JPH1072301A - Outer packing material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an outer packing material for a preparation, capable of suppressing volatility of an agrochemical formulation having volatility at a room temperature, preserving and distributing the formulation in general by using a substance having specific qualities of material. SOLUTION: An agrochemical having volatility at a room temperature is formulated to give an inner packed material of an agrochemical formulation having reduced volatility, which is put in an outer packing material made of a plastic, such as container or bag and sealed. A plastic film having <=10.0 g/m<2> .day.atm (38 deg.C, 90%RH) water vapor transmission, especially <=5.00g/m<2> .hr gas permeability rate of the agrochemical and excellent in corrosion resistance is preferable as the outer packing material made of the plastic. In the case of a container or a bag, preferably the humidity in the interior of the outer packing material can be retained at 5-25% (20 deg.C, 1atm). A vinylidene chloride, an ethylene/vinyl alcohol copolymer, a polyacrylonitrile or a laminate of plural films is preferable as the plastic film.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a packaging material for an agricultural chemical having volatility at room temperature, which can be stored with reduced volatility, and which can be generally distributed, and a container or bag made of such packaging material. The present invention relates to an outer package body containing a preparation.

[0002]

BACKGROUND OF THE INVENTION Soil fumigants which are liquid at room temperature, such as chloropicrin, 1,3-dichloropropene, dichlorodiisopropyl ether and methyl isothiocyanate, are to be applied in the liquid state by filling them in the tank of the soil irrigation machine. Used and released into the soil from the tip nozzle of the irrigation machine. In this case, the toxicity, volatilization and tearing properties of the fumigant adversely affect the health of workers.

[0003] In recent years, for the purpose of preventing such chemical damage, attempts have been made to solidify these soil fumigants to facilitate application operations. For example, chloropicrin is mixed with dibenzylidene sorbitol and a gelling preparation in an organic solvent, gelled, and vacuum-packed with a gas-impermeable film (Japanese Patent Application Laid-Open No. 62-192301). Absorbed into porous granules,
A method of coating with a water-soluble polymer has been disclosed (JP-A-01-172302).

[0004] However, even the chloropicrin preparation prepared and manufactured by such a method does not completely suppress the volatility and tearing property. JP-A-62-192301
When a chloropicrin preparation prepared by the method described in the publication is left at room temperature, the active ingredient of the preparation gradually volatilizes and the weight of the preparation decreases. As a product form of such a preparation, it is necessary to further cover the preparation with a material in which the content of the active ingredient contained in the preparation is difficult to volatilize, but such techniques and materials are not known.

[0005]

DISCLOSURE OF THE INVENTION The present invention provides a packaging material for a pesticide formulation which is volatile at room temperature and which can be stored with reduced volatility and generally distributed.

[0006]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, it has been found that a pesticide formulation can be put in a container, a bag, or the like that reduces the gas permeation rate of the pesticide and sealed. And completed the present invention.

