACKGROUND OF THE INVENTION Generally, aldehydes have low chemical stability and are easily oxidized to carboxylic acids or polymerized by ultraviolet light. Many insect pheromones are such aldehydes, and long-term stabilization of pheromones is strongly desired in pest control by pheromones.

In general, aldehyde stabilization methods include, for example,
As for α, β-unsaturated aldehydes such as acrolein and acrolein, a method of adding an alkyl-substituted hydroquinone is known as described in JP-A-49-135907. Japanese Patent Publication No. 63-12452 discloses a method in which a benzophenone compound is added to a higher aliphatic aldehyde together with an antioxidant.

On the other hand, various preparations for controlling insect pheromones over a long period of time have been known for controlling insects. As such preparations, for example, those in which pheromone is microencapsulated, those in a tube, those in a polymer porous membrane, and the like are known. As described above, the insect pheromone used for such a purpose contains many chemically unstable higher aliphatic non-conjugated aldehydes, which are easily converted to fatty acids or oligomerized. Therefore, heretofore, there has not been known a pheromone preparation capable of suppressing such denaturation and oligomerization and stabilizing the pheromone to effectively release the insect pheromone for a long period of time.

Problems to be Solved by the Invention The present inventors have assiduously studied a method for stabilizing higher aliphatic non-conjugated aldehydes, which are common in insect pheromones,
It has been found that by adding a hydroquinone compound to such an aldehyde, its long-term stabilization can be achieved.Furthermore, by dissolving and containing an insect pheromone and a hydroquinone compound in a polymer, The present inventors have found that the insect pheromone can be stabilized and can be effectively and slowly released over a long period of time, leading to the present invention.

Means for Solving the Problems The pheromone-containing polymer film according to the present invention comprises a polymer in which pheromone and a hydroquinone-based compound comprising a higher aliphatic non-conjugated aldehyde having a double bond not conjugated to an aldehyde carbonyl group are dissolved in a polymer. It is characterized by the following.

In the present invention, the higher aliphatic non-conjugated aldehyde is
A higher aliphatic aldehyde having a double bond that is not conjugated to the carbonyl group of the aldehyde group.
It is in the range of 10-20. As a specific example, for example, Z-7
-Tetradecenal, Z-9-tetradecenal, Z-
11-tetradecenal, Z-7-hexadecenal, Z
-9-hexadecenal, E-11-hexadecenal,
Z-11-hexadecenal, n-hexadecanal, Z,
Z-11,13-hexadecadienal, Z-13-octadesenal, Z, Z-9,12-octadecadienal, Z, Z, Z-9,
12,15-octadecatrienal, Z-14-methyl-8
-Hexadecenal, E-14-methyl-8-hexadecenal and the like.

According to the present invention, by adding and dissolving a hydroquinone-based compound to the higher aliphatic non-conjugated aldehyde, the aldehyde can be kept stable for a long period of time. Examples of the hydroquinone-based compound that can be preferably used in the present invention include, for example, hydroquinone, resorcin, catechol, phloroglucin, pyrogallol, α-naphthohydroquinone, and monomethyl or monoethyl ether thereof. Or a mixture of two or more. Among the above, examples of monomethyl or monoethyl ether include hydroquinone monomethyl ether, hydroquinone monoethyl ether, resorcinol monomethyl ether, guaiacol, and the like. As described above, the hydroquinone-based compound dissolved in the aldehyde effectively absorbs the energy of ultraviolet rays, suppresses oxidation and polymerization of the higher aliphatic non-conjugated aldehyde, and stabilizes the aldehyde over a long period of time.

In the present invention, the hydroquinone-based compound is usually added in the range of 0.001 to 10% by weight, and preferably in the range of 0.01 to 3% by weight, based on the aldehyde.

The pheromone-containing polymer film according to the present invention comprises a pheromone comprising the higher aliphatic non-conjugated aldehyde and the hydroquinone-based compound dissolved in a polymer.

