JPH11139903A - Insecticide - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an insecticide which keeps the excellent insecticidal activity of a pyrethroid volatile at ordinary temperature, possesses no anxiety of contamination and copper degeneration caused by the contact with medicines and is functionally novel. SOLUTION: This insecticide is an insecticide that the inorganic or organic substrate containing a pyrethroid volatile at ordinary temperature is enclosed in the plastic film pouch which possesses many pores with a pore diameter of 0.02-2.0 mmϕ all over the surface in a proportion of 0.005-0.3 as the ratio of the whole pore area to the film area.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an insect repellent containing a volatile volatile pyrethroid.

[0002]

2. Description of the Related Art Various insect repellents are commercially available for controlling insect pests that inhabit households, especially clothing pests such as Iga, Koiga, Himematsu-obushi, Himemaruka-obushi. As these insect repellents, conventionally, sublimable insect repellents such as paradichlorobenzene, naphthalene and camphor have been mainly used.However, due to problems such as insect repellent efficacy, in recent years, room-temperature volatile pyrethroids such as empentrin have been used. Insect repellents have become widespread. For example, empentrin is
It shows higher insect repellent activity and pest control effect than p-dichlorobenzene against clothing pests, and is sufficiently effective at low doses, but discolors or deteriorates by affecting surrounding metals (especially copper compounds). (Hereinafter, referred to as “copper change”). Therefore, in this insect repellent containing empentrin,
Various forms have been proposed from the viewpoint of the amount of volatilization necessary for achieving the insect repellent effect and avoiding copper discoloration.

[0003] As one of them, there is one in which an insect repellent mat is stored in a plastic case, which can be said to be effective as a method for preventing copper discoloration, but it is undeniable that the cost is somewhat increased.
On the other hand, some proposals have been made to package the drug-impregnated body with a nonwoven fabric or the like. For example, Japanese Patent Application Laid-Open No. 63-101301 discloses that an impregnated body containing a room-temperature volatilizable drug as a main component and containing a colored or temporally discolorable drug composition has a basis weight of 35 to 70 g / m ² . A drug package packaged with a nonwoven fabric made of synthetic fiber is disclosed. Although it is said that by specifying the basis weight of the nonwoven fabric, it can secure the amount of volatilization and prevent contamination by contact.
Copper transformation due to empentrin cannot be avoided. Japanese Unexamined Utility Model Publication No. Hei 6-65402 discloses an evaporant pack that stores a plurality of impregnated evaporating liquids in a granular holder in which an inorganic powder is added to and mixed with an absorbent material. No consideration is given to copper transformation by empentrin. Thus, no insecticide containing room temperature volatile pyrethroids, particularly empentrin, which has been satisfactory in all respects, has yet been proposed.

[0004]

DISCLOSURE OF THE INVENTION The present invention provides a novel insect repellent which retains the excellent insect repellent activity of a normal-temperature volatile pyrethroid, particularly empentrin, and is free from contamination or copper discoloration due to chemical contact. It is intended to provide an agent.

[0005]

Means for Solving the Problems In order to solve the above problems, the present inventors have conducted intensive studies and as a result, have found that
The present inventors have found that a desired insect repellent can be obtained by encapsulating in a plastic film bag having a large number of holes with a specific hole diameter and a specific hole area ratio, and completed the present invention.

That is, according to the first aspect of the present invention, an inorganic or organic carrier containing a normal-temperature volatile pyrethroid is prepared by adding a porous material having a pore size of 0.02 to 2.0 mmφ and a large number of pores over almost the entire surface. 0.005 as area ratio
The present invention relates to an insect repellent enclosed in a plastic film bag pierced at a rate of about 0.3.

