JPH037203A - Complex insecticide, insect-killing method and packing material for same insecticide - Google Patents

Abstract

PURPOSE:To obtain complex insecticide suitable for clothing exhibiting excellent insecticidal effect with synergistic effect co-existing active ingredients in the same environment in a shape of packaging material, etc., wrapping with film by combining trioxane and empenthrin as active ingredients. CONSTITUTION:Trioxane is combined with empenthrin as active ingredients and co-existed in the same environment to afford the aimed complex insecticide. Further, trioxane and empenthrin-containing substance or a mixture of the two substances is wrapped with synthetic resin film composed of polyolefin or laminated film of polyolefin film and porous reinforcing material having pierced holes to afford the aimed packing material for the complex insecticide. The complex insecticide is capable of avoiding use of p-dichlorobenzene having problems of toxicity and environmental pollution and the packing material for the insecticide is capable of readily exhibiting a point of time dissipating of drug by selecting combination of wrapping material and dose from appearance.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel insect repellent. More specifically, the present invention relates to a composite insect repellent in which active ingredients are combined and suitable for use in clothing, an insect repellent method using this composite insect repellent, and a package for this composite insect repellent.

[Prior Art and Problems to be Solved by the Invention] Sublimable substances such as silica, naphthalene, and p-dichlorobenzene have been used as insect repellents for clothing.

However, the effectiveness of snails and s7tales against clothing pests such as burs, burs, and snail beetles is low. Furthermore, p-dichlorobenzene has become a problem due to its toxicity and environmental pollution.

On the other hand, (RS)-1-ethynyl-2-methylpento 2
- Insect repellents containing pyrethroid drugs as active ingredients, such as cis- and trans-chrysanthemate (hereinafter referred to as ``empenthrin''), have been developed and are commercially available; cannot be said to be sufficiently strong for practical purposes.

Furthermore, insect repellents are known that combine empenthrin with sublimable substances such as p-dichlorobenzene, naphthalene, silica, or 2,4,6-dolyisoprobyl-1,3,5-trioxane (especially Kaisho 61-831
No. 02, JP-A-62-72601).

However, these sublimable substances have a higher vapor pressure than empenthrin (and are more permeable to the packaging material), so in the space where insects are to be prevented, there are more sublimable substances than empenthrin. Therefore, it is difficult to arbitrarily select the ratio of empenthrin and these sublimable substances, and this ratio changes with the passage of time.Also, as a sublimable substance, 2.4.6 −
) When diisoprobyl-1,3,5-trioxane is used, the insect repellent effect is weak.

The present inventors have previously discovered 1 as an insect repellent that exhibits a high insect repellent effect.
．． 3. An insect repellent containing 5-trioxane (simply referred to as trioxane) as an active ingredient was discovered (Japanese Patent Laid-Open No. 63-1
15802).

Even when trioxane is used alone, it exhibits a practically sufficient insect repellent effect against clothing insect pests, and the object of the present invention is to provide a packaging material and an insect repellent method.

[Means and effects for solving the problem] The present inventors,
As a result of repeated research to develop an excellent insect repellent and insect repellent method, it was discovered that the above-mentioned problems could be overcome by combining trioxane and empenthrin, and the present invention was completed.

That is, the present invention is a composite insect repellent characterized by a combination of trioxane and empenthrin as active ingredients, and an insect repellent characterized in that the active ingredients tidrioxane and empenthrin coexist in the same environment. It's a method.

It is known that trioxane and empenthrin each have an insect repellent effect on their own. However, it is surprising that when both are used in combination, they exhibit a significantly higher insect repellent effect.

In the present invention, it is necessary to use trioxane and empenthrin in combination.

In the present invention, allowing trioxane and empenthrin to coexist in the same environment means allowing both to coexist in a space large enough to allow sufficient amounts of trioxane vapor and empenthrin vapor to mix with each other, In practical terms, the environment is the inside of a chest of drawers, a drawer, a costume case, a clothing store, and the like. In addition, an open space may be used as long as a sufficient amount of trioxane vapor and empenthrin vapor are mixed with each other.

In the present invention, combining trioxane and empenthrin as active ingredients means using trioxane and empenthrin together in separate and independent dosage forms, and combining both of their different dosage forms in a packaging material. This includes packaging and use, as well as mixing the two and using them as a single dosage form.

