CN100339004C - Thermally volatile materials for pest control - Google Patents

Abstract

The invention provides a thermal volatilization material for controlling pests, wherein the volatilization end point of the active ingredient can be visually and accurately recognized, and has a long-lasting volatilization time of the active ingredient. The thermally volatile material for controlling pests has a carrier for the solution of the compound shown in the formula ( ¹ ), wherein R and ^R represent a hydrogen atom, a methyl group or a chlorine atom, and ^R represents a hydrogen atom, a fluorine atom, a methyl group, a methyl group, a methyl group, and a methyl group. Oxygen or methoxymethyl, polyalkylene terephthalate layer with holes on and covering the support, where the support is the base layer and the "improved layer that makes it transparent when containing an oily liquid" laminated material, and the polyalkylene terephthalate layer has a thickness of 0.002 to 0.3 mm.

Description

Thermally volatile materials for pest control

Technical field

The invention relates to a heat-volatile material for controlling pests that can be used for a long time, and a method for using the material to control pests.

Background technique

Conventionally, thermally volatile materials for controlling pests (so-called mosquito repellent mats) have been used for controlling pests such as mosquitoes and flies. This type of thermally volatile material for controlling pests has a fibrous carrier or the like, on which an insecticidal compound is carried, and is used by heating on a heating plate.

On the other hand, in the field of clothing mothproofing agents, through the discoloration of all or part of the mothproofing materials, it has been disclosed that the mothproofing materials have the ability to visually identify the end of volatilization of insecticidal compounds (such as JP4-36123B and JP8-73301B ).

In conventional thermally volatilizable materials for controlling pests, the time for volatilizing active ingredients by heating usually lasts about 8 hours, so thermally volatilizable materials for controlling pests with a longer volatilization time for active ingredients are required. In thermal volatilization materials for controlling pests with such a relatively long volatilization time of active ingredients, it takes a long time from the beginning of use to the end of volatilization of active ingredients, so it is particularly important to accurately identify the volatilization end point of active ingredients.

Contents of invention

The object of the present invention is to provide a heat volatilization material for controlling pests, the volatilization end point of the active ingredient can be visually and accurately recognized, and the volatilization time of the active ingredient is long-lasting.

That is to say, the present invention provides a kind of thermal volatilization material of pest control, it comprises the carrier of the solution of the compound shown in bearing formula (1):

wherein ^R1 and ^R2 each represent a hydrogen atom, a methyl group or a chlorine atom, and ^R3 represents a hydrogen atom, a fluorine atom, a methylmethoxy group or a methoxymethyl group, and a polyalkylene terephthalate layer with holes On and covering a carrier, where the carrier is a laminate of a base layer and an "improved layer that makes it transparent when oily liquid is contained," and the polyalkylene terephthalate layer has a thickness of 0.002 to 0.3 mm . The present invention also provides a method of controlling pests, the method comprising heating the above-mentioned thermally volatile material for controlling pests in the habitat or infested area of the pests.

When the heat volatilization material for controlling pests of the present invention is heated on a heating plate, the volatilization time of the active ingredient is prolonged, and the volatilization end time of the active ingredient almost coincides with the fading time of the volatilization material. More specifically, with the cover layer of polyalkylene terephthalate, the volatilization time of the active ingredient is prolonged, and due to the volatilization of the oily liquid, the "improved layer that becomes transparent when the oily liquid is contained" changes from transparent to The change of opacity can visually identify the volatilization end point of active ingredients.

Description of drawings

Accompanying drawing 1 is the specific cross-sectional schematic diagram of the thermal volatilization material for controlling pests of the present invention.

Detailed ways

As shown in accompanying drawing 1, in the thermal volatilization material for controlling pests of the present invention, the solution of the compound shown in the carrier formula (1) is carried on the carrier, and the carrier is the base layer 1 and "make it transparent when containing oily liquid The laminate composed of the improved layer "2, as well as the carrier, is covered with a layer 3 of polyalkylene terephthalate 0.002 to 0.3 mm thick with pores.

Compounds represented by formula (1) are known, and examples thereof include 2,3,5,6-tetrafluoro-4-methoxymethylbenzyl 3-(1-propenyl)-2,2-dimethyl 2,3,5,6-tetrafluoro-4-methylbenzyl 3-(1-propenyl)-2,2-dimethylcyclopropanecarboxylate, 2,3, 5,6-Tetrafluorobenzyl 3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate, 2,3,5,6-tetrafluoro-4-methoxymethyl benzyl 3-(2-methyl-1-propenyl)-2,2-dimethylcyclopropanecarboxylate, 2,3,5,6-tetrafluoro-4-methoxybenzyl 3- (1-propenyl)-2,2-dimethylcyclopropanecarboxylate, 2,3,5,6-tetrafluoro-4-methoxybenzyl 3-(1-propenyl)-2,2 -Dimethylcyclopropanecarboxylate, 2,3,5,6-tetrafluoro-4-methoxybenzyl 3-(2-methyl-1-propenyl)-2,2-dimethylcyclopropane carboxylate, and 2,3,4,5,6-pentafluorobenzyl 3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate. These compounds can be prepared by known methods.