In general, in a formulation in which an insect pheromone is dissolved and contained in a polymer, the polymer used greatly affects the solubility and diffusibility of the aldehyde, that is, the sustained release property and the sustained release period of the insect pheromone. Depending on,
It is preferably selected so as to give the optimum sustained release in consideration of the intended use. Usually, for example, poly (sulfone), polyester, polycarbonate, polystyrene, poly (meth) acrylate containing polymethyl methacrylate, polyamide, polyvinylidene chloride, polyvinylidene fluoride, polyurethane, polyvinyl chloride,
It is selected from polyvinyl acetate, ethylene-vinyl acetate copolymer, vinyl chloride-vinyl acetate copolymer, styrene-bradiene copolymer, or a mixture of two or more of these.

Although not particularly limited, for example, when Z-11-hexadecenal is used as the insect pheromone, an ethylene-vinyl acetate copolymer is preferably used as the polymer. Particularly, an ethylene-vinyl acetate copolymer having a vinyl acetate content in the range of 15 to 45% by weight is preferable. In the ethylene-vinyl acetate copolymer, when the vinyl acetate content is less than 15% by weight, it is difficult to dissolve and contain Z-11-hexadecenal in the polymer. This is because the copolymer is not easily softened, it is difficult to maintain the form as a film, and it is difficult to practically use it as a pheromone preparation.

The pheromone-containing polymer film according to the present invention can, for example, dissolve all of the polymer used, the pheromone and the hydroquinone-based compound described above, and polymerize the pheromone and the hydroquinone-based compound in an organic solvent having a higher volatility than the pheromone. It can be obtained by dissolving into a solution, applying this solution on an appropriate support, and evaporating and removing the organic solvent.

The organic solvent is appropriately selected depending on the polymer to be used, the pheromone and the hydroquinone-based compound, and is usually, for example, lower aliphatic halogenated hydrocarbon such as methylene chloride, chloroform, carbon tetrachloride, methanol, ethanol, etc. In addition to the lower aliphatic alcohols and their acetic esters, one or a mixture of two or more of acetonitrile, acetone, ethyl ether, tetrahydrofuran and the like are used. Among these, methylene chloride is particularly preferably used. However, if the pheromone used is relatively refractory, a relatively high boiling organic solvent such as, for example, dimethylformamide can also be used.

Therefore, the pheromone-containing polymer film according to the present invention is in the form of a sheet. Preferably, a backing for protecting the pheromone from ultraviolet rays and preventing the transmission of the pheromone is attached to the front and back surfaces of the sheet. The pheromone is gradually released from the side of the polymer sheet. The backing is made of, for example, a thin metal foil or sheet, a resin film, or a laminate thereof. For example, an aluminum foil or a polyester film is preferably used.

The backing may be adhered to the polymer sheet using an appropriate adhesive.For example, since the above-described ethylene-vinyl acetate copolymer generally has tackiness, even without using an adhesive, The backing can be affixed to the polymer sheet.

The pheromone-containing polymer film according to the present invention, together with the pheromone comprising the higher aliphatic non-conjugated aldehyde,
It may contain an ester-based, alcohol-based, ketone-based, epoxy-based, or hydrocarbon-based pheromone. Such pheromones include, for example, Z
Examples of alcohols such as -9-tetradecenyl acetate, Z-11-tetradecenyl acetate, Z-11-hexadecenyl acetate and the like include Z-11-hexadecenol, Z-
8-dodecenol, n-dodecenol and the like; ketone-based compounds such as Z-7-eicosen-11-one, Z-7-nonadecene-11-one and Z-13-eicosen-11-one; Z-7,8-epoxy-2-methyloctadecane and the like, and in the case of hydrocarbons, Z-9-tricosene and the like can be mentioned.

The pheromone-containing polymer film according to the present invention comprises a polymer 100
Per weight part, up to about 200 parts by weight of pheromone, preferably in the range of about 30 to 200 parts by weight,
As described above, the hydroquinone-based compound is generally added to the aldehyde in a range of 0.001 to 10% by weight, and preferably in a range of 0.01 to 5% by weight.

Effect of the Invention The pheromone-containing polymer film according to the present invention is obtained by dissolving a pheromone and a hydroquinone-based compound composed of a higher aliphatic non-conjugated aldehyde having a double bond that is not conjugated to an aldehyde carbonyl group in a polymer. It can be effectively and slowly released over a long period of time while suppressing the denaturation and polymerization and keeping it stable, and thus can be suitably used, for example, as a preparation for controlling insects.

