JP2020055764A - Insecticide composition - Google Patents

Abstract

To provide an insecticide which is reduced in adsorption of a pyrethroid-based compound to an olefin-based resin even in a sealed state, can prevent reduction in an active ingredient, and can maintain the effect over a long period of time without impairing merchantability.SOLUTION: An adsorption suppressing type insecticide composition contains pyrethroid volatile under normal temperature and an ester compound represented by formula (1). An insecticide in which the composition is stored in a container composed using an olefin-based resin, and an insecticide product in which the insecticide is coated with and/or sealed in a resin-made packaging sheet whose an inner surface is heat-sealable. In formula 1, Ris an alkyl group that has 8 to 18 carbon atoms and may be branched; and Ris an alkyl group that has 1 to 5 carbon atoms and may be branched.SELECTED DRAWING: Figure 3

Description

  The present invention relates to an insect repellent composition, and more particularly, to an insect repellent composition capable of suppressing adsorption of a normal-temperature-volatile volatile pyrethroid, which is an active ingredient, to a resin and maintaining insect repellency over a long period of time. . The insect repellent composition stored in a container or the like is useful for controlling insect pests and flying pests, such as clothing, dancing, closet, and the like, in a storage place, a door, a window, and the like.

  Conventionally, insect repellents have been used to protect clothing and the like from damage by pests. Pyrethroids, which are volatile at room temperature, are odorless insect repellents and are therefore widely used as odorless insect repellents. ing. In this odorless insect repellent, a form in which an impregnated body impregnated with a normal-temperature volatile pyrethroid is housed in a container having a volatile hole is generally used, and the material of this container is mainly an olefin-based material such as polyethylene or polypropylene. Resin is used.

  Such an insect repellent is generally contained in a package in which the drug does not permeate together with the container so that the normal-temperature volatile pyrethroid contained as an active ingredient is not volatilized at the distribution stage or before the start of use by a consumer. It is a target.

  By the way, pyrethroid-based compounds have a high affinity with olefin-based resins, and when the insect repellent is stored for a long time in a state of being sealed with a bag of plastic or the like during distribution and storage, it is an active ingredient. Room temperature volatile pyrethroids were sometimes adsorbed to the heat seal layer on the inner surface of the container or plastic bag.

  Then, the normal temperature volatile pyrethroid adsorbed on the container is no longer released, and the normal temperature volatile pyrethroid adsorbed on the heat seal layer of the packaging bag is discarded together with the bag. Therefore, the insect repellent using a volatile pyrethroid at room temperature and an olefin-based resin container or package has a problem that a substantial amount of the effective ingredient is reduced, and as a result, a sufficient insect repellent effect cannot be exhibited during the use period. Was.

  Therefore, in order to solve such problems, various insect repellent containers have been proposed in which room temperature volatile pyrethroids are not easily adsorbed. For example, a breathable plastic case using a resin such as polyvinyl chloride, polyvinylidene chloride, or a copolymer of vinyl chloride and vinylidene chloride has been proposed (see Patent Document 1). Further, a material using an amorphous cyclic olefin polymer as a material of the container (see Patent Document 2), a material using an aliphatic polyketone (see Patent Document 3), and a material using acrylonitrile-butadiene-styrene resin (Patent Documents using polyethylene naphthalate (see Patent Document 5), those using an ethylene-vinyl alcohol copolymer resin (see Patent Document 6), and the like have been proposed.

  However, the strength of insect repellent containers using these materials is not sufficient, and the insect repellent container is broken by an impact such as dropping, and particularly, as a form of the insect repellent container, a form having a hook suspended from a bar such as a clothes dance. In this case, there is a problem that the hook portion is broken when the hook is hung, and it is difficult to adopt a hinge structure. Furthermore, these resins have the problem that they are inferior in moldability as compared with conventional polyethylene, polypropylene and the like, and that the cost of the container itself is increased due to its high cost.

  The applicant of the present invention has studied the material used for the insect repellent container first from the viewpoint of physical properties, and has proposed an insect repellent container made of a material having a flexural modulus of 1400 MPa or more in a flexural elasticity test according to JIS K7203. (See Patent Document 7).