That is, the present invention provides (1) a container or a bag for accommodating and sealing an inner package of a pesticide having reduced volatility by formulating a pesticide having volatility at room temperature. (2) an exterior material for an agricultural chemical formulation, wherein the exterior material is made of plastic;
The moisture permeability is 10.0 g / m ² · day · atm (38
C., 90% RH) or less, (3) keeping the humidity inside the packaging material forming the container or bag at 5 to 25% (20 ° C., 1 atm). (1) or (2), wherein the plastic has a gas transmission rate of pesticides of 5.00 g / m at room temperature.
(1) A packaging material for agricultural chemicals according to any one of (1) to (3), which is a plastic film excellent in corrosion resistance at a permeation speed of ² hr or less, and (5) vinylidene chloride as a plastic film. (PVDC); (6) an exterior material according to (4), wherein an ethylene-vinyl alcohol copolymer (EVOH) is used as a plastic film; (4) The exterior material according to (4), wherein polyacrylonitrile (PAN) is used as the plastic film, (8) the exterior material according to (4), wherein the plastic film is bonded to form a multilayer, and (9) the plastic film is (4) The exterior material according to (4), wherein a plurality of sheets are laminated, and a metal layer is further laminated with a plastic film. (11) The container according to (4), wherein the inner package body of the pesticide formulation having reduced volatility by formulating a pesticide having volatility at room temperature is contained and sealed. A cladding material for agricultural chemicals, characterized in that the material is a metal having excellent corrosion resistance;
2) The metal is stainless steel (1)
(1) The exterior material according to (1), wherein the pesticide having volatility at room temperature is a combination of one or more of chlorpicrin, 1,3-dichloropropene, dichlorodiisopropyl ether, and methyl isothiocyanate. (14) An inner package of a pesticide formulation having reduced volatility by formulating a pesticide having volatility at room temperature, wherein (14) the outer packaging material according to any one of (1) to (12), (15) an outer package of a pesticide formulation, wherein the outer package is housed and sealed in an exterior material forming a plastic container or bag.
The moisture permeability of the exterior material is 10.0 g / m ² · day · atm
(38 ° C., 90% RH) or less, (16) The outer package forming the outer package, wherein the humidity inside the outer package forming the outer package is 5 to 25% (20 ° C., 1 atm).
(14) or (15), wherein the outer packaging material has excellent corrosion resistance at a gas transmission rate of the pesticide of 5.00 g / m ² · hr or less at room temperature. It is characterized by being a plastic film (1
(4) The outer package of the agricultural chemical formulation according to any one of (16), (18) The outer package according to (17), wherein vinylidene chloride (PVDC) is used as the plastic film, (19) Plastic (17) The outer package according to (17), wherein an ethylene-vinyl alcohol copolymer (EVOH) is used as the film.
0) An outer package according to (17), wherein polyacrylonitrile (PAN) is used as the plastic film, (21) a plastic film is adhered,
(22) An outer package according to (17), wherein a plurality of plastic films are laminated, (23) Further, a metal layer is laminated with the plastic film. (17) Material of a container formed by containing and sealing an inner package of a pesticide formulation having reduced volatility by formulating a pesticide having volatility at room temperature. Is a metal having excellent corrosion resistance; (25) an outer package according to (24), wherein the metal is stainless steel; and (26) volatile at room temperature. Wherein chloropicrin, 1,3-dichloropropene, dichlorodiisopropyl ether, or a combination of two or more of methyl isothiocyanate is used. That (14) is an outer packaging according to any of the - (25).

[0008]

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method of combining one or more of pesticides which are volatile at room temperature, such as chloropicrin, 1,3-dichloropropene, dichlorodiisopropyl ether and methyl isothiocyanate. It can be used for pesticides. The exterior material in the present invention refers to a metal container or a plastic container or bag having corrosion resistance to pesticides, which are the active ingredients of the preparation.

When the inner package of the pesticide formulation is accommodated in a metal container and hermetically sealed or hermetically sealed to form an outer package of the pesticide formulation, a product having little reactivity with the above-mentioned pesticide, for example, stainless steel is used. I found something good to use. When a container made of stainless steel is used, the inner package of the pesticide formulation is put in the container, and a stainless steel lid is put on. As the lid, a screw-type lid may be used, or a lid-fixing type may be used. Such a stainless steel container not only has a low permeation rate of the pesticidal active ingredients but also does not allow air, water vapor, and even light in the atmosphere to pass through, so that the components in the pesticide formulation react with these atmospheric components. Even if it is easy, it has the property that it is difficult to react,
The deterioration of the pesticide formulation can be prevented. Furthermore, since such a metal container has physical strength, it is advantageous in that the container can be used without any breakage even in a general distribution process. Further, such a metal container may be used in combination with a container or bag made of a plastic film. That is, it goes without saying that the pesticide formulation packaged with the plastic outer material may be further placed in such a metal container.

On the other hand, in the case of using plastic, it is preferable to use a material which has corrosion resistance to pesticides and is difficult to pass through substances which react with a formulation such as gas, water or light of pesticides as in the case of metal containers. . As for the gas permeability of the pesticide, in the case of plastic, it is preferable to use a material having a permeation rate of 5.00 g / m ² · hr or less at room temperature, and preferably 1.00 g / m ² · hr.
m ² · hr or less, more preferably 0.10 g
/ M ² · hr or less. Pesticide gas permeation rate here is room temperature (20 ° C), relative humidity 50%
The values measured in the table are shown. In this case, a plastic film is preferable.