Typical embodiments include, for example, the following or non-perforated polyolefin films or perforated films made of synthetic resins other than polyolefins,
(including a sheet, the same shall apply hereinafter); and an open container filled with empenthrin;
An impregnated body in which a carrier is impregnated with empenthrin or a package in which empenthrin or empenthrin IJ is encapsulated in a synthetic resin film (hereinafter collectively referred to as an empenthrin-containing body) are placed close to each other in the same environment. and place them. (bl) A package in which trioxane in the form of one cube, such as powder, granule, or plate, and an empenthrin-containing body are encapsulated in a synthetic resin film is placed in the target environment.In this case, the trioxane The mixture of trioxane and empenthrin or the molded product of this mixture is wrapped in a synthetic resin film and placed in the target environment. have it placed.

The trioxane in each of (a) and (bl) and the trioxane and empenthrin in each of (bl and 伜) above are usually packaged using a perforated synthetic resin film.Adjust the sublimation rate of trioxane. The size and number of pores may be selected appropriately.The synthetic resin film used in this case may be one that is not attacked by trioxane and empenthrin (for example, polyethylene, polypropylene, polyvinylidene chloride, Films made of thermoplastic synthetic resins such as polyvinyl alcohol, polymethacrylate, polyester, polyamide and polyvinyl acetate are preferably used, and films made of semi-synthetic resins such as cellophane and thermosetting synthetic resins can also be used. Furthermore, a laminated film of the same type of film and a different type of film in the above film, or a paper making film,
It is possible and preferable to use a laminated film reinforced by ff2S with a porous reinforcing material such as a woven fabric or a non-woven fabric.

In addition, in cases where the sublimation rate of trioxane may be relatively low, a polyolefin film or a laminated film reinforced by laminating a porous reinforcing material such as paper, woven fabric, or non-woven fabric on a polyolefin film is used as the synthetic resin film. In some cases, depending on the thickness of the film, it may not be necessary to make perforations. Although there are no particular restrictions on the polyolefin film used in this case, a polyethylene film is usually used, and in practice, a low-density polyethylene film is preferably used. In addition, as for the packaging materials in each of (b) and tc+, both the polyolefin and the porous reinforcing material have virtually no barrier properties against empenthrin vapor, and limit the continuous firing rate of empenthrin, which is extremely small compared to trioxane. Therefore, a polyolefin film or a laminated film reinforced by laminating a porous reinforcing material such as paper, woven fabric, or non-woven fabric on a polyolefin film is preferably used.

The thickness of the synthetic resin film or the laminated film of the synthetic resin film and the porous reinforcing material for packaging trioxane, both trioxane and empenthrin-containing body, or the mixture of trioxane and empenthrin is generally determined by other known methods. The thickness may be the same as that used for packaging the anti-oxidant agent, but 10 to 200 um is preferable, and 20 to 80 um is more preferable.

Although there are no particular limitations on the open container filled with empenthrin in (-) and (b) above, the open container made of synthetic resin is preferably used in practice.

Note that filling the open container with empenthrin also includes encapsulating the empenthrin in the perforated synthetic resin film. Further, there is no particular restriction on the carrier impregnated with empenthrin, but felt, woven fabric, nonwoven fabric, paper, non-rubber, etc. are preferably used in practice. There is no particular restriction on the film for packaging empenthrin, but in practice, the above-mentioned synthetic resin films are preferably used, and polyolefins are particularly preferably used.

In the above (C), the mixture of trioxane and empenthrin can be obtained by spraying empenthrin onto powdered, granular or plate-shaped trioxane, or by mixing molten trioxane and empenthrin and then cooling and solidifying the mixture. .

Among these mixtures, when powdered or granular trioxane is used, the mixture is molded into granules, spheres, rods, cylinders, and plates by a conventional method such as heat compression molding. It can also be molded and used.

In the present invention, the amount ratio of empenthrin depends on how trioxane is packaged (degree of perforation).

Generally, 0.02 to 2% by weight based on trioxane is preferred, and 0.1 to 1% by weight is more preferred.