EXAMPLES Hereinafter, the present invention will be described with reference to Examples and Reference Examples, but the present invention is not limited to these Examples. Reference Example is an example showing the stabilizing effect of the hydroquinone compound used in the present invention on pheromone.

Reference Example 1 To 1 part by weight of Z-11-hexadecenal, 0.02 parts by weight of hydroquinone or HQM (hydroquinone monomethyl ether) was added, and the mixture was placed in a glass bottle, sealed, and allowed to stand in the air in a place exposed to direct sunlight for 50 days. Thereafter, the residual ratio of Z-11-hexadecenal was determined by gas chromatography.

For comparison, instead of the hydroquinone compound,
0.02 parts by weight of BHT (2,6-di-t-butyl-4-methylphenol) as an antioxidant was added, and its stabilizing effect was examined in the same manner.

 The results are shown in Table 1.

Reference Example 2 0.02 parts by weight of hydroquinone or HQM (hydroquinone monomethyl ether) was added to 1 part by weight of a mixture of E-11-hexadecenal and Z-11-hexadesenal (7/3 weight ratio), and the mixture was placed in a glass bottle and sealed. It was left in the atmosphere under direct sunlight for 50 days. Thereafter, the residual ratio of E-11-hexadecenal and Z-11-hexadecenal was determined by gas chromatography.

For comparison, instead of the hydroquinone compound,
0.02 parts by weight of BHT (2,6-di-t-butyl-4-methylphenol) as an antioxidant was added, and its stabilizing effect was examined in the same manner.

 The results are shown in Table 2.

Reference Example 3 Z-9-hexadecenal was tested in the same manner as in Example 1. The results are shown in Table 3.

Reference Example 4 Z-13-octadesenal was tested in the same manner as in Example 1. The results are shown in Table 4.

Example 1 75 parts by weight of an ethylene-vinyl acetate copolymer having a vinyl acetate content of 40% by weight (Evaflexs 40Y manufactured by Mitsui Polychemicals, Inc.), 25 parts by weight of Z-11-hexadecenal, and 0.5 parts by weight of catechol were chlorinated. It was dissolved in 200 parts by weight of methylene.

This solution was applied on a polyethylene terephthalate film at room temperature to a thickness of 200 μm, and allowed to stand at a temperature of 60 ° C. to evaporate methylene chloride to remove Z-11-hexadecenal.
A film having a thickness of about 50 μm containing 25% by weight was obtained.

For comparison, a pheromone-containing film was prepared in the same manner as described above except that catechol was not contained. Furthermore,
As a stabilizer, except that 2,6-di-t-butyl-4-methylphenol (BHT) was used instead of catechol,
A pheromone-containing film was prepared in the same manner as described above.

Each of the above phenol-containing films was left outdoors in direct sunlight, and the time-dependent changes in the residual amount of Z-11-hexadecenal in the films were examined. The results are shown in FIG.

Separately, for the membrane according to the present invention containing the above catechol, Z-11-hexadecenal released from the membrane into the air was recovered using an adsorbent and quantified.
It was confirmed that Z-11-hexadecenal was gradually released at a release rate corresponding to the slope of the change curve of the residual amount in FIG.

Therefore, according to the film of the present invention, the Z-11-hexadecenal is kept in the film stably for a long period of time without substantial denaturation or polymerization, and the residual amount change shown in FIG. The release is shown corresponding to the curve. In contrast, membranes that do not contain catechol and membranes that contain BHT
When left outdoors, Z-
It is shown that 11-hexadecenal is lost.

Example 2 75 parts by weight of an ethylene-vinyl acetate copolymer having a vinyl acetate content of 45% by weight (Evaflexs 45X manufactured by Mitsui Polychemical Industries, Ltd.), 25 parts by weight of Z-13-octadecenal, and hydroquinone monomethyl ether (MEHQ) 0.5
Parts by weight were dissolved in 200 parts by weight of methylene chloride.

This solution was applied on a polyethylene terephthalate film at room temperature to a thickness of 200 μm, and allowed to stand at a temperature of 60 ° C. to evaporate methylene chloride to obtain Z-13-octadecenal.
A film having a thickness of about 50 μm containing 25% by weight was obtained.