In the present invention, the method for measuring the gas permeation rate of the pesticide with respect to the exterior material is performed as follows. That is, the pesticide (stock solution) is put into a 100-liter container that does not react with the pesticide and has a low gas permeation rate of the pesticide, and air is added to prepare a pesticide vapor of a certain concentration, and air gas containing the pesticide flows. As for the gas, two glass cells are engaged with each other, and a plastic film for evaluating an exterior material to be evaluated is sandwiched between the cells. One has a structure in which gas can flow and the other can sample gas passing through the film after a certain period of time.

[0012] The water vapor transmission rate is 10.
0 g / m ² · day · atm (38 ° C., 90% RH) or less, preferably 1.0 g / m ² · day · atm (38
° C, 90% RH) or less, more preferably 0.1 g / m ²
It is desirable to be less than or equal to day.atm. In addition,
The method of measuring the moisture permeability will be described later. The reason why the moisture permeability is important is that if the humidity inside the exterior material is not kept constant, the formulation may react with water (moisture) and cause deterioration, and the humidity inside the exterior material is 5 to 25% ( It has been found that if the temperature can be kept at 20 ° C., 1 atm), more preferably 7 to 12% (20 ° C., 1 atm), deterioration can be prevented. Further, some preparations may be decomposed or reacted by light, so it is preferable to provide a light shielding material such as a metal layer or a black film on the exterior material.

[0013] Plastics having such properties are:
For example, polypropylene, polyethylene chlorofluoroethylene, polyethylene tetrafluoroethylene, ethylene vinyl acetate resin, polyethylene vinyl alcohol,
Polytetrafluoroethylene hexafluoropropylene, polystyrene, polyethylene, nylon, polyethylene terephthalate, polyamide, polyamideimide,
Polyarylate, polycarbonate, poly-3-fluoroethylene, polyetheretherketone, polyethylenenaphthalate, polyetherimide, polyethersulfone, polyimide, tetrafluoroethyleneperfluoroalkylvinylether, polyparabanic acid, polyphenylenesulfide, polysulfone, poly -4-Fluoroethylene, polyvinyl acetate, polyvinyl chloride, polyvinyl fluoride, polyvinylidene chloride (PVDC), polyvinylidene fluoride, polybutylene terephthalate, iomer resin, polyacrylonitrile (PAN), polyester, polymethyl methacrylate, polyurethane , Polybutadiene, poly-4-methylpentene, cellulose acetate resin, ethyl cellulose resin, polyvinyl alcohol, polylactic acid and ABS, and the like. And it is preferable to use it as a film. Among them, vinylidene chloride (PVD), which has high gas barrier properties of pesticides and low moisture permeability
C), ethylene-vinyl alcohol copolymer (EVO
H), it is preferable to use a polyacrylonitrile (PAN) film.

If necessary, the above-mentioned plastic film may be laminated by using an adhesive or coated with a resin to form a multilayer, or a metal layer may be bonded to the above-mentioned plastic film, or a sputtering method or an electron beam evaporation method. Such as physical vapor deposition, CVD (Chemical Vapor
It is also possible to use those formed by using a chemical vapor deposition method such as Deposition. Polyethylene (PE) to further improve the mechanical strength of the exterior material and further improve moisture permeability
It is preferable to use a material obtained by bonding polypropylene, polypropylene (PP), or polyethylene terephthalate (PET) to the above-described PVDC, EVOH, or PAN film.

Further, it is also an effective means to improve the gas barrier property of the film against the pesticide by stretching the polymer alloy with a resin having a high gas barrier property against the pesticide or by stretching the resin. It is also possible to use a film (Selar OH Plus: manufactured by DuPont) in which mica is thinly oriented in a flat plate shape and gas barrier properties are improved by a microlayer alloy using a torchous path (Torchous Path).

The metal layer can be formed on a plastic film by physical vapor deposition or chemical vapor deposition in addition to adhesion. An advantage of forming the metal layer by a physical vapor deposition method or a chemical vapor deposition method is that the thickness of the metal layer can be reduced. In order to improve the gas barrier properties of agricultural chemicals or the permeability of water, an extremely thin metal layer may be formed on the above-mentioned plastic film. Therefore, it is costly to form a metal layer by physical vapor deposition or chemical vapor deposition. This is also advantageous.