The volatile volatile pyrethroid used in the present invention includes 1-ethynyl-2-methyl-2-pentenyl-
Chrysanthemate (Empentrine), 1-ethynyl-
2-methyl-2-pentenyl-2,2-dimethyl-3-
(2,2-dichlorovinyl) cyclopropane-1-carboxylate (hereinafter, referred to as “compound A”), 1-ethynyl-2-methyl-2-pentenyl-2,2,3,3
-Tetramethylcyclopropanecarboxylate, 1-
Ethynyl-2-fluoro-2-pentenyl-2,2-dimethyl-3- (2,2-dichlorovinyl) cyclopropane-1-carboxylate, 5-propargyl-2-furylmethyl-2,2,3,3- Tetramethylcyclopropanecarboxylate (teframethrin), 2,3
5,6-tetrafluorobenzyl-2,2-dimethyl-
3- (2,2-dichlorovinyl) cyclopropane-1-
Carboxylates (transfluthrin), 2,3
4,5,6-pentafluorobenzyl-2,2-dimethyl-3- (2,2-dichlorovinyl) cyclopropane
Examples include, but are not limited to, 1-carboxylate (fenfluthrin). In the case where there is an optical isomer based on an asymmetric carbon or a geometric isomer due to a double bond in the chemical structure, each of the isomers alone,
Of course, any mixtures are encompassed by the present invention. Among the pyrethroids, empentrin is easy to use in terms of insect repellency, availability, and the like.However, for pyrethroids having a 1-ethynyl-2-pentenyl moiety as an alcohol moiety, consideration is generally given to preventing copper deterioration as described above. Need.

The present invention provides, in addition to a normal-temperature volatile pyrethroid as an insect repellent component, other pyrethroids such as allethrin, framethrin and phenothrin, peat such as diet and dimethyl phthalate, hinokitiol, as long as the characteristics of the invention are not impaired. Antibacterial fragrances such as linalool, citronellol and eugenol, o-phenylphenol, p-chloro-m-xylenol, 3-methyl-4-
Multipurpose insect repellents can also be prepared by appropriately blending fungicides such as isopropylphenol and allyl isothiocyanate, antimicrobial agents, other deodorants, fragrances, stabilizers, coloring agents and the like.

In the present invention, the inorganic or organic carrier for holding the volatile volatile pyrethroid includes inorganic porous carriers (silicate, silica, zeolite, alumina, etc.), paper, pulp, and organic polymer carriers (cellulose, polyethylene, etc.). Polypropylene, polyvinyl alcohol, ethylene-vinyl acetate copolymer, etc.), gelling carrier (carrageenan, gelatin, alginic acid, etc.), sublimable carrier (adamantane,
Cyclododecane, norbornane, etc.)
One or more of these can be used in combination, and can be used in dosage forms such as granules, powders, tablets, mats, and sheets. Among these inorganic or organic carriers, paper, pulp, and cellulosic carriers are preferred from the viewpoints of productivity and incineration after use, recovery, regeneration, landfill, and the like. Cellulose porous particles are most preferred in that they can more effectively have an indicator function.

Japanese Patent Application Laid-Open No. Sho 48-60753 discloses a method for obtaining porous cellulose particles of 16 to 170 mesh by discharging viscose in the form of droplets and solidifying and regenerating the viscose. Japanese Patent Application Laid-Open No. Sho 64-43530 discloses a hollow cellulose fine particle having an apparent density of 0.4 g / cm ³ or less and a large void in a substantially central portion of 16 to 170 meshes. A method for producing cellulose porous spherical particles having a large number of pores of 2 μm or more and having a continuous pore structure communicating with each other has been disclosed by cooling and freezing the droplets below the solidification temperature and removing the solvent thereafter. JP-A-60-155245, which becomes cellulose porous particles if saponified.
Japanese Patent Application Laid-Open No. 3-231942 discloses a method for producing porous cellulose acetate particles by discharging viscose and calcium carbonate from a nozzle in the form of droplets to simultaneously perform coagulation regeneration and acid decomposition by calcium carbonate. Methods for producing cellulose particles are disclosed respectively. Cellulose sponge is also known as a large-diameter cellulose structure.
8 mmφ cellulose particles are preferred in terms of workability and coloring of the indicator.