Due to the cyclopropane ring and the double bond, the compound represented by formula (1) has stereoisomers, and any active isomer or mixture of isomers can be used.

Examples of solvents for the solution of the compound represented by formula (1) include ester solvents having 15 to 25 carbon atoms, such as isopropyl palmitate, dioctyl adipate, dibutyl sebacate, citric acid Acetyl tributyl, di-2-ethylhexyl maleate and isopropyl myristate.

In the thermally volatile material for controlling pests of the present invention, the amount of solvent in the solution of the compound represented by formula (1) is usually 0.1 to 10 parts by weight/compound per part by weight, preferably 0.5 to 5 parts by weight .

The solution of the compound represented by the formula (1) may contain antioxidants, synergists, stabilizers, fragrances and the like, if necessary.

Examples of antioxidants include phenolic antioxidants such as dibutylhydroxytoluene, butylated hydroxyanisole, 2,2-methylene bis(4-methyl-6-tert-butylphenol), 2,6- Di-tert-butyl-4-cresol, 2-[1-(2-hydroxy-3,5-di-tert-pentylphenyl)ethyl]4,6-di-tert-amylphenyl acrylate, 3,9-bis[2-3-(3-tert-butyl-4-hydroxy-5-methylbenzyl)propionyloxy-1,1-dimethyl]-2,4,8,10-tetra Oxyspiro [5.5] undecane and so on.

In the heat volatile material for controlling pests of the present invention, the amount of antioxidant contained in the compound solution represented by formula (1) is usually 0.001 to 1 part by weight/compound per part by weight, preferably 0.1 to 1 part by weight.

Examples of synergists include bis-(2,3,3,3-tetrachloropropyl)ether (S-421), N-(2-ethylhexyl)bicyclo[2.2.1]hept-5-ene -2,3-dicarboximide (MGK264), and α-[2-(2-butoxyethoxy)ethoxy]-4,5-methylenedioxy-2-propyltoluene (PBO).

Examples of stabilizers include ultraviolet absorbers such as benzotriazole-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, and the like.

The carrier used in the thermally volatile material for controlling pests of the present invention is a laminate consisting of a base layer and a modified layer which makes it transparent when a solution is contained therein.

For example, solutions can be prepared by mixing the desired ingredients.

Usually, the base layer is made of a material that can support the compound represented by formula (1), for example, a fibrous material and/or a porous material. Examples of fibrous materials include paper, cardboard, synthetic fiber mixed paper, non-woven fabric fibers, felts like textile materials, and fibrous products like inorganic fibers, and examples of porous materials including porous ceramics.

In terms of the volatilization end point of chemical substances, a colored base layer is preferred from the perspective of improving visual discrimination. Such colored substrates can be prepared, for example, by using inherently colored fibrous materials, by impregnating formed substrates with a colorant, or by applying or printing a colorant on the surface of the substrate.

The base layer is usually in the shape of a quadrilateral with a side length of about 1 to 6 cm and a thickness of 0.2 to 5 mm.

The "improved layer that becomes transparent when containing an oily liquid" is a layer that becomes transparent when containing an oily liquid, and is opaque when it does not contain an oily liquid. The "improved layer that makes it transparent when oily liquid is contained" is generally porous and permeable to oily liquid. The term "oily liquid" as used herein refers to a solution of the compound represented by formula (1), or a volatilized or liquefied vapor of the solution.

The "improving layer that makes it transparent when oily liquid is contained" consists of a mixture of materials that exhibit a low light refractive index when oily liquid is contained, for example, inorganic pigments such as amorphous silica, kaolin, calcium carbonate, etc., organic Pigments such as fine powders of plastic pigments, etc., or pulp powders, etc., and binders. Examples of binders used include vinyl acetate, ethylene-vinyl acetate copolymer, NBR, SBR, and acrylic or other latexes.

The "improving layer that makes it transparent when containing an oily liquid" can be laminated on the base layer by coating, printing (screen printing, offset printing, gravure printing, etc.) or the like. The thickness of the "improving layer that makes it transparent when containing an oily liquid" is usually adjusted so that the layer thickness is 4 to 150 g/m ² , preferably 10 to 60 g/m ² .