For example, an electron beam evaporation method, a sputtering method as a physical evaporation method, and a CVD method as a chemical evaporation method.
(Chemical Vapor Deposition)
As the metal to be deposited, for example, manganese, magnesium, titanium, zirconium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten,
Metals such as iron, cobalt, cadmium, nickel, ruthenium, rhodium, palladium, platinum, copper, silver, gold, zinc, indium, hafnium, gallium, germanium, aluminum, silicon, tin, lead, carbon, tellurium, yttrium, etc. Semiconductors. Further, these metals may be used alone or as an alloy composed of a plurality of metals. Further, oxides and nitrides of these metals may be used, and other elements may be included as constituents.

When a plastic film is used, the gas permeation rate of the pesticide decreases in proportion to the thickness. However, if it is too thick, it tends to be physically hard and difficult to handle, which is not preferable. On the other hand, if it is too thin, not only the gas permeation rate will increase as described above, but also the physical strength will decrease, and it will not be used as an exterior material. Therefore, the thickness of the film used in the present invention is preferably about 10 to 1000 μm,
About 30 to 100 μm is more preferable.

Hereinafter, chlorpicrin will be specifically described as an example of a pesticide volatile at room temperature which can be used in the present invention. The chlorpicrin formulated in the present invention can be used without limitation as long as liquid chlorpicrin is not substantially fluidized. Regarding this, many proposals have already been made, and
No. 2301, JP-A-59-82303, JP-A-63-230602, JP-A-01-17230
No. 2, JP-A-6-345605 and the like. Specifically, for example, chlorpicrin mixed with a gelling agent to form a gel, a powdered or granular solid carrier for solidification, an oil-absorbing polymer-absorbed one, and a package of these Examples thereof include a unit which is packaged with a water-soluble film for each unit, and more simply, a unit in which liquid chloropicrin is sealed in a bag-like or container-like water-soluble film in a liquid state. Above all, a mixture of ultrafine silica and chlorpicrin and gelled,
Alternatively, a chloropicrin oil-absorbed carrier such as starch or the like, or an inner package formed by covering these with a water-soluble film or the like, is friendly to the global environment and excellent in safety of the formulation. Among them, chlorpicrin is difficult to be adsorbed on soil particles and has high oil absorption ability.When applied to soil, the active ingredient of the formulation is released quickly to the soil, the carrier dissolves in water after application, and is degraded by microorganisms in the soil. Partially decomposed products of starch having a property of being easily processed are particularly excellent. As the water-soluble film, polyvinyl alcohol or water-soluble paper is preferably used.

The content of chlorpicrin in the chlorpicrin formulated in the present invention is not limited, and a chlorpicrin content of 5 to 99% by weight is preferably used.
In addition, there is no problem even if other pesticide components are mixed in the formulated chlorpicrin.

The shape of the chlorpicrin formulated to form the inner package in the present invention is not limited, and the inner package packaged with a water-soluble film is exemplified by a rectangle, a cylinder, a sphere, and the like. A tape-shaped unit in which a plurality of packaging units are connected in a straight line or a plane is preferably used because the application operation can be simplified. The inner package of the agricultural chemical formulation referred to in the present invention also means such a product.

When chlorpicrin is used as an agrochemical, the above-mentioned stainless steel container as an exterior material hardly reacts with chlorpicrin, so that it can be used as a sealed storage and distribution container.

When a container or bag made of a plastic film is used as an exterior material, the chloropicrin gas permeation rate is measured as described below as described above. That is, at room temperature (20 ° C.) and a relative humidity of 50%, a chlorpicrin stock solution is placed in a 100 liter Tedlar bag,
Inject air to prepare a certain concentration of chlorpicrin vapor,
An air gas containing chlorpicrin is passed. As for the gas, two glass cells are engaged with each other, and a plastic film to be evaluated is sandwiched between the cells. One has a structure in which gas can flow and the other can sample gas passing through the film after a certain period of time.