The present invention provides a packaging material for enclosing a drug-impregnated body, which has a pore diameter of 0.02 to 2.0 mmφ and a large number of pores covering almost the entire surface as a ratio of the total perforated area / film area of 0.005 to 0. It is characterized by employing a plastic film bag pierced at a ratio of 0.3. In the prior art relating to packaging materials, emphasis has been placed on securing the volatilization amount of insect repellent components and preventing contamination due to contact (meaning spots due to exudation of chemicals and not copper deformation). 10
No. 1301 discloses that the basis weight of the nonwoven fabric is 35 to 70 g /
m ^2, and Japanese Utility Model Application Laid-Open No. 6-65402 attempts to improve the impregnation by impregnating the evaporating liquid with a particle-shaped holding body obtained by adding and mixing an inorganic powder to a liquid absorbing material. Nothing was resolved. This is presumably because a non-porous plastic film having a small thickness or a nonwoven fabric or Japanese paper having pores of generally 10 μm or less occupying the entire surface, even if it has holes, was used. However, the present inventors have proposed that a large number of pores having a diameter of 0.02 to 2.0 mmφ, preferably 0.05 to 1.0 mmφ, and a ratio of the total perforated area / film area of 0.005 to 0.3. It has been found that by employing a plastic film bag with a hole, it is possible to ensure the volatilization amount of the insect repellent component, prevent contamination due to contact, and also avoid copper transformation, and have accomplished the present invention.

Although the plastic film may be made of various materials, it is made of one or more plastic materials selected from polypropylene, polyethylene, polyester, polyamide, polyurethane and polyacryl, which do not have a high affinity for drugs. Those are preferred, and among them, polypropylene and polyester which may be laminated with polyethylene or the like are suitable. As long as the characteristics of the present invention are not impaired, a film in which paper and / or nonwoven fabric such as pulp, rayon or viscose are laminated on the upper surface of a plastic film may be used.
The thickness of the plastic film is 10 to 200.
μ, preferably 15 to 70 μ, is appropriate, and the pore diameter and the perforated area ratio can be appropriately determined in consideration of the volatilization amount according to the use of the normal-temperature-volatile pyrethroid.

According to a second aspect of the present invention, in the insect repellent of the first aspect, an inorganic or organic carrier containing a normal-temperature volatile pyrethroid is provided with an indicator for indicating an end point of the volatilization of the pyrethroid.

According to a third aspect of the present invention, in the insect repellent of the first aspect, an inorganic or organic carrier holding an indicator for indicating the end point of volatilization of the normal-temperature volatile pyrethroid is enclosed together.

Indicators applicable to insect repellents include electron-donating color formers (triphenylmethane-phthalide dyes, fluoran dyes, etc.), electron-accepting color developers (bisphenols, etc.), and volatile desensitizing substances (esters). And amides), a volatile layer impregnated with a colored layer and an oil-permeable ground color layer containing a low-refractive-index pigment develops and decolors due to a change in the refractive index. Those whose color change is clear and linked with the residual amount of the volatile drug are suitable.

According to a fourth aspect of the present invention, there is provided the insect repellent according to the first aspect, wherein an inorganic or organic carrier containing a normal-temperature volatile pyrethroid and an inorganic or organic carrier containing an indicator or a normal-temperature volatile pyrethroid and an indicator are mixed. It is.

A fifth aspect of the present invention is the insect repellent according to the first, second, third or fourth aspect, wherein the normal-temperature-volatile pyrethroid is empentrin, and the cellulose or porous particles are used as an inorganic or organic carrier.

The invention according to claim 6 is the invention according to claims 1, 2, 3, 4
Alternatively, in the insect repellent according to 5, the plastic film bag is made of one or more plastic materials selected from polypropylene, polyethylene, polyester, polyamide, polyurethane and polyacryl.

[0019]

According to the first aspect of the present invention, a drug carrier containing a normal-temperature volatile pyrethroid is sealed in a plastic film bag having a large number of holes with a specific pore diameter and a specific pore area ratio. , Ensuring the volatilization of insect repellent components,
An insect repellent is provided which can prevent copper contamination as well as preventing contamination by contact. The size and shape of the plastic film bag can be arbitrarily determined according to the application. In producing the present insect repellent, the drug carrier is sealed in a plastic film bag and then sealed by means such as heat sealing. Usually, a plurality of the plastic film bags are hermetically sealed and stored in a non-breathable bag.