In the case of laminating an "improved layer that makes it transparent when oily liquid is contained" on the base layer by printing, the ratio of the adhesive to the material exhibiting a low light refractive index is generally about: 10 to 30 parts by weight Adhesion agent/per 100 parts by weight of the material exhibiting a low light refractive index. In the case of laminating an "improved layer that makes it transparent when oily liquid is contained" on the base layer by coating, the ratio of the adhesive to the material exhibiting a low light refractive index is usually about: 50 parts by weight Adhesion agent/per 100 parts by weight of the material exhibiting a low light refractive index.

"A modified layer that makes it transparent when it contains an oily liquid" may be laminated on the substrate so as to cover the entire surface of the substrate, or when a shape such as an indication code such as "END" "CHANGE" appears on the substrate Then cover part of the surface of the base layer.

As a method of preparing the above-mentioned carrier carrying the solution of the compound represented by the formula (1), for example, the carrier is impregnated with the solution of the compound represented by the formula (1). In terms of the amount of the compound represented by the formula (1), the amount of the solution of the compound represented by the formula (1) supported on the carrier is usually 0.001 to 0.7 g/1 cm ³ apparent volume of the carrier.

In the thermally volatile material for controlling pests of the present invention, the carrier carrying the solution of the compound represented by formula (1) is covered with a polyalkylene terephthalate layer having holes.

Examples of polyalkylene terephthalates include polyethylene terephthalate and polybutylene terephthalate.

In the present invention, the term "covering" not only includes the polyalkylene terephthalate layer covering the surface of the target (carrier) in a manner of close contact with each other, but also includes a slight gap (for example, 1 cm) between the two. or smaller) polyalkylene terephthalate layer covering the situation covering the target (carrier) surface. The gap between the carrier and the polyalkylene terephthalate layer is usually at most 5 mm or less, preferably 3 mm or less.

The thickness of the polyalkylene terephthalate layer is usually 0.002 to 3 mm, preferably 0.01 to 0.1 mm.

In the thermally volatile material for controlling pests of the present invention, the polyalkylene terephthalate layer covering the solution carrier carrying the compound represented by formula (1) has a hole through which the active ingredient can volatilize.

Examples of the case where the polyalkylene terephthalate covering has holes include the case where the polyalkylene terephthalate covering has a cut portion, the polyalkylene terephthalate covering has many small holes , For example, the case where the diameter is about 0.01 to 0.1 mm, and the case where the polyalkylene terephthalate cover layer is partially replaced with a permeable layer to volatilize the active ingredient. For ease of use, the holes in the polyalkylene terephthalate cover layer are generally formed only on the side facing the "improved layer that makes it transparent when oily liquid is contained".

The pore area formed in the polyalkylene terephthalate cover layer is generally about 0.01 to 10%, preferably about 0.03 to 3% of the surface area of the support carrying the solution of the compound represented by formula (1)

The carrier of the solution of the compound shown in the bearing formula (1) can be covered with a polyalkylene terephthalate layer, for example, adopt heat sealing, ultrasonic encapsulation, or high-frequency encapsulation, and the polyalkylene terephthalate A film or sheet of alkylene phthalate is adhered to each carrier surface; polyalkylene terephthalate is formed on the carrier surface using conventional resin coating techniques such as dip coating, spray coating, brush coating, etc. base ester layer; or the carrier is placed in a bag made of polyalkylene terephthalate, and the bag is sealed with an adhesive or the like by heat sealing, ultrasonic encapsulation, or high frequency encapsulation.

The thermally volatilizable material for controlling pests of the present invention can be prepared, for example, by covering the carrier with a polyalkylene terephthalate film with holes, or by covering the carrier with a polyalkylene terephthalate film, followed by forming hole.

Preferably, in the thermally volatilizable material for controlling pests of the present invention, the hole formed in the polyalkylene terephthalate covering layer is sealed with a seal, impermeable to the active ingredient before use, and when the material is used , remove the seal by peeling, tearing or cutting.

In pest habitats or infested areas (such as indoors), the pest control thermal volatile material of the present invention can be controlled to 50-200° C. with a heating device (such as a heating plate).

In this case, the thermally volatilizable material for controlling pests of the present invention is usually heated from the base layer side.

Examples of pests which can be controlled by the method for controlling pests of the present invention include arthropods such as various harmful insects, mites and ticks and the like. Among them, especially flying pests include pests of the order Diptera, for example, mosquitoes (Calicidae) such as Culex acutinus var. Genus such as Anopheles sinensis; chironomids (Chironomidae); houseflies (Muscidae) such as houseflies, stable rot flies, yellow-bellied toilet flies, etc.; Calliphoridae; Pleasidae; Mosquitoidae; Gadidae; Stinging Flyidae; Gnatidae, etc.