FIG. 1 shows a schematic diagram of a measuring apparatus. In FIG. 1, 1 is a Tedlar bag containing a chlorpicrin stock solution, 2 is a glass cell for chlorpicrin distribution, 3
Is a glass cell for sampling, 4 is a plastic film to be evaluated, 5 is a pump for gas flow, 6 is a Teflon tube, and 7 is a thermostat for measuring the permeation rate under constant conditions. After a certain time, gas is sampled,
The gas was absorbed in methanol, and the absorption liquid was analyzed by high performance liquid chromatography (HPLC). HPLC
The measurement conditions are as follows: Shimadzu LC-6A (use model), YMC-
AM-312-120A-ODS-S-5 (used column), the flow rate was 1.0 ml / min, and the mobile phase used was a mixture of methanol, water and acetonitrile at a ratio of 2: 4: 4. When evaluated under such conditions, the aforementioned polypropylene, polyethylene chlorofluoroethylene,
Polyethylene tetrafluoroethylene, ethylene vinyl acetate resin, polyethylene vinyl alcohol, polytetrafluoroethylene hexafluoropropylene, polystyrene, polyethylene, nylon, polyethylene terephthalate, polyamide, polyamide imide, polyarylate, polycarbonate, poly-3-fluoroethylene, poly Ether ether ketone, polyethylene naphthalate, polyether imide, polyether sulfone, polyimide, tetrafluoroethylene perfluoroalkyl vinyl ether, polyparabanic acid, polyphenylene sulfide, polysulfone, poly-4-fluoroethylene, polyvinyl acetate, polyvinyl chloride , Polyvinyl fluoride, polyvinylidene chloride, polyvinylidene fluoride, polybutylene terephthalate , An ionomer resin, polyacrylonitrile, polyester, polymethyl methacrylate, polyurethane, polybutadiene, poly-4-methylpentene, cellulose acetate resin, ethyl cellulose, polyvinyl alcohol, polylactic acid, ABS, and the like. Do you get it.

Among them, for example, polyethylene has a thickness of 2
The gas permeation rate is 66 g / m ² · hr,
It is 46 g / m ² · hr for a thickness of 0 μm and 21 g / m ² · hr for a thickness of 50 μm. A polyethylene film of such a thickness cannot be used alone as an exterior material of a chloropicrin preparation. (20μ
m) / nylon (30 μm) / polyethylene (20 μm)
m), the chlorpicrin gas permeation rate is 0.08 g / m ² · hr
It turns out that it becomes possible to use it as an exterior material of a chlorpicrin preparation. As described above, in order to reduce the gas permeation rate of chloropicrin, it is possible to laminate two or more kinds of films and use them as needed, or to laminate and use a metal layer with the above-mentioned plastic film.

For example, ethylene vinyl alcohol copolymer (EVOH) or polyvinylidene chloride (PVD)
C), polyacrylonitrile (PAN), nylon, etc. have low water vapor transmission rate and chloropicrin gas transmission rate,
Particularly preferred. Such a film can be used more effectively by forming a multilayer with a polyolefin-based film such as polypropylene.

For example, polyethylene (20 μm) / nylon (30 μm) / polyethylene (20 μm), or polyethylene (20 μm) / EVOH (40 μm) / polypropylene (40 μm), or polyethylene (40 μm)
μm) / PVDC (30 μm) / polyethylene (20 μm)
m) or polypropylene (40 μm) / PAN (2
A package (outer package) is formed using a plastic film laminated using three films such as 0 μm) / polyethylene (20 μm).

Depending on the properties of the preparation, there may be cases where physical properties required for the outer packaging material are present in addition to the gas permeation rate of the active ingredient of the pesticide. For example, in an inner package of a chlorpicrin preparation coated with a water-soluble film such as PVA, the permeation rate of water that affects the solubility of the PVA film is important in addition to the permeation rate of chlorpicrin gas.

[0029] Immediately after the preparation of the preparation, there is no leakage of the contents. Even if the active ingredient is released immediately after application, when the preparation is preserved, the leakage of the contents may occur due to the water permeability of the exterior material. May occur.

The present inventors have found that the moisture permeability of the exterior material is 10.0
g / m ² · day · atm (38 ° C., 90% RH: AS
Below, preferably 1.0 g / m ² · day · atm, more preferably 0.1 g / m ² · day · atm, if it is a dissolution of the PVA film described above. Has been found to prevent leakage of contents.