According to the second or third aspect of the present invention, since the indicator for indicating the end point of volatilization of the normal-temperature volatile pyrethroid is retained, the end point of the insect repellent effect can be clearly known by the change in color tone. The color of the indicator can be arbitrarily selected in consideration of the transparency and decorativeness of the plastic film bag, and the indicator may be one that is held alone on an inorganic or organic carrier, or may be a normal-temperature volatile pyrethroid. In addition, those held on an inorganic or organic carrier may be used.

According to the fourth aspect of the present invention, the inorganic or organic carrier containing the normal-temperature volatile pyrethroid and the inorganic or organic carrier containing the indicator or the normal-temperature volatile pyrethroid and the indicator are mixed, so that the indicator function is more accurate. In addition, an insect repellent to which a decorative property is added can be obtained.

According to the fifth aspect of the present invention, empentrin is selected as a normal-temperature volatile volatile pyrethroid, and cellulose porous particles are selected as an inorganic or organic carrier, so that it is more excellent in performance, easy to use, and more functionally novel insect repellent. An agent is provided.

According to the invention of claim 6, one or two or more plastic materials selected from polypropylene, polyethylene, polyester, polyamide, polyurethane and polyacryl are selected as the material of the plastic film bag. And pollution prevention by contact,
A more useful insect repellent is provided in terms of prevention of copper deterioration.

The insect repellent of the present invention thus obtained is stored in a drawer, a closet, a clothes box, or the like to control pests inhabiting the home, especially clothing pests such as iga, kiga, himekabushiobushi and himemarukabushibushi. Used for The application rate of the insect repellent is not particularly limited. However, in order to maintain the insect repellent effect for usually 6 to 8 months, the temperature is 0.1 vol.
It is appropriate to apply between 02 and 0.2 g.

[0025]

Next, the insect repellent of the present invention will be described in more detail based on specific examples and test examples of the present invention.

Embodiment 1 FIG. Cellulose porous particles having a sphere diameter of about 4 mm (manufactured by Rengo Co., Ltd., Biscopearl AZ-430)
0L) A leuco dye and bisphenol are supported on about 800 mg together with 50 mg of empentrin, and the particles are drawn into a stretched polypropylene film bag (pore diameter: 0.2 mm, total perforated area / film area ratio; 0.04, size: 3.5).
× 7.5 cm) to obtain an insect repellent. Clothing storage box with two blankets at the bottom (43 x 63 cm, height 13
cm) tatami paper containing copper and three insect repellents on it
Stored at room temperature 25 ° C. In this insect repellent, empentrin was volatilized uniformly at a rate of about 6 mg / month for 8 months, and after 8 months, there was no effect on the tatami paper, and the indicator changed color from white to blue.

Embodiment 2 FIG. Cellulose porous particles having a sphere diameter of about 4 mm (manufactured by Rengo Co., Ltd., Biscopearl AZ-430)
0L) Leuco dye and bisphenol are supported on about 500 mg together with 20 mg of empentrin, while the sphere diameter is about 2 mm.
Polyester film bag (pore diameter: 0.5 mm; pore size: 0.5 mm; two types of particles obtained by embedding 40 mg of empentrin in about 500 mg of cellulose porous particles (Visco Pearl AZ-2300L, manufactured by Rengo Co., Ltd.) Total pore area / film area ratio;
02, size: 4.5 × 8.0 cm) to obtain an insect repellent. When the insect repellent was used in a clothes case full of clothes, the clothes were not damaged by rushes, cutlet bugs, etc. during the display period of the indicator. The bead-type insect repellent was less likely to leave traces of the insect repellent on clothing than the conventional plastic case storage type insect repellent, and was easy to use. The cellulose porous particles having a sphere diameter of about 4 mm
g is loaded with leuko dye, bisphenol and a desensitizing substance, while two kinds of particles in which empentrin 60 mg is embedded in about 700 mg of the cellulose porous particle having a sphere diameter of about 2 mm are similarly useful. there were.