For comparison, a pheromone-containing film was prepared in the same manner as described above except that hydroquinone monomethyl ether was not contained. Further, as a stabilizer, instead of hydroquinone monomethyl ether, 2,6-di-t-butyl-
A pheromone-containing film was prepared in the same manner as described above, except that 4-methylphenol (BHT) was used.

Each of the above phenol-containing films was allowed to stand in the field exposed to direct sunlight, and the time-dependent changes in the residual amount of Z-13-octadecenal in the films were examined. The results are shown in FIG.

Separately, as for the membrane according to the present invention containing the above-mentioned hydroquinone monomethyl ether, in the same manner as in Example 5, Z-13-octadecenal released from the membrane into the air shows the residual amount change curve in FIG. It was confirmed that sustained release was performed at a release rate corresponding to the inclination.

Therefore, according to the membrane according to the present invention, Z-13-octadesenal is stably retained in the membrane for a long period of time without any substantial denaturation, and the residual amount change curve shown in FIG. Correspondingly, a sustained release is shown. On the other hand, when the film for comparison is left outdoors, it is shown that Z-13-octadesenal is rapidly lost in the initial stage.

Example 3 75 parts by weight of an ethylene-vinyl acetate copolymer having a vinyl acetate content of 45% by weight (Evaflexs 45X manufactured by Mitsui Polychemical Industries, Ltd.), Z-9,12-octadecadienal 2
5 parts by weight and 0.5 parts by weight of catechol were dissolved in 200 parts by weight of methylene chloride.

This solution was applied on a polyethylene terephthalate film at a room temperature to a thickness of 200 μm, and allowed to stand at a temperature of 60 ° C. to evaporate methylene chloride to a thickness of about 25% by weight containing Z-9,12-octadecadienal. A 50 μm membrane was obtained.

For comparison, a pheromone-containing film was prepared in the same manner as described above except that catechol was not contained. Furthermore,
As a stabilizer, except that 2,6-di-t-butyl-4-methylphenol (BHT) was used instead of catechol,
A pheromone-containing film was prepared in the same manner as described above.

Each of the above phenol-containing films was left outdoors in direct sunlight, and the time-dependent changes in the residual amount of Z-9,12-octadecadienal in the films were examined. The results are shown in FIG.

Separately, as for the membrane according to the present invention containing the above-mentioned catechol, in the same manner as in Example 5, Z-9,12-octadecadienal released from the membrane into the air had a residual amount shown in FIG. It was confirmed that sustained release was performed at a release rate corresponding to the slope of the change curve.

Thus, according to the membrane according to the invention, Z-9,12-octadecadienal is shown in FIG. 3 while remaining stable in the membrane for a long period of time without substantial change. It is shown that the drug is gradually released according to the residual amount change curve. On the other hand, when the film for comparison is left outdoors, it is shown that Z-9,12-octadecadienal is rapidly lost in the initial stage.

[Brief description of the drawings]

FIGS. 1 to 3 are graphs showing the time-dependent changes in the residual amount of pheromone in the pheromone-containing film according to the present invention and the film for comparison, respectively, when the film is left outdoors.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-49-135907 (JP, A) JP-A-59-13701 (JP, A) JP-B-63-12452 (JP, B2) (58) Field (Int.Cl. ⁶ , DB name) A01N 25/34 A01N 25/10 A01N 35/02 C07C 47/21

Claims (4)

(57) [Claims] 1. A pheromone-containing polymer film, wherein a pheromone comprising a higher aliphatic non-conjugated aldehyde having a double bond not conjugated to an aldehyde carbonyl group and a hydroquinone-based compound are dissolved and contained in a polymer. 2. The pheromone-containing polymer membrane according to claim 1, wherein the aldehyde is hexadecenal, octadecenal or tetradecenal. 3. The pheromone-containing polymer film according to claim 1, wherein the hydroquinone compound is hydroquinone, resorcin, catechol, phloroglucin, α-naphthohydroquinone, or monomethyl or monoethyl ether thereof. 4. The pheromone-containing polymer film according to claim 1, wherein the polymer is an ethylene-vinyl acetate copolymer having a vinyl acetate content of 15 to 45% by weight.