  In addition, a volatile drug packaging film used for a package for packaging a volatile drug or a holding body containing the same is also examined, and polyethylene non-adsorbing materials such as polyethylene terephthalate, polybutylene terephthalate, and polyamide, and polyethylene, It has been reported that a film formed of a material obtained by mixing a heat-sealing material such as polypropylene is suitable as a volatile drug packaging film (Patent Document 8). The effect of suppressing drug adsorption is not perfect, and further improvement is required.

  On the other hand, it has been proposed to suppress the adsorption of volatile pyrethroids to the container, not to the material of the container, by devising components used in combination with the volatile pyrethroids.For example, pyrethroid-based compounds and triethyl citrate have been specified. There has been proposed an insect repellent in which an insect repellent composition containing a polymerization ratio is contained in a frame having a base material of a polyolefin resin (see Patent Document 9).

  However, triethyl citrate has a problem that the volatilization of volatile pyrethroids may be remarkably slowed down when a sufficient amount for suppressing adsorption is added.

JP-A-2-275805 JP-A-11-1187797 JP-A-11-1187798 JP 2004-2314 JP-A-2004-254598 JP 2004-254599 JP-A-2003-274835 JP-A-2004-331174 JP-A-2004-168671

  Therefore, even during the storage period in a sealed state, etc., the adsorption of the pyrethroid-based compound as the active ingredient to the olefin-based resin is small, the reduction of the active ingredient can be prevented, and the efficacy of the insect repellent over a long period of time can be improved. There has been a demand for the development of insect repellents that can be sustained without impairing the properties.

  The present inventors have conducted intensive studies on the adsorption of the insect repellent composition containing a normal-temperature-volatile pyrethroid to a resin, and as a result, by using a specific ester compound in combination with the normal-temperature-volatile pyrethroid, a normal-temperature volatilization into a container. It has been found that the adsorption of a pyrethroid can be suppressed, and the present invention has been completed.

（式中、Ｒ_１は炭素数８〜１８の分岐していてもよいアルキル基を示し、Ｒ_２は炭素
数１〜５の分岐していてもよいアルキル基を示す）
で表されるエステル化合物を含有することを特徴とする吸着抑制型防虫剤組成物である。 That is, the present invention provides a normal-temperature volatile pyrethroid and the following formula (1)

(Wherein, R ₁ represents an optionally branched alkyl group having 8 to 18 carbon atoms, and R ₂ represents an optionally branched alkyl group having 1 to 5 carbon atoms)
It is an adsorption suppression type insect repellent composition characterized by containing the ester compound represented by these.

  In addition, the present invention is an insect repellent obtained by storing the adsorption-suppressing insect repellent composition in a container made of an olefin resin.

  Further, the present invention is an insect repellent product obtained by covering and storing the above insect repellent with a heat-sealing resin packaging sheet.

（式中、Ｒ_１及びＲ_２は前記した意味を有する）
で表されるエステル化合物を配合することを特徴とする常温揮散性ピレスロイドの樹脂への吸着抑制方法である。 Furthermore, the present invention relates to a cold-volatile pyrethroid having the following formula (1)

(Wherein, R ₁ and R ₂ have the meanings described above)
The method for suppressing adsorption of a normal-temperature volatile volatile pyrethroid to a resin, which comprises mixing an ester compound represented by the formula:

  The adsorption-suppressing insect repellent composition of the present invention (hereinafter referred to as “insect repellent composition”) is a compound in which the compounded ester compound (1) adsorbs the room temperature volatile pyrethroid as an active ingredient to an olefin resin or the like. Since it can be suppressed, it is possible to prevent a decrease in the temperature of the volatile volatile pyrethroid, which is an active ingredient, even when stored for a long period of time, and as a result, the insect repellent effect can be maintained for a long time.

  Therefore, the insect repellent obtained by storing the insect repellent composition in a container made of an olefin-based resin can be volatilized at room temperature in a use environment such as a clothes dance, drawer, closet, costume case, doll case, entrance, screen door, and the like. Sex pyrethroids can be stably volatilized over a long period of time, and can exert a high insect repellent effect against clothing pests such as ligatures, moths, burrowing worms, burrowing worms, mosquitoes, flies, chironomids, and fly flies. Things.

