JPH11343202A - Laminated packaging material for preserving insecticidal formulation and preservation of insecticidal formulation utilizing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a laminated packaging material capable of stably preserving an insecticidal formulation for a long period and satisfactory in economical efficiency, merchandise properties, preserving functions and suitability to environment by including a film on which the vapor of a metal oxide is deposited therein. SOLUTION: This laminated packaging material is obtained by including at least one or more layers of a film (preferably a nylon or a polyester) on which the vapor of a metal oxide (preferably silicon oxide) is deposited therein. A very small amount of an element (e.g. Fe or Sb) other than metal atoms may be contained as the metal oxide. The thickness of the vapor deposition layer is preferably 200-2,000 Å (9). A film having 10-20 μm thickness is preferred as the film. Paper, polyethylene, etc., are cited as a material laminated together with the film on which the vapor of the metal oxide is deposited. The thickness of the laminated packaging material is preferably 30-1,000 μm. The thickness is preferably 50-100 μm for a flexible packaging material such as a pouch and preferably 100-1,000 μm for a tube, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminated packaging material for storing an insecticide preparation for the purpose of storing the insecticide preparation stably for a long period of time, and a method for storing an insecticide preparation using the same.

[0002]

2. Description of the Related Art A variety of insecticide preparations have been known so far, and are used for controlling and repelling sanitary pests, agricultural pests, unpleasant pests and the like. Also, many insecticide preparations are required to have high degradability in the environment, and therefore, the insecticide preparations are relatively easily decomposed by contact with oxygen gas, water and the like. Therefore, it is necessary to prevent contact with oxygen gas, water and the like during storage and distribution of the insecticide preparation, and various methods have been proposed so far. For example, it is generally known that an insecticidal preparation is hermetically sealed using an aluminum foil, an aluminum vapor-deposited film, a polyvinylidene chloride film, a polyvinylidene chloride-coated film, a polyacrylonitrile, and a laminated film including an ethylene-vinyl acetate copolymer film. Have been. In addition, the incorporation of an antioxidant or an ultraviolet absorber into the insecticidal preparation is generally used as a method for improving their stability. Further, enclosing an oxygen absorbent or a moisture absorbent in the same package is also known as an auxiliary means.

[0003]

SUMMARY OF THE INVENTION However, a laminated packaging material for storing insecticide preparations, which is satisfactory in all aspects in consideration of economy, merchantability, and adaptability to the environment while maintaining sufficient storage performance, and using the same. The method of preserving the pesticide formulation was not known. For example, a method of hermetically storing an insecticidal preparation in a laminated film containing an aluminum foil is widely used, but its disadvantages are that the contents cannot be seen at all and that it is expensive. In addition, the use of laminated packaging materials including an aluminum vapor-deposited film, a polyvinylidene chloride film, and a polyvinylidene chloride-coated film is also known, but these are satisfactory for preventing invasion of oxygen gas, water vapor, and the like. However, it was not possible to completely prevent deterioration of the insecticide preparation, generation of an off-flavor due to decomposition, discoloration, leakage of the insecticide, and weight loss of various volatile components. In addition, aluminum or chlorine compounds are frequently used in the above films, and it takes a lot of time to dispose of them, taking into account the persistent nature of the environment, pollution of air, soil, and ecosystems, as well as the adverse effects. It was not available. Laminated films containing polyacrylonitrile and ethylene-vinyl acetate copolymer films have also been frequently used, but have also been unsatisfactory.

[0004] For the purpose of improving the effect of preventing the invasion of oxygen gas, water vapor, and the like, a method of increasing the basis weight (weight per unit area) of the laminated packaging material has been attempted. It was not satisfactory because it had adverse effects such as an increase in the amount of adsorbed and transferred into the material and an increase in cost.
In addition, the use of antioxidants, ultraviolet absorbers, oxygen absorbers, and moisture absorbers is merely an auxiliary means and has no definitive effect.