When preserving the inner package of a preparation packaged with PVA, the present inventors also control the humidity inside the exterior material (the atmosphere outside the inner package), which is extremely important for the storage stability of the preparation. I found something. That is, the humidity inside the exterior material is 5 to 25% (20 ° C., 1 at
m), more preferably 7 to 12%, improved storage stability of the preparation. In order to keep the humidity inside the exterior material within the above-mentioned range, for example, the environmental humidity at the time of enclosing the preparation (inner package) in the exterior material is kept within the above-mentioned range or slightly lower than that. That water permeability is as low as possible, that is, a material whose water content is kept within the above-mentioned range, that multiple packaging materials are used to reduce water permeability, and that multiple packaging is used, For example, silica gel or the like is put therein.

When a plastic film is used, deep drawing can be performed by using a sheet having a large film thickness. For example, BAREX (trade name) (manufactured by Mitsui Toatsu Chemicals, Inc.), which is a polyacrylonitrile (PAN) -based thermoplastic resin, is excellent in moldability, so that a pharmaceutical package packaged with PVA can be continuously prepared. A roll-shaped preparation obtained by winding the connected ribbon-shaped preparation on a reel may be a deep-drawn BAREX container as an exterior material. Such a BAREX container can be suitably used because it has high strength as an exterior material as well as high gas barrier properties and low moisture permeability to pesticides.

Further, the evaluation of the transmission speed of the plastic film used in the present invention has a great influence on the temperature. For example, when the temperature is increased to 30.degree. C., the transmission speed may be increased twice or more.

[0034]

The present invention will be described more specifically with reference to the following examples. Chlorpicrin stock solution (manufactured by Mitsui Toatsu Chemicals, purity: 99.5%) (3.0 g) was placed in a 5 × 5 cm square bag made of polyvinyl alcohol film KA40 (manufactured by Aicello Co., Ltd.), and heat-sealed to form a chlorpicrin agent package. Obtained. This was designated as formulation A.

Chlorpicrin stock solution (manufactured by Mitsui Toatsu Chemicals, Inc .:
0.5 g of a 20% dimethylformamide solution of dibenzylidene sorbitol was added to 3.0 g of pure 99.5%) and gelled.
Put it in a 5 x 5 cm square bag made by
Heat sealing was performed to obtain a chlorpicrin agent package. This was designated as formulation B.

Chlorpicrin stock solution (manufactured by Mitsui Toatsu Chemicals, Inc .:
2.5 g of dextrin (Max 1000, manufactured by Matsutani Chemical Co., Ltd.) was added to 3.0 g of 3.0 g (purity: 99.5%) and kneaded. The mixture was placed in a 4 × 15 cm square bag made of polyvinyl alcohol film KA40 (manufactured by Aicello), and heated. It sealed and obtained the chlorpicrin agent package. This was designated as formulation C. Twelve preparations C were connected in the longitudinal direction to obtain a tape-like preparation having a total length of about 500 cm. In addition, Formulation C and Formulation C are connected by a PVA film containing nothing. Formulation D
And

Example 1 Polyethylene (20 μm) /
Nylon (30 μm) / polyethylene (20 μm)
20 cm × 20 cm using a plastic film having a layer structure (gas permeation rate is 0.08 g / m ² · hr)
, Each containing 60 chloropicrin preparations (inner packaging) (5 preparations D connected to 12 pills), and heating and melting the plastic film. And sealed to form an outer package. Thereafter, the chlorpicrin odor coming out through the sealed plastic film was examined, and the results are shown in [Table 1]. The chlorpicrin odor was judged as ○ when no chloropicrin odor was felt, Δ when slight chloropicrin odor was felt, and × when odor was slightly strong. It should be noted that there is no commercial value at all even for △.

Example 2 Polyethylene (40 μm) /
A plastic film (gas permeation rate 0.05 g / m ² · hr) laminated using three films of Zeklon (trade name, 30 μm: PAN film manufactured by Mitsui Toatsu Chemicals, Inc.) / Polypropylene (40 μm) is used. 20c
Four mx20 cm bags were prepared, and each of them contained 60 chloropicrin preparations (inner package) of A to D (5 preparations in which 12 preparations were connected to each other), and a plastic film was prepared. It was melted by heating and sealed to form an outer package.
Thereafter, the chlorpicrin odor coming out through the sealed plastic film was examined, and the results are shown in [Table 1].
The chlorpicrin odor was judged as ○ when no chloropicrin odor was felt, Δ when slight chloropicrin odor was felt, and × when odor was slightly strong.