The following preparation examples and test examples further illustrate the present invention in detail, but are not construed as limiting the present invention.

Preparation Example 1

By laminating on one surface portion of the purple fiber-based base layer an "improved layer that makes it transparent when an oily liquid is contained" (a mixture of amorphous silica/acrylic latex = 1/0.5 by screen printing so as to become 2,3,5,6-tetrafluoro-4 ^- methoxymethylbenzyl 1R-trans-3-(1-propenyl (E/Z=1/8))-2,2-dimethylcyclopropanecarboxylate, 1 part by weight of dibutyl hydroxytoluene and 2 parts by weight of A 300 mg mixture consisting of acetyl tributyl citrate was impregnated. The carrier is sandwiched between two 37mm x 25mm polyethylene terephthalate films (a thin polypropylene layer is laminated on the surface of each film for heat sealing), and then along the polyethylene terephthalate The edges of the film are heat sealed. Then, the central portion of the polyethylene terephthalate film facing the "improved layer that makes it transparent when oily liquid is contained" was cut to form a hole of 3 mm x 3 mm. Thus, the thermally volatile material for controlling pests of the present invention (hereinafter referred to as the thermally volatile material 1 of the present invention) is obtained.

Preparation Example 2

Except adopting 2,3,4,5,6-pentafluorobenzyl 1R-trans-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate instead of 2,3, 5,6-tetrafluoro-4-methoxymethylbenzyl 1R-trans-3-(1-propenyl (E/Z=1/8))-2,2-dimethylcyclopropanecarboxylate , according to the same method as in Preparation Example 1, the thermally volatile material for controlling pests of the present invention (hereinafter referred to as the volatile material 2 of the present invention) was obtained.

Preparation Example 3

Except adopting 2,3,5,6-tetrafluorobenzyl 1R-trans-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate instead of 2,3,5, 6-Tetrafluoro-4-methoxymethylbenzyl 1R-trans-3-(1-propenyl (E/Z=1/8))-2,2-dimethylcyclopropanecarboxylate, according to In the same manner as in Preparation Example 1, the thermally volatile material for controlling pests of the present invention (hereinafter referred to as volatile material 3 of the present invention) was obtained.

Preparation Example 4

In addition to using 2,3,5,6-tetrafluoro-4-methoxymethylbenzyl 1R-trans-3-(2-methyl-1-propenyl)-2,2-dimethylcyclopropanecarboxylic acid Ester instead of 2,3,5,6-tetrafluoro-4-methoxymethylbenzyl 1R-trans-3-(1-propenyl (E/Z=1/8))-2,2-dimethyl Except cyclopropane carboxylate, according to the same method as Preparation Example 1, the thermally volatile material for controlling pests of the present invention (hereinafter referred to as the volatile material 4 of the present invention) was obtained.

Comparative Preparation Example 1

By laminating on one surface portion of the purple fiber base layer, a modified layer that makes it transparent when a liquid is contained (a mixture of amorphous silica/acrylic latex=1/0.5 through screen printing, so as to become 15 g/ m ² thick) prepared support (20.5mm × 33mm × 1.1mm thick), the support is made of 2,3,5,6-tetrafluoro-4-methoxymethylbenzyl 1R -trans-3-(1-propenyl (E/Z=1/8))-2,2-dimethylcyclopropanecarboxylate, 1 part by weight of dibutylhydroxytoluene and 2 parts by weight of citric acid 300 mg of the mixture consisting of acetyl tributyl ester was impregnated to obtain a thermally volatile material for controlling pests (hereinafter referred to as comparative volatile material 1) used as a control.

Comparative Preparation Example 2

Except adopting 2,3,4,5,6-pentafluorobenzyl 1R-trans-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate instead of 2,3, 5,6-tetrafluoro-4-methoxymethylbenzyl 1R-trans-3-(1-propenyl (E/Z=1/8))-2,2-dimethylcyclopropanecarboxylate , according to the same method of Comparative Preparation Example 1, a thermally volatile material for controlling pests (hereinafter referred to as comparative volatile material 2) was obtained as a control.

Comparative Preparation Example 3

Except adopting 2,3,5,6-tetrafluorobenzyl 1R-trans-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate instead of 2,3,5, 6-Tetrafluoro-4-methoxymethylbenzyl 1R-trans-3-(1-propenyl (E/Z=1/8))-2,2-dimethylcyclopropanecarboxylate, according to The same method as in Comparative Preparation Example 1 was obtained to obtain a thermally volatile material for controlling pests (hereinafter referred to as comparative volatile material 3) used as a control.