An object of the present invention is to provide a laminated packaging material for storing insecticide preparations which is stable and stable for a long period of time, and which is satisfactory in economy, merchantability, storage function and adaptability to the environment. It is intended to provide a method for storing an insecticide preparation.

[0006]

In order to achieve the above-mentioned object, according to the present invention, there is provided a laminated packaging material for storing insecticide preparations, comprising at least one or more films on which a metal oxide is deposited. Preferably, a laminated packaging material for storing insecticidal preparations using silicon oxide as the metal oxide is used, and more preferably, a laminated packaging material for storing insecticide preparations using any of nylon and polyester as the film. Is provided.

[0007] Further, there is provided a method for storing insecticide preparations, wherein a preparation containing an insecticide is sealed using at least a part of a laminated packaging material for storing insecticide preparations, which comprises at least one layer of a film on which a metal oxide is deposited. Is done. Preferably, a pyrethroid-based insecticide is used as the insecticide, and more preferably, one containing at least one pyrethroid-based insecticide having a vapor pressure of 10 ⁻⁴ mmHg (25 ° C.) is used.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention relates to a laminated packaging material for storing insecticide preparations, which comprises at least one layer of a metal oxide-deposited film, preferably a laminated packaging material for storing insecticide preparations, wherein the metal oxide is silicon oxide. More preferably, it is a laminated packaging material for storing insecticidal preparations, wherein either the nylon or the polyester is used as the film. That is, the deposited layer of the metal oxide prevents the flow of oxygen gas, water vapor and other gases, and closes the pinhole of the resin film.
Furthermore, it is possible to prevent a substance having a high vapor pressure such as a fragrance or a solvent or a pesticide having a high vapor pressure from leaking out or deviating outside.
Another effect is that the loss due to the transfer and adsorption of the insecticidal preparation to the laminated packaging material by vapor deposition of the metal oxide is extremely small. Furthermore, the fact that auxiliary means such as an antioxidant, an oxygen absorbent, and a moisture absorbent are likely to exert their effects is considered to be one of the factors contributing to the improvement of preservability as a synergistic effect.
In addition, the product of the present invention can be colorless and transparent, so that the contents can be viewed, which is also advantageous in improving the marketability,
No harmful substances are generated during disposal and incineration, and safety and environmental suitability are high.

As the metal oxide, Al, Si, T
Oxides such as i, Mg, In, Zn, and Sn are preferable, and a silicon oxide represented by SiOx (x = 0 to 2) is particularly preferable. The above various metal oxides may be arbitrarily combined, or may include unoxidized metal atoms. Elements other than the above metal atoms, for example, Fe, Sb,
Trace amounts of C, Mo, W, Cu, Zr, Ni, etc. may be contained. Further, metal compounds, for example, nitrides, carbides, sulfides, hydroxides, fluorides, chlorides, bromides, iodides, borides and the like of the above metals may be contained. Also,
The thickness of the vapor deposition layer is preferably from 50 to 3000 A (9). More preferably, it is 200 to 2000 A (9). 50A (9) or less is insufficient as a packaging material,
Above 2000A (9), transparency is lowered, post-processing is unsuitable,
Problems such as cracks, peeling, and cracks occur.

As the vapor deposition method, various methods such as vacuum vapor deposition, ion plating, sputtering, and plasma vapor deposition have been industrialized, but are not limited thereto.

As the film on which the metal oxide is deposited, nylon or polyester, preferably 8 to 25 μm, more preferably 10 to 20 μm is preferable in terms of economy, appearance, workability and the like, but not limited thereto. . If necessary, it is also possible to vapor-deposit not only on one side but also on both sides.