If the content of empenthrin is too high, trioxane may sublimate and disappear before empenthrin evaporates and disappears, or when a mixture of the two is used, empenthrin oozes out as a liquid. If the content of empenthrin is too low, empenthrin will volatilize and disappear before trioxane sublimates and disappears, resulting in a decrease in the insect repellent effect.

The composite insect repellent 1ζ of the present invention may further contain other additives such as suitable stabilizers and fragrances, if desired.

There are no particular limitations on the method of manufacturing the insect repellent package of the present invention.

For example, particulate solid trioxane and empenthrin-impregnated paper can be packaged in a perforated polyethylene film or a perforated polyethylene/porous reinforcement laminate film. The same method can be used for preparations obtained by spraying empenthrin on granular trioxane, preparations obtained by adding and mixing empenthrin to molten trioxane, and then solidifying, or tablets obtained by molding these preparations. Can be packaged in In particular, when trioxane and empenthrin are mixed in a molten state and then filled and solidified, the mixture of the two is filled in a bag container made of unperforated synthetic resin film in a molten state, and the contents are After the material has cooled and solidified, perforations can be made in the film forming the container, if desired.

In accordance with the present invention, the size and number of pores and the total pore area (the area of the entire pores per unit area of the effective surface of the synthetic resin film, the same shall apply hereinafter) of the pores provided in the synthetic resin film for packaging trioxane and trioxane and empenthrin. By appropriately selecting the above, the volatilization rate of the contents can be adjusted.

Generally, the size of the hole is preferably about 0.5 to 1.5 nm in effective diameter (diameter when the hole is a circle, hereinafter the same).

The number of holes is preferably 0.01 to 10 per effective surface area of the synthetic resin film container. Furthermore, the total pore area is generally 0501 to 10/cII.

In the present invention, the ratio of trioxane vapor and empenthrin vapor in the environment to be insect-proofed is practically 0°3 to 109/J' and 0,03 to IB&, preferably 1,000 to 1,000, respectively, per 1 j of environmental volume. ~6
da and 0.1 to 0.6119.

Here, Experimental Example 1 shows that empenthrin vapor permeates through polyethylene film much more easily than other types of packaging materials 1ζ.

4 cm x 5 cy impregnated with empenthrin
The same operation was performed without putting the pr filter paper in the bag. 90
The results of measuring the weight loss after 1 day are shown in Table 1.

(Experimental example 1) Low density polyethylene film (P
E), polyester laminated with polyethylene (PET), nylon laminated with polyethylene (NY), and stretched polypropylene film laminated with unstretched polypropylene (p
4.5clnx5.5CM each made with p)
A 4 eM x 5 cWI filter paper impregnated with 0°29 empenthrin was placed in each bag, the mouth of the bag was heat-sealed, and the bag was left in a room maintained at a temperature of 35 ± 1°C. For comparison, Experimental Example 2 shows that trioxane is much less permeable through a polyethylene film than other sublimable substances in terms of its saturated vapor concentration I.

(Experiment Example 2) Powder-like various sublimable substances 2.09 were placed in 7 cm x 5 eM bags made of low-density polyethylene film with a thickness of 0.04 mm, the mouth of the bag was heat-sealed, and the bag was kept at room temperature. 25 soil and hung in a room maintained at 1°C. Table 2 shows the results of measuring the decrease in critical condition after 24 hours. For reference, the saturated vapor concentration of each sublimable substance at 25°C is also listed.

Table 2 〔Example〕 Next, the present invention will be explained in more detail with reference to Examples.

Example 1 Laminated film of Japanese paper and polyethylene (Japanese paper 209/y
l, 65 cm in a 10 crn x 6 crn square bag made using polyethylene film with a thickness of 30 μ →
Melted trioxane 309 and empenthrin at 0°2
After filling and sealing the mixture with 5 g, the mixture was sandwiched between two stainless steel plates and solidified and molded flat while cooling.

Next, six holes were perforated in the film layer using a needle drum having a needle diameter of 0.5 mm to obtain a package of the trioxane-empenthrin mixture.

A total of two packages of trioxane-empenthrin mixture were prepared in the same manner.