It is a front view of container 1 which is one mode of the insect repellent of the present invention. FIG. 2 is an end view in the A-A ′ direction of the container 1 of FIG. 1. It is a front view of the container 2 which is another aspect of the insect repellent of this invention. FIG. 4 is a cross-sectional view of the container 2 of FIG. 3 in the B-B ′ direction.

  The insect repellent composition of the present invention contains a normal-temperature volatile pyrethroid and an ester compound as essential components.

  The normal-temperature volatilizable pyrethroid used in the present invention is not particularly limited as long as it is a pyrethroid-based compound conventionally used and volatilized at room temperature. For example, empentrin, transfluthrin, profluthrin, methfluthrin, 2,3,5, 6-tetrafluoro-4-methylbenzyl-3- (1-propenyl) -2,2-dimethylcyclopropanecarboxylate, 2,3,5,6-tetrafluoro-4-methoxymethylbenzyl-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-methylbenzyl-3- (2,2-dichlorovinyl) -2,2-dimethylcyclo B pan carboxylate and the like, can be used as a mixture of two or more thereof. When these compounds have optical isomers or geometric isomers, the compounds include one or a mixture of two or more of various isomers.

  Among them, empentrin, transfluthrin, profluthrin, 2,3,5,6-tetrafluoro-4-methylbenzyl-3- (1-propenyl) -2,2-dimethylcyclopropane in terms of volatility and insect repellent effect Carboxylates, 2,3,5,6-tetrafluoro-4-methoxymethylbenzyl-3- (1-propenyl) -2,2-dimethylcyclopropanecarboxylate, are preferably used.

（式中、Ｒ_１は炭素数８〜１８の分岐していてもよいアルキル基を示し、Ｒ_２は炭素
数１〜５の分岐していてもよいアルキル基を示す）
で表されるものである。 On the other hand, the ester compound used in the present invention has the formula (1)

(Wherein, R ₁ represents an optionally branched alkyl group having 8 to 18 carbon atoms, and R ₂ represents an optionally branched alkyl group having 1 to 5 carbon atoms)
It is represented by

  The ester compound represented by the formula (1) (hereinafter, referred to as “ester compound (1)”) is non-volatile or non-volatile at room temperature, and either is known or a method for producing a known compound. It is a compound produced according to.

  Specific examples of the ester compound (1) include methyl caprylate, ethyl caprylate, propyl caprylate, butyl caprylate, isopropyl caprylate, methyl caproate, ethyl caproate, propyl caproate, butyl caproate, and caproate. Isopropyl acetate, methyl laurate, ethyl laurate, propyl laurate, butyl laurate, isopropyl laurate, methyl myristate, ethyl myristate, propyl myristate, butyl myristate, isopropyl myristate, methyl palmitate, ethyl palmitate , Propyl palmitate, butyl palmitate, isopropyl palmitate, methyl stearate, ethyl stearate, propyl stearate, butyl stearate, isopropyl stearate, etc. Can be exemplified, it can be used as a mixture of one or more of these.

  Of these, isopropyl myristate is preferably used from the viewpoints of volatility, adsorption suppression effect, and compatibility with volatile pyrethroid.

  The insect repellent composition of the present invention is prepared by mixing the above-mentioned volatile volatile pyrethroid and the ester compound (1) according to a conventional method, and further adding optional components as necessary.

  In the production of the insect repellent composition, the mixing ratio of the room-temperature volatile pyrethroid and the ester compound (1) is not particularly limited, but is about 20: 1 to 1: 9, preferably 10: 1 to 1:10, More preferably, it is 5: 1 to 1: 1. If the proportion of the ester compound (1) is smaller than this range, the effect of preventing adsorption may not be exhibited. If the proportion of the ester compound (1) is larger than this range, the volatile volatile pyrethroid may be used. In some cases, the compound does not volatilize and cannot exert an appropriate insect repellent effect.

  Further, as optional components to be added to the insect repellent composition of the present invention as necessary, other insect repellents such as phenoxyethanol, antioxidants, ultraviolet absorbers, fungicides, fungicides, pigments, deodorants, Perfumes, metal deactivators, potency enhancers, other adsorption inhibitors such as triethyl citrate, silicone and the like can be added.