Test Example 1 Various insect repellents shown in Table 1 were prepared according to Example 1 and Example 2, and the following performance tests were performed. Table 1 also shows the results. (1) Food damage prevention test Four blankets were laid in a 50-liter drawer, and two insect repellents were placed thereon. After 6 months, remove the insect repellent,
Instead, a cylindrical cylinder containing five wigs was placed, and the state of damage to the blanket was observed for one week. In addition, the result of the damage situation was evaluated based on the following criteria. O: No damage at all. Δ: Very slight scratches. X: Damage is observed. (2) Copper discoloration test Put the wrapping paper printed with brass on the drawer with a capacity of 50 liters used in the above-mentioned corrosion prevention test, place the insect repellent on it, and observe the discoloration of the wrapping paper after 6 months. did. The results were indicated by symbols of ○, Δ, and ×. ○: almost no effect. Δ: slightly affected. X: Discoloration is remarkable.

[0029]

[Table 1]

As a result of the test, it was confirmed that the insect repellent of the present invention exhibited a high effect of preventing the damage to the food and copper, and was extremely excellent in terms of usability. On the other hand, a conventional control product, for example, a product in which pulp granules were sealed in a non-woven fabric bag (Control 1), could not avoid copper deformation due to empentrin. Further, a polypropylene film having no pores formed of cellulose porous particles (Control 2), and a porous film having a small perforated area ratio (Control 3).
With respect to the insect repellent encapsulated in a film having a large pore size and a large perforated area ratio (control 4), the volatilization performance of empentrin was inferior and did not show an anti-corrosion effect or could not suppress copper change. This has revealed the usefulness of the insect repellent of the present invention in which a number of holes having a specific pore diameter and a perforated area ratio are provided in the packaging material.

[0031]

According to the present invention, the excellent insect repellent activity of a normal-temperature volatile pyrethroid, particularly empentrin, is maintained.
It is possible to provide a novel insect repellent which is functionally free from the possibility of contamination or copper discoloration due to contact with a drug, and its practicality is extremely high.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Isao Tomoyasu, Inventor 1-8-10 Jiyugaoka, Kanazu-cho, Sakai-gun, Fukui Prefecture Inside Rengo Co., Ltd. Fukui Research Institute (72) Inventor Kinki Nakano 1 Jiyugaoka, Kanazu-cho, Sakai-gun, Fukui Prefecture No.8-10, Rengo Co., Ltd., Fukui Research Laboratory (72) Inventor Yoshihiro Nante 1-1-11, Ogurocho, Toyonaka City, Osaka Pref. Dainichi Honzogiku Co., Ltd. Central Research Laboratory (72) Inventor Toshio Takahashi, Toyonaka, Osaka Prefecture 1-11-11 Daikokucho, Daiichi Hon Pyroxermicum Co., Ltd. (72) Inventor Kazuki Ogura 1-11-1 Ogurocho, Toyonaka City, Osaka Prefecture Nihonhon Pyroxermic Co., Ltd.

Claims (6)

[Claims] An inorganic or organic carrier containing a normal-temperature volatile volatile pyrethroid, having a pore size of 0.02 to 2.0 mmφ,
An insect repellent, wherein a large number of pores are enclosed in a plastic film bag pierced over a substantially entire surface at a ratio of 0.005 to 0.3 as a total perforated area / film area ratio. 2. The insect repellent according to claim 1, wherein an inorganic or organic carrier containing a normal-temperature volatile pyrethroid has an indicator for indicating the end point of the volatilization of the pyrethroid. 3. The insect repellent according to claim 1, wherein an inorganic or organic carrier holding an indicator for indicating an end point of volatilization of the normal-temperature volatile pyrethroid is enclosed together. 4. The insect repellent according to claim 1, wherein an inorganic or organic carrier containing a normal-temperature volatile pyrethroid and an inorganic or organic carrier containing an indicator or a normal-temperature volatile pyrethroid and an indicator are mixed. 5. The inorganic or organic carrier containing a normal-temperature volatile pyrethroid is a cellulose porous particle containing empentrin.
Or the insect repellent according to 4. 6. The plastic film bag according to claim 1, wherein the plastic film bag is made of one or more plastic materials selected from polypropylene, polyethylene, polyester, polyamide, polyurethane and polyacryl. The insect repellent according to 4 or 5.