Two packages of the trioxane-empenthrin mixture were placed in the center of a polypropylene wardrobe box with contents ff150J, 5 degrees apart from the bottom and 401 degrees apart, and a 40-day-old burr was placed between the two packages. 10 larvae (35 da/
10 heads), and 3σ angle wool woven fabric (approximately 1001119
) were fixed in three wire mesh baskets with a diameter of 3 crn.

This costume box was left in a room at 23° C. while being shielded with a polypropylene film to prevent direct exposure to wind.

After 10 days, the air inside the clothing box was sampled and analyzed for trioxane concentration and empenthrin concentration using a gas chromatograph. Furthermore, the survival and death of burr larvae and the amount of feeding damage to wool fabric were investigated. In addition, a similar experiment was conducted without using any chemicals, and the group was treated as an untreated group.

The results were evaluated by insect killing rate and feeding damage rate.

That is, the insecticidal rate (X (5%)') is set as Instead of a mixture with empenthrin,
Two packages were obtained using only trioxane, and the same insect repellent test as in Example 1 was conducted using these packages.

I asked for it as.

Comparative Example 2 Empenthrin 0.259 was uniformly applied to a 10 m x 6 square filter paper to obtain an empenthrin-impregnated filter paper. A total of two sheets of empenthrin-impregnated filter paper were prepared using the same strainer, and an insect control test similar to that in Example 1 was conducted using one of these sheets in place of the package. The results are shown in Table 3.

here, Table 3 It is.

In addition, There were no dead insects in the untreated area.

Example 2 30 g of granular trioxane with 9 to 16 meshes was mixed into a laminated film of polyester and polyethylene (thickness: 30 μm; each 15 ffm ) to obtain a trioxane package. On the other hand, empenthrin 0.1.9 was uniformly applied to a sheet of filter paper measuring 8 cy*×5 m square to obtain an empenthrin-impregnated filter paper.

Place the above trioxane package and empenthrin-impregnated filter paper side by side in the center of a polypropylene costume box with a capacity of 501, 5 cWI above the bottom surface, and place a 40-day-old burr larva at a position 20σ away from the package and the filter paper. 10 heads (
35cm/10 cows) and 3m square wool woven fabric (approximately 100η
) is the diameter of 3/l? It was shielded to the extent that it would not be exposed to the FI and left in a room at 23°C.

After 10 days, the air inside the clothing box was sampled and analyzed for trioxane concentration and empenthrin concentration using a gas chromatograph. Furthermore, the survival and death of the burr larvae and the damage caused by feeding on the wool fabric were investigated. In addition, a similar experiment was conducted without using any chemicals, and the group was treated as an untreated group.

As in Example 1, the results were evaluated based on the insecticidal rate and the feeding damage rate. There were no dead insects in the untreated area.

Comparative Example 3 An insect control test similar to Example 2 was conducted using only the trioxane package without using the empenthrin-impregnated filter paper.

Comparative Example 4 An insect repellent test similar to that in Example 2 was conducted using only empenthrin-impregnated filter paper without using the trioxane package.

Comparative Example 5 From the same procedure as in Example 2, using 2,4,6-dolyisoprobyl-1,3,5-)lioxane instead of trioxane, 2,4,6-)lyisoprobyl-1,3, 5-) A lioxane package was obtained. An insect repellent test similar to that in Example 2 was conducted using this package in combination with empenthrin-impregnated filter paper. The results are shown in Table 4.

Example 3 A bag made of a laminated film of Japanese paper and polyethylene (Japanese paper 2097rl, polyethylene film thickness 30 μff) with an 8 m x 8 square hole, in which 8 holes were perforated using a needle drum with a needle diameter of 0.5 mm. A trioxane package was obtained by filling 9 to 16 meshes of granular trioxane 259.

Empenthrin O,1,! 5c with i' applied evenly
An empenthrin package was obtained by wrapping a m x 4 cm square filter paper using a 6- x 5α laminated film of Japanese paper and polyethylene. The trioxane package and the empenthrin package were placed in close proximity in a constant temperature bath at 30°C. The inside of the tank was ventilated with nitrogen.

The remaining amounts of trioxane and empenthrin are shown in Table 5. After standing for 80 days, the trioxane in the trioxane package disappeared by sublimation, and most of the empenthrin in the empenthrin package disappeared by volatilization.