  Further, in mixing the room-temperature volatile pyrethroid and the ester compound (1) with optional components to be blended as required, an appropriate solvent can be used. The solvent is not particularly limited, and a conventionally known solvent can be used.

  Specific examples of the solvent include hydrocarbon compounds such as hexane and paraffin; alkyl alcohols such as methanol, ethanol and decanol; alkenyl alcohols such as allyl alcohol; aromatic ring-containing alcohols such as benzyl alcohol; eugenol Phenols such as chloroform; halogenated hydrocarbon compounds such as chloroform; ether compounds such as diethyl ether; ketone compounds such as acetone; aliphatic compounds such as acetic acid and oleic acid; ester compounds such as acetic acid ester; Glycol-based compounds such as 2-phenoxyethanol and 3-methyl-3-methoxy-1-butanol; and vegetable oils such as linoleic oil. These may be used alone or in combination of two or more. To use It can be.

  Furthermore, when mixing each component in a solvent, a surfactant can be used if necessary. As the surfactant that can be used, one or more of anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants, and the like can be used in combination.

  The thus-obtained insect repellent composition of the present invention can be used as it is in the form of a mixture of each component in a solvent, or can be used after being impregnated with an appropriate impregnated body. The impregnated body is not particularly limited as long as it can impregnate a normal-temperature volatile pyrethroid or the like.Specifically, pulp, paper, wood chips, silica gel, woven fabric, non-woven fabric, etc. may be used in the form of granules, spheres, plates, mats, etc. And those formed into films.

  The insect repellent composition obtained as described above can be used as an insect repellent by storing it in a container made of an olefin-based resin. More specifically, the insect repellent composition of the present invention is stored in an olefin resin container having an opening or a portion that becomes an opening when used, and the insect repellent composition prepared in the form of a solution or an impregnated body. Can be obtained.

  The olefin resin used in this container is not particularly limited, but may be polyethylene terephthalate, polybutylene terephthalate, polyethylene, polypropylene, polybutene-1, poly-4-methylpentene polymer, ethylene-propylene copolymer, or the like. , Homopolymers, block copolymers, random copolymers, alternating copolymers, graft copolymers and the like, and these may contain a small amount of additives. Among them, when a molded container is used, it is preferable to use polypropylene in terms of moldability, workability, hinge characteristics and impact resistance.

  The shape of the container can be a conventionally known shape, and is not particularly limited. For example, the container preferably has an opening such as a volatile hole as shown in FIGS. 1 and 3.

  The insect repellent prepared as described above is preferably further packaged with a packaging material (film) to obtain an insect repellent product in order to stably store the insect repellent at the storage stage or the distribution stage. As the packaging material, a conventionally known film can be used. However, it is preferable to use a resin sheet having a configuration in which a normal-temperature volatile pyrethroid does not permeate and the inner surface has heat sealability.

  Specific examples of the resin sheet whose inner surface is heat-sealing include biaxially oriented polyester (PET) / non-oriented polypropylene (CPP), biaxially oriented polyester (PET) / polyethylene (PE), and biaxially oriented polypropylene ( Examples include sheets of OPP) / aluminum-deposited polyester (VMPET) / unstretched polypropylene (CPP), biaxially stretched polyester (PET) / ethylene vinyl alcohol copolymer (EVOH) / polyethylene (PE).

  The form of packaging of the insect repellent product can be selected from various known forms, but one preferred embodiment is a bag for ease of storage. Examples of a method for producing such a bag include three-side seal packaging, four-side seal packaging, horizontal pillow packaging or vertical pillow packaging, gusset bag packaging, standing pouch bag packaging, and the like, using a conventionally known bag making machine. be able to.

  The insect repellent of the present invention, even when stored as an insect repellent product in a sealed state for a long period of time, is suppressed from adsorbing the room-temperature volatile pyrethroid in the insect repellent composition to the heat seal layer on the inner surface of the insect repellent container or packaging material. Therefore, its efficacy can be maintained for a long time.