Test Example 1

Each of the thermally volatile materials for controlling pests prepared in Preparation Examples and Comparative Preparation Examples was heated on a hot plate at about 170° C., and measured until the “improved layer that makes it transparent when oily liquid is contained” becomes opaque time. Results are shown in Table 1 (three replicates).

Table 1 Time until opaque (hours) Volatile material of the present invention 1 336 to 360 hours Volatile material of the present invention 2 144 to 216 hours Volatile material of the present invention 3 144 to 216 hours Comparative volatile material 1 0.5 to 24 hours Comparative Volatile Material 2 0.5 to 24 hours Contrasting Volatile Materials 3 0.5 to 24 hours

Test Example 2

Each thermally volatilizable material for controlling pests to be tested was heated on a heating plate at about 170° C., and the knockdown test of Culex pipiens var. leucolor was carried out 144 hours, 216 hours and 336 hours after the start of heating.

Knockdown test of Culex apices var.

Each thermally volatilizable material for controlling pests heated by a heating plate was placed in the central part of a cuboid box of 3 m (one bottom surface) x 4 m (the other bottom surface) x 2.3 m (height). Immediately thereafter, about 100 female adult Culex miltiorrhiza (3 to 5 days after eclosion) were released into the box. The KT50 values were determined by observing the number of knocked-down Culex pipiens p.

After the test, continue to heat the thermally volatilizable material for controlling pests on the heating plate outside the box. The results are shown in Table 2.

Table 2 KT50(minute) 144 hours 216 hours 336 hours Volatile material of the present invention 1 28 26 40 Volatile material of the present invention 2 31 >60 >60 Volatile material of the present invention 3 25 >60 >60 Comparative volatile material 1 >60 >60 >60 Comparative Volatile Material 2 >60 >60 >60 Contrasting Volatile Materials 3 >60 >60 >60

The heat volatilization material for controlling pests of the present invention has a long-lasting effective component volatilization time, and the volatilization end time of the active component almost coincides with the fading time of the volatilization material.

Claims (5)

1. A heat-volatile material for controlling pests, which comprises the carrier of the solution of the compound shown in the bearing formula (1):

wherein ^R1 and ^R2 each represent a hydrogen atom, a methyl group or a chlorine atom, ^R3 represents a hydrogen atom, a fluorine atom, a methyl group, a methoxyl group or a methoxymethyl group, a polyalkylene terephthalate having a hole The ester layer is on and covers a carrier, wherein the carrier is a laminate of a base layer and an "improved layer that makes it transparent when oily liquid is contained," and the polyalkylene terephthalate layer has a thickness of 0.002 to 0.3 mm, wherein said base layer is a fibrous material and/or a porous material, and said "improved layer which makes it transparent when oily liquid is contained" is a porous layer and is permeable to oily liquid; wherein the area of the pores 0.01-10% of the apparent surface area of the carrier; and the amount of the solution is 0.001-0.7 g/lcm ³ apparent volume of the carrier, wherein the solvent in the solution of the compound is an ester solvent having 15 to 25 carbon atoms , and the solvent is used in an amount of 0.1 to 10 parts by weight per part by weight of the compound. 2. according to the thermal volatilization material of controlling pest according to claim 1, wherein the compound shown in formula (1) is 2,3,5,6-tetrafluoro-4-methoxymethylbenzyl 3-(1-propenyl )-2,2-dimethylcyclopropanecarboxylate, 2,3,5,6-tetrafluoro-4-methylbenzyl 3-(1-propenyl)-2,2-dimethylcyclopropane Carboxylate, 2,3,5,6-tetrafluorobenzyl 3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate, 2,3,5,6- Tetrafluoro 4-methoxymethylbenzyl 3-(2-methyl-1-propenyl)-2,2-dimethylcyclopropanecarboxylate, or 2,3,4,5,6-pentafluoro Benzyl 3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate. 3. The thermally volatile material for controlling pests according to claim 1, wherein only the hole facing the side of the "improved layer that makes it transparent when containing an oily liquid" is provided, wherein the "improved layer that makes it transparent when containing an oily liquid" is provided. "Transparency-obtaining improved layer" is a porous layer and is permeable to oily liquids. 4. A method of controlling pests, which comprises heating the thermally volatilizable material for controlling pests according to any one of claims 1 to 3 in a pest habitat or infested area. 5. The method according to claim 4, wherein the thermally volatile material for controlling pests is heated from the base layer side.

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