Example 3 Sixty chlorpicrin preparations (A to D) were placed in four 1-liter stainless steel containers with lids (5 preparations D were connected to 12 pills), and the lids were closed. An outer package was used. Thereafter, the chlorpicrin odor coming out through the sealed stainless steel container was examined in the same manner as in Example 1, and the results are shown in [Table 1].

Example 4 A thin film of aluminum (50 nm) was formed on a plastic film having a single-layer structure of polyethylene (50 μm) by electron beam evaporation to form a film (gas permeation rate: 0.1 g / m ² · hr). Using this, four 20 cm × 20 cm bags were prepared and evaluated in the same manner as in Example 1, and the results are shown in [Table 1]. The chlorpicrin odor was judged as ○ when no chloropicrin odor was felt, Δ when slight chloropicrin odor was felt, and × when odor was slightly strong.

[Comparative Example 1] A plastic film having a single-layer structure of polyethylene (50 μm) was used for 20 c
Four bags of mx 20 cm were prepared and evaluated in the same manner as in Example 1, and the results are shown in [Table 1].

[0042]

[Table 1]

Example 5 Example 1, 3 and Comparative Example 1
Each of the plastic films was used as an exterior material 1 and an exterior material.
2, and exterior material 3. These outer materials 1, 2, and 3
ASTME-96 (38 ° C., 90% RH)
0.8 g / m^Two・ D
ay.atm, 0.1g / m^Two・ Day ・ atm 、 2
0.0 g / m ^Two* Day * atm. Outside these
20cm x 20cm bag using materials 1, 2 and 3
Prepare 4 sheets each, and add chlorpicrin of A to D
60 preparations each (12 preparations were connected
5 pieces) and heat and melt the plastic film
And sealed. The temperature and humidity of the room at that time were 20 ° C,
7.0%. After that, the temperature was set to 20 ° C and the humidity was set to 50%
After leaving it in the room where it was kept for one month, the exterior material plastic
Open the chlorpicrin preparation and examine the form,
The results are shown in [Table 2]. Chlorpicrin preparation after opening
○, PVA form that has not changed, ○, PV
A where A is slightly softened, and PVA is softened and
If some of them melt and the irritating odor of the formulation inside can be felt ×
And

[0044]

[Table 2]

Example 6 20 preparations D were connected and 1
A 00 m chlorpicrin formulation was made. This was wound up on a reel to prepare a cylindrical roll-shaped chloropicrin preparation (inner package) having a diameter of 33 cm and a height of 20 cm. B
AREX (manufactured by Mitsui Toatsu Chemicals Co., Ltd.) was deep drawn to prepare a cylindrical container (outer package) having a diameter of 34 cm, a height of 21 cm, and a thickness of 0.3 mm, and a roll-shaped chlorpicrin preparation was placed therein and sealed. (Deep drawing) to form an outer package. Thereafter, the odor of chlorpicrin that was emitted through the outer package formed of the sealed BAREX container was examined. As a result, no chlorpicrin odor was felt. Also,
The rolled chlorpicrin preparation packaged in this manner did not show any weight loss even after being left at 40 ° C. for one year, and no deterioration of the preparation was observed.

[0046]

Industrial Applicability According to the present invention, there has been obtained an exterior material for an agricultural chemical formulation which is capable of storing a volatile agricultural chemical formulation (inner package) at room temperature with reduced volatility and distributing it generally. By forming the outer package in which the pesticide formulation (inner package) is housed and sealed in such an outer material, the pesticide active ingredient is not leaked to the outside, and is safe and excellent in storage stability even in the distribution / transportation process. An outer package of the pesticide formulation could be provided.

[Brief description of the drawings]

FIG. 1 is an explanatory view of an apparatus for measuring a chlorpicrin permeation rate.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Tedlar bag containing chlorpicrin stock solution 2 Glass cell for chlorpicrin circulation 3 Glass cell for sampling 4 Plastic film to be evaluated 5 Gas circulation pump 6 Teflon tube 7 Constant temperature bath

 ──────────────────────────────────────────────────の Continuing on the front page (72) Inventor Hitoshi Shimodori 1144 Togo, Mobara-shi, Chiba Mitsui Toatsu Chemicals Co., Ltd.