  Therefore, after taking out the insect repellent of the present invention, clothes dance, drawers, or installed in a storage container such as a costume case, or by hanging at the entrance, window, etc., the active ingredient is efficiently volatilized, It exerts an insect repellent effect on clothing pests such as imo, moth moth, duck beetle, and beetle beetle, and flying pests such as mosquitoes, flies, midges, and fly flies.

  Next, the present invention will be described in detail with reference to examples, but the present invention is not limited thereto.

Example 1
Adsorption test:
An insect repellent composition was obtained by mixing an ordinary temperature volatile pyrethroid having the composition shown in Table 1 below with an ester compound (Product 1 of the present invention). This insect repellent composition was impregnated into pulp-impregnated paper (3 × 4 cm) to prepare an insect repellent stored in a polyethylene terephthalate / polypropylene container shown in FIG. This insect repellent was stored in a biaxially stretched PET / CPP bag, sealed, put in a thermostat at 40 ° C., and the remaining amount of empentrin in the impregnated paper after 6 months was measured. Was determined. As a comparative product 1, a product impregnated only with empentrin was used. Table 2 shows the results.

    Residual rate (%) = (remaining amount of impregnated body (g) / initial impregnation amount (g)) × 100

  As is clear from these results, the product 1 of the present invention in which empentrin and isopropyl myristate were used in combination showed an effect of suppressing the adsorption of empentrin to the container and the packaging film as compared with the comparative product 1 of empentrin alone.

Example 2
Insect repellent test:
The insect repellent of the product 1 of the present invention obtained in Example 1 was subjected to an insect repellent test by the following method. As a comparison, the product impregnated with the insect repellent of Comparative product 1 was used. Table 3 shows the results.

(Insect repellent test method)
The pulp-impregnated papers of the product 1 of the present invention and the comparative product 1 were cut into 1 cm × 1 cm, placed in a metal basket having a diameter of 4 cm, and placed at a substantially center of a 0.4-liter glass container with a lid. . A square surge of 2.5 cm on a side was laid on the bottom of the glass container, and 20 eggs of Iga, a clothing pest one day after laying eggs, were placed on the surge.

  After storing at room temperature for 14 days, the lid of the container was opened, the number of hatched eggs was counted, and if hatched, the viability of young larvae immediately after hatching was determined. The insect repellency was determined by the following formula as a percentage of the total number of eggs of “the number of eggs that did not hatch + the number of dead young larvae”.

Insect repellency (%) = 100 × (20−N) / 20
N: Number of surviving young larvae

  As is clear from the above results, it was shown that the insect repellent of the product 1 of the present invention exerts the same insect repellent effect as that of the comparative product 1.

Example 3
Hanging insect repellent (1):
An insect repellent composition was obtained by mixing an ordinary temperature volatile pyrethroid having the composition shown in Table 4 below with an ester compound (Product 2 of the present invention or Comparative Product 2).

  This insect repellent composition was impregnated into a pulp impregnated paper (9.6 × 11 cm) and stored in a polypropylene container having a volatile hole shown in FIG. 3 to prepare an insect repellent. This insect repellent was stored in a biaxially stretched PET / CPP bag and sealed to obtain an insect repellent product.

  The produced insect repellent product was put into a constant temperature bath at 40 ° C., and the remaining amount of empentrin in the impregnated paper after one month was measured, and the residual ratio of the normal-temperature volatile pyrethroid was determined by the following formula. As a comparative product, a product impregnated only with empentrin (Comparative Product 2) was used. Table 5 shows the results.

    Residual rate (%) = (remaining amount of impregnated body (g) / initial impregnation amount (g)) × 100

  As is clear from these results, the product 2 of the present invention in which empentrin and an ester compound were used in combination showed an effect of suppressing the adsorption of empentrin to containers and packaging films, as compared with the comparative product 2 of empentrin alone.

Example 4
Insect repellent test:
The insect repellents of the product 2 of the present invention and the comparative product 2 obtained in Example 3 were subjected to an insect repellent test in the same manner as in Example 2. Table 6 shows the results.

  As is clear from the above results, it was shown that the insect repellent of the product 2 of the present invention exhibited the same insect repellent effect as that of the comparative product 2.