Paper, polyethylene, polypropylene and their stretched materials, nylon 6, nylon 6
6, polyvinyl chloride, polyvinylidene chloride, polyethylene terephthalate, ethylene vinyl acetate alcohol copolymer, polyvinyl alcohol, ethylene vinyl acetate copolymer, and any combination thereof. The properties include sheet, mesh, and non-woven fabric, but are not particularly limited. However, a transparent material is desirable in order to make use of the colorless and transparent of the metal oxide deposited thin film layer. In addition, as a laminating method, there are dry lamination, extrusion and the like by selecting an arbitrary adhesive and sealant, but there is no particular limitation. Any method can be selected for the purpose of improving heat resistance and piercing resistance. In order to prevent the penetration and penetration of ultraviolet rays, various printings and coatings with ultraviolet absorbers are also optional. The thickness of the laminated packaging material is preferably from 30 to 1000 μm. For soft packaging materials such as pouches and tray cover materials, 30 to 200 μm is preferable,
More preferably, 50 to 100 μm is used. 100 to 1000 μm is suitable for use as a tube or a molded container. If it is 30 μm or less, the physical strength as a packaging material is lacking, and if it is 1000 μm or more, it is not preferable because the suitability for a packaging machine is poor and the economic efficiency is lowered.

The present invention also provides a method for preserving an insecticide preparation, wherein the preparation containing the insecticide is sealed using at least a part of a laminated packaging material for preserving the insecticide preparation, which comprises at least one film on which a metal oxide is deposited. Is the way. The insecticide to be sealed is preferably a pyrethroid insecticide, and more preferably contains at least one pyrethroid insecticide having a vapor pressure of 10 ⁻⁴ mmHg (25 ° C.).

[0014] From the viewpoint of a film having only low air permeability, a film on which a metal oxide is deposited has been known. However, the present inventors far anticipated that when storing a formulation containing an insecticide, at least a portion of the laminated packaging material for preserving the insecticide formulation containing at least one or more films on which metal oxide was deposited was sealed. It has been found that this is an excellent preservation method. That is, the product of the present invention exhibits particularly remarkable performance in the storage of insecticide preparations. As a result, the expiration date of the insecticide preparation can be lengthened, and there is no merit such as a reduction in the risk of inventory management of the product. Also,
It cannot be overlooked that the present invention is satisfactory not only in the advantages of economy and commercial efficiency but also in adaptability to the global environment.

The insecticide stored by the above-mentioned method is not particularly limited as long as it is highly decomposable and discolors or produces an odor due to decomposition. Examples include fenitrothion, diazinon, dichlorvos, fenthion, pyridafenthion, propetanphos, chlorpyrifos, phoxime, azamethiphos, hydramethylnon, pyriproxyfen, imidacloprid, fenobcarb, boric acid, and the like. It is. That is, pyrethrin, allethrin,
Resmethrin, phthalthrine, framethrin, phenothrin, cyphenothrin, praletrin, permethrin,
Cypermethrin, decamestrin, fenvalerate, cyfluthrin, cyhalothrin, tralomethrin, imiprothrin and the like. It is more effective in preventing vapor leakage from those having a vapor pressure of 10 ⁻⁴ mmHg (25 ° C.) or higher, such as empentrin, teframethrin, teraretrin, and transfluthrin.

The above-mentioned preparations include matting agents, sheeting agents, and processed and molded products thereof, emulsions, oils, aqueous solvents,
Examples thereof include gels, powders, granules, pellets, and pastes, and any materials having physical properties capable of supporting the insecticide, such as those stored in a resin container or a paper container, can be used.

As a method for sealing the above-mentioned preparation containing an insecticide, the preparation containing the insecticide is stored in a bag using the laminated packaging material for storing an insecticide according to the present invention, and then laminated by heat and ultrasonic waves. Fusion of the innermost layers of the packaging material is common. In addition, a method of using a lid, a cap, or the like of a separate member for a tube, a container, or the like manufactured using the laminated packaging material for storing insecticide preparations according to the present invention, or conversely, the present invention for sealing an opening of a known container. It is also possible to use such a laminated packaging material for storing insecticide preparations. Note that the sealing method is not limited to these.

In order to impart light-shielding properties, it is also possible to add a pigment such as titanium oxide to the laminated packaging material for storing insecticide preparations according to the present invention, or to print the entire surface or apply an ultraviolet absorbent coating. The laminated packaging material for storing insecticide preparations according to the present invention has a sufficient tearing property at the time of opening, but a notch or the like can be added as necessary.