Table 5 Example 4 Laminated film of Japanese paper and polyethylene (Japanese paper 209/l
A bag made of polyethylene film (with a thickness of 30 μm) was used with a plate attached with a needle with a needle diameter of 0.5 μm.
After drilling 0 holes and filling them with 9 to 16 meshes of granular trioxane 20.9, empenthrin was added.
An empenthrin-impregnated filter paper obtained by uniformly applying 0.2 g of the empenthrin to one 7 cm x 5 crn filter paper was inserted into the gap between the granular trioxane and the laminated film, and heat-sealed to obtain an insect repellent package. Effective area excluding seal part is 8m x 6z
It was a corner.

The same operation was repeated to create a total of two insect repellent packages.

In the center of a polypropylene costume box with an internal volume of 50 cm, two of the above insect repellent packages were placed 40 m apart from the bottom surface.
Mfi, and between the two packages there was a wire mesh with a diameter of 3tn+ containing 10 40-day-old burr larvae (37■/10 larvae) and a 3α square wool woven fabric (approximately 100#). Three baskets were fixed.

This clothing box was left in a room at a temperature of 23 to 25° C. and a relative humidity of 60 to 70% while being shielded with a polypropylene film to prevent direct contact with the melons.

After 10 days, the air inside the clothing box was sampled and analyzed for trioxane concentration and empenthrin concentration using a gas chromatograph. Furthermore, the survival and death of burr larvae and the amount of feeding damage to wool fabric were investigated. In addition, a similar experiment was conducted without using any chemicals, and the group was treated as an untreated group.

As in Example 1, the results are expressed as insect killing rate and feeding damage rate.

There were no dead insects in the untreated area.

Comparative Example 6 Two trioxane packages were obtained by carrying out the same operation as in Example 4 using only granular trioxane without using the empenthrin-impregnated filter paper. Using this, the same insect control test as in Example 4 was conducted.

Comparative Example 7 By performing the same operation as in Example 4 without using trioxane and using only empenthrin-impregnated filter paper, 2
A package of empenthrin filter paper was obtained. Using this, the same insect control test as in Example 4 was conducted.

The results are shown in Table 6.

The above-mentioned bag was placed in Table 6 and heat-sealed to obtain an insect repellent package. The effective surface area excluding the seal portion was 10 crn×6α angle.

The above-mentioned insect repellent package was placed in the center of a polypropylene clothing box with an internal volume of 501 cm, at a distance of 5α from the bottom surface.

Store this wardrobe at a temperature of 22-23°C and a relative humidity of 50-6°C.
I left it in the room of 096.

After 10 days, the air inside the wardrobe was sampled and analyzed using a gas chromatograph, and the concentration of trioxane was 2.5.
/1. And empenthrin (1 degree is 0, 3119/
It was l.

Example 5 After filling and packaging 9 to 16 meshes of granular trioxane 25.9 into a 'Jy++
, 059 was applied uniformly. Bag made of non-porous low-density polyethylene film with a thickness of 20 um [Effects of the invention] Since the composite insect repellent of the present invention exhibits excellent insect repellent action,
Suitable for use as an insect repellent for clothing.

In the insect repellent package according to the present invention, by selecting a combination of the packaging material and the amount of the drug, it is possible to easily know from the appearance when the drug has disappeared.

By using the composite insect repellent of the present invention, it is possible to avoid the use of p-dichlorobenzene, which is problematic in terms of its toxicity and environmental pollution.

Claims (6)

[Claims] (1) A composite insect repellent characterized by containing a combination of trioxane and empenthrin as an active ingredient. (2) An insect control method characterized by allowing trioxane and empenthrin as active ingredients to coexist in the same environment. (3) An insect repellent package characterized in that trioxane and an empenthrin-containing body are encapsulated in a synthetic resin film having perforations. (4) An insect repellent package characterized in that trioxane and an empenthrin-containing substance are encapsulated with a polyolefin film or a laminated film of a polyolefin film and a porous reinforcing material. (5) An insect repellent package characterized in that a mixture of trioxane and empenthrin is encapsulated in a synthetic resin film having perforations. (6) An insect repellent package characterized in that a mixture of trioxane and empenthrin is encapsulated with a polyolefin film or a laminated film of a polyolefin film and a porous reinforcing material.