Example 5
Hanging insect repellent (2):
An insect repellent composition was obtained by mixing a normal-temperature volatile pyrethroid having the composition shown in Table 7 below with an ester compound (Product 3 of the present invention or Comparative Product 3).

  This insect repellent composition was impregnated into a pulp impregnated paper (9.6 × 11 cm) and stored in a polypropylene container having a volatile hole shown in FIG. 3 to prepare an insect repellent. This insect repellent was stored in a biaxially stretched PET / CPP bag, sealed, put in a thermostat at 40 ° C., and one month later, the remaining amount of profluthrin in the impregnated paper was measured. Was determined. Note that a product impregnated with only profluthrin was used as Comparative product 3. Table 8 shows the results.

    Residual rate (%) = (remaining amount of impregnated body (g) / initial impregnation amount (g)) × 100

  As is clear from these results, the product 3 of the present invention using profluthrin in combination with the ester compound showed an effect of suppressing the adsorption of profluthrin to the container and the packaging film as compared with the comparative product 3 of profluthrin alone.

Example 6
Insect repellent test:
The insect repellent of the product 3 of the present invention and the comparative product 3 obtained in Example 5 was subjected to an insect repellent test in the same manner as in Example 2. Table 9 shows the results.

  As is clear from the above results, it was shown that the insect repellent of the product 3 of the present invention exerts the same insect repellent effect as that of the comparative product 3.

  The insect repellent of the present invention, in the insect repellent composition, can suppress adsorption of the room temperature volatile pyrethroid, which is the active ingredient, to the container. The later effect can last for a long time.

  Therefore, it can be advantageously used as an insect repellent for clothing pests or a flying pest repellent by being installed in a storage container or suspended at a front door, a window, or the like.

1…… insect repellent 2…… container
2a ... upper container body 2b ... lower container body 2c ... right container body 2d ... left container body 3 ... volatilization hole 4 ... ... drug-impregnated body 5 ... ... hook part

Claims (8)

Room temperature volatile pyrethroid and the following formula (1)

(Wherein, R ₁ represents an optionally branched alkyl group having 8 to 18 carbon atoms, and R ₂ represents an optionally branched alkyl group having 1 to 5 carbon atoms)
An adsorption-controlling insect repellent composition comprising an ester compound represented by the formula:   The adsorption-controlling insect repellent composition according to claim 1, wherein a mixing ratio of the room-temperature volatile pyrethroid and the ester compound represented by the formula (1) is 10: 1 to 1:10.   The adsorption-controlling insect repellent composition according to claim 1 or 2, wherein the ester compound represented by the formula (1) is isopropyl myristate.   An insect repellent comprising the adsorption-suppressing insect repellent composition according to any one of claims 1 to 3 housed in a container made of an olefin resin.   5. The olefin resin according to claim 4, wherein the olefin resin is selected from the group consisting of polyethylene terephthalate, polybutylene terephthalate, polyethylene, polypropylene, polybutene-1, poly-4-methylpentene polymer and ethylene-propylene copolymer. Insect repellent.   An insect repellent product obtained by covering and storing the insect repellent according to claim 4 or 5 with a heat-sealing resin packaging sheet.   The above-mentioned heat-sealing resin packaging sheet is made of a biaxially oriented polyester (PET) / non-oriented polypropylene (CPP), a biaxially oriented polyester (PET) / polyethylene (PE), a biaxially oriented polypropylene (OPP) / aluminum The sheet according to claim 6, wherein the sheet is selected from the group consisting of vapor-deposited polyester (VMPET) / unstretched polypropylene (CPP) and biaxially stretched polyester (PET) / ethylene-vinyl alcohol copolymer (EVOH) / polyethylene (PE). Insect repellent products. In a volatile volatile pyrethroid, the following formula (1)

(Wherein, R ₁ represents an optionally branched alkyl group having 8 to 18 carbon atoms, and R ₂ represents an optionally branched alkyl group having 1 to 5 carbon atoms)
A method for suppressing adsorption of a normal-temperature volatile pyrethroid to a resin, which comprises mixing an ester compound represented by the formula:

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