As the auxiliary means of the present invention, known antioxidants, potency enhancers, synergists, ultraviolet absorbers, surfactants,
Solvents, water, fragrances, coloring agents, deodorants, fungicide fungicides, natural essential oils, insect growth controlling substances, and the like can be optionally added to the insecticidal preparation.

The preparations containing the insecticide of the present invention include sanitary pests such as cockroaches, flies, mosquitoes, indoor dust mites, agricultural pests such as spider mites, aphids, bryozoans and weevils, and clothing pests such as burrs, burrs, burrowing bugs and spots. Ants, flies, bees,
Needless to say, it can be used for all pests such as unpleasant pests such as geese and wood pests such as termites and bark beetles.

Hereinafter, the present invention will be described in detail with reference to Examples, but it goes without saying that the present invention is not limited to the following Examples. First, polyester film (12 μm) and nylon film (15 μm)
, Silicon oxide was deposited to a thickness of 800 A (9) to obtain the following films (a) and (b).

Film (a) Polyester film 12
μm / silicon oxide 800A (9). Film (b) Nylon film 15 μm / silicon oxide 800A (9).

Further, the film (a), the film (b) and another film were laminated to obtain the following laminated packaging materials (A) to (E) for storing insecticide preparations. (A) The film (a) and a non-stretched polypropylene film 30 μm are laminated (thickness 42 μm). (B) Polyester film 12 μm and film (a)
And a polyethylene film 40 μm in this order (thickness 64 μm). (C) Film (b) and polyethylene film 15 μm
And a low-pressure low-density polyethylene film 50 μm in this order (thickness 80 μm). (D) A stretched polypropylene film of 20 μm, a film (b) and a low-pressure low-density polyethylene film of 40 μm are laminated in this order (thickness of 75 μm). (E) A polypropylene film, a film (b) and a polypropylene film are laminated in this order (thickness 500 μm).
m).

The laminated packaging materials as comparative examples not according to the present invention are shown below as (F) to (J). (F) A polyvinylidene chloride-coated polyester film 12 μm, a low density polyethylene film 20 μm, and an ethylene vinyl acetate copolymer film 40 μm were laminated in this order (thickness 72 μm). (G) Polyvinylidene chloride-coated stretched polypropylene film 20 μm and unstretched polypropylene film 60 μm
m (thickness: 80 μm). (H) Polyvinylidene chloride coated polyester film 12 μm, low density polyethylene film 20 μm and ethylene vinyl acetate copolymer film 40 μm were laminated in this order (thickness 72 μm). (I) A polyester film of 12 μm and an ethylene-vinyl acetate copolymer film of 30 μm were laminated (42 μm in thickness). (J) A polypropylene film, an ethylene-vinyl acetate copolymer film and a polypropylene film were laminated in this order (thickness: 500 μm).

(Test Example 1) Laminated packaging materials (A), (B), (C) and (D) for storing insecticidal preparations of the examples and laminated packaging materials (F) (G) (H) (I) as comparative examples A pulp mat (10 × 10 cm), onto which 300 mg of empentrin was adsorbed as a preparation, was packaged with each packaging material, and was used as Examples (1) to (4) and Comparative Examples (1) to (4). .
These were stored under conditions of constant temperature and humidity controlled to 40 ° C. and 75% RH, and after 3, 6 and 12 months, the residual ratio of empentrin was extracted with an organic solvent and analyzed by gas chromatography. At the same time, the generation of off-flavors and discoloration of the preparation was also confirmed according to the following criteria.

As for the off-flavor, the decomposition off-flavor emitted from the preparation was compared with that before storage. ○ No off-flavor is felt. △ A slight off-flavor is felt. ×: A clear off-flavor is felt.

The discoloration was compared with the color change of the preparation before storage. ○ No discoloration is observed. Δ: slight discoloration is observed. X: Discoloration is apparent.

The test results are shown in Table 1 below.