Claims (26)

[Claims] Claims 1. An exterior material for forming a container or bag for accommodating and sealing an inner package of a pesticide having reduced volatility by formulating a pesticide having volatility at room temperature, An exterior material for an agricultural chemical, wherein the exterior material is made of plastic. 2. Moisture permeability is 10.0 g / m ² · day · a
The exterior material according to claim 1, wherein the exterior material is not more than tm (38 ° C, 90% RH). 3. The exterior material according to claim 1, wherein the humidity inside the exterior material forming the container or the bag can be maintained at 5 to 25% (20 ° C., 1 atm). 4. The plastic film according to claim 1, wherein the plastic is a plastic film excellent in corrosion resistance at a gas permeation rate of a pesticide of 5.00 g / m ² · hr or less at room temperature. The packaging material for an agricultural chemical formulation according to any one of the above. 5. The exterior material according to claim 4, wherein vinylidene chloride (PVDC) is used as the plastic film. 6. A plastic film comprising ethylene.
The exterior material according to claim 4, wherein a vinyl alcohol copolymer (EVOH) is used. 7. The exterior material according to claim 4, wherein polyacrylonitrile (PAN) is used as the plastic film. 8. The exterior material according to claim 4, wherein a plastic film is bonded to form a multilayer. 9. The exterior material according to claim 4, wherein a plurality of plastic films are laminated. 10. The exterior material according to claim 4, wherein a metal layer is further laminated with a plastic film. 11. A container for accommodating and sealing an inner package of an agricultural chemical having reduced volatility by formulating an agricultural chemical having volatility at room temperature is made of a metal having excellent corrosion resistance. Exterior materials for agricultural chemical formulations. 12. The cladding material according to claim 11, wherein the metal is stainless steel. 13. The pesticide which is volatile at room temperature is characterized by being one or a combination of two or more of chloropicrin, 1,3-dichloropropene, dichlorodiisopropyl ether and methyl isothiocyanate. The exterior material according to any one of claims 1 to 12. 14. An inner package of a pesticide formulation having reduced volatility by formulating a pesticide having volatility at room temperature is enclosed in an exterior material forming a plastic container or bag and sealed. Outer package of pesticide formulation. 15. The exterior material having a moisture permeability of 10.0 g / m ² ···
15. The outer package according to claim 14, wherein the temperature is not more than day · atm (38 ° C., 90% RH). 16. The outer package according to claim 14, wherein the humidity inside the outer package forming the outer package can be maintained at 5 to 25% (20 ° C., 1 atm). 17. The coating material according to claim 14, wherein the exterior material is a plastic film excellent in corrosion resistance at a gas permeation rate of a pesticide of 5.00 g / m ² · hr or less at room temperature. An outer package of the pesticide preparation according to any one of the above. 18. The method according to claim 1, wherein vinylidene chloride (PVDC) is used as the plastic film.
7. The outer package according to 7. 19. The outer package according to claim 17, wherein an ethylene-vinyl alcohol copolymer (EVOH) is used as the plastic film. 20. The outer package according to claim 17, wherein polyacrylonitrile (PAN) is used as the plastic film. 21. The outer package according to claim 17, wherein a plastic film is bonded to form a multilayer. 22. The outer package according to claim 17, wherein a plurality of plastic films are laminated. 23. The outer package according to claim 17, wherein the metal layer is further laminated with a plastic film. 24. A container made of a pesticide which has volatility at room temperature and which has a reduced volatility obtained by formulating the pesticide and containing the hermetically sealed inner container, wherein the container is made of a metal having excellent corrosion resistance. An outer package of a pesticide formulation characterized by the above-mentioned. 25. The outer package according to claim 24, wherein the metal is stainless steel. 26. A pesticide which is volatile at room temperature is one of chlorpicrin, 1,3-dichloropropene, dichlorodiisopropyl ether and methyl isothiocyanate.
The outer package according to any one of claims 14 to 25, wherein the outer package is a combination of two or more species.