[0029]

[Table 1]

From the test results shown in Table 1, in each of the examples, the off-flavor and discoloration were suppressed for 12 months, and the empentrin residual rate was extremely high. However, it can be seen that in each of the comparative examples, an unusual odor and discoloration occurred early, and the residual ratio of empentrin decreased quickly.

Test Example 2 In the same manner as in Test Example 1, a pulp mat (2 ×
4 cm) were packaged in Examples (5) to (8),
Comparative Examples (5) to (8) were made. These are at 40 ° C 75% R
H, air-conditioned at a constant temperature and humidity, 3, 6,
Twelve months later, the residual ratio of praletrin was extracted with an organic solvent and analyzed by gas chromatography. Table 2 shows the test results.

[0032]

[Table 2]

From the test results shown in Table 2, in each of the examples, the residual ratio of praletrin was extremely high for 12 months. However, in each of the comparative examples, it can be seen that the decrease in the residual ratio of prarethrin was rapid.

(Test Example 3) A nonwoven fabric (100 × 100 cm) on which 100 mg of phenothrin was printed in the same manner as in Test Example 1.
Were packaged as Examples (9) to (12) and Comparative Examples (9) to (12), respectively. These are stored under the condition of constant temperature and humidity controlled to 40 ° C. and 75% RH,
After one month, the residual ratio of phenothrin was extracted with an organic solvent and analyzed by gas chromatography. At the same time, the generation of off-flavor and discoloration was also confirmed according to the above-mentioned criteria. Table 3 shows the test results.

[0035]

[Table 3]

From the test results shown in Table 3, in each Example, both offensive odor and discoloration were suppressed for 12 months,
Also, the phenothrin residual rate is extremely high. However, it can be seen that in each of the comparative examples, an offensive odor and discoloration occur early, and the phenothrin residual rate decreases quickly.

(Test Example 4) As in Test Example 1, DDVP5
Each of the packaged resin plates (10 × 5 cm) impregnated with 00 mg was subjected to Examples (13) to (16) and Comparative Example (1).
3) to (16). These were stored under the condition of constant temperature and humidity controlled to 40 ° C. and 75% RH, and after 3, 6 and 12 months, the residual ratio of DDVP was extracted with an organic solvent and analyzed by gas chromatography. Table 4 shows the test results.

[0038]

[Table 4]

From the test results shown in Table 4, the DDVP residual rate is extremely high for 12 months in each example. However, in each of the comparative examples, it can be seen that the DDVP residual rate decreases quickly.

Test Example 5 A tray is formed using the laminated packaging material (E) for storing insecticidal preparations of the example and the laminated packaging material (J) as a comparative example. Empentrin 5 in the tray
100 g of an oily gel containing 00 mg was filled, the former was sealed with a laminated packaging material (A) for storing insecticidal preparations, and the latter was sealed with a laminated packaging material (G), respectively, to obtain an example (17) and a comparative example (17). These were stored under the condition of constant temperature and humidity controlled to 40 ° C. and 75% RH, and after 3, 6 and 12 months, the residual ratio of empentrin was extracted with an organic solvent and analyzed by gas chromatography. Table 5 shows the test results.

[0041]

[Table 5]

From the test results shown in Table 5, in the examples, the residual ratio of empentrin is extremely high for 12 months. However, in the comparative example, it can be seen that the empentrin residual rate decreases quickly.

Claims (6)

[Claims] 1. A laminated packaging material for storing insecticide preparations, comprising at least one or more films on which a metal oxide is deposited. 2. The laminated packaging material according to claim 1, wherein the metal oxide is a silicon oxide. 3. The laminated packaging material for storing insecticide preparations according to claim 2, wherein the film is one of nylon and polyester. 4. A method for storing insecticide preparations, wherein a preparation containing an insecticide is sealed using at least a part of a laminated packaging material for storing insecticide preparations, which contains at least one film on which a metal oxide is deposited. 5. The method according to claim 4, wherein the insecticide is a pyrethroid insecticide. 6. The method according to claim 5, wherein at least one pyrethroid insecticide having a vapor pressure of not less than 10 ⁻⁴ mmHg (25 ° C.) is contained.