JP2008056605A - Insecticide composition and method for preventing adsorption of pyrethroid volatile under normal temperature - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an insecticide composition reduced in adsorption of an active ingredient to a container in preservation in a sealed state, preventing reduction of the active ingredient, and preserving the effect of the insecticide for a long time. <P>SOLUTION: The adsorption suppressing insecticide composition comprises the pyrethroid volatile under normal temperature and a silicone compound. The insecticide comprises the adsorption suppressing type insecticide composition in a container composed of an olefin-based resin. The method for suppressing adsorption of the pyrethroid volatile under normal temperature to a resin comprises mixing of the pyrethroid volatile under normal temperature with the silicone compound. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an insect repellent that is installed in a clothing storage place such as clothes dance and closet and prevents insect pests on clothes, and in particular, suppresses adsorption of a room temperature volatile pyrethroid as an active ingredient to a resin container. Therefore, the present invention relates to an insect repellent capable of maintaining the insect repellent effect for a long period of time.

  Traditionally, insecticides for textile products such as paradichlorobenzene, camphor, and naphthalene have been used to protect clothing and the like from pest damage. Since these chemicals have odors peculiar to insect repellents, recently, odorless insect repellents using room temperature volatile pyrethroids having no odor as insect repellents are widely used. In this odorless insect repellent, an impregnated body impregnated with a room temperature volatile pyrethroid is stored in a container having a volatile hole, and the material of this container is mainly an olefin resin such as polyethylene or polypropylene. Is used.

  By the way, a pyrethroid compound has a high affinity with an olefin resin, and is an active ingredient when the insect repellent is stored for a long time in a state sealed with a bag such as a plastic during distribution and storage. The room temperature volatile pyrethroid may be adsorbed by the container. Moreover, since the adsorbed room temperature volatile pyrethroid is hardly released, the substantial active ingredient is reduced, and as a result, there is a problem that a sufficient insect-proof effect cannot be exhibited during the period of use.

  In order to solve such problems, various insect repellent containers have been proposed in which room temperature volatile pyrethroids are difficult to be adsorbed. For example, a breathable plastic case using a resin such as polyvinyl chloride, polyvinylidene chloride, a copolymer of vinyl chloride and vinylidene chloride has been proposed (see Patent Document 1). In addition, a container using an amorphous cyclic olefin polymer (see Patent Document 2), an aliphatic polyketone (see Patent Document 3), or an acrylonitrile-butadiene-styrene resin (Patent Document 2). Document 4), those using polyethylene naphthalate (see Patent Document 5), and those using ethylene-vinyl alcohol copolymer resin (see Patent Document 6) have been proposed.

  However, the strength of the insect repellent container using these materials is not sufficient, and it breaks due to impact such as dropping, or in particular, a form having a hook hanging on a bar such as clothes dance as a form of the insect repellent container In this case, there is a problem that the hook portion is broken when it is hooked, and it is difficult to adopt a hinge structure. Furthermore, these resins are inferior in moldability as compared with conventional polyethylene, polypropylene, and the like, and have a problem that the cost of the container itself becomes high due to its high price. Therefore, the present applicant has already proposed an insect repellent container made of a material having a bending elastic modulus of 1400 MPa or more according to a bending elastic test of JISK7203 (see Patent Document 7).

  On the other hand, proposals have been made to suppress the adsorption of volatile pyrethroids to the container by devising the components used in combination with the volatile pyrethroid, not the material of the container, for example, pyrethroid compounds and triethyl citrate are specified. An insect repellent material is proposed in which an insect repellent composition containing a polymerization rate is housed in a frame body based on a polyolefin resin (see Patent Document 8).

  However, since triethyl citrate has a specific odor, when used as an odorless insect repellent, it has a problem that its product characteristics are impaired.

JP-A-2-275805 Japanese Patent Laid-Open No. 9-1187797 JP-A-9-1187798 JP 2004-2314 A JP 2004-254598 A JP 2004-254599 A JP 2003-274835 A JP2004-168671

  Therefore, even during the storage period in a sealed state, the adsorption of the pyrethroid compound, which is an active ingredient, to the olefin resin container is small, and the reduction of the active ingredient can be prevented, and the effectiveness of the insect repellent is maintained over a long period of time. There was a need to develop insect repellents that could be used.

  As a result of earnest research on the adsorption of an insect repellent composition containing a room temperature volatile pyrethroid to a resin, the present inventors have used a silicone compound in combination with a room temperature volatile pyrethroid, thereby allowing a room temperature volatile pyrethroid to be applied to a container. As a result, the present invention was completed.

  That is, this invention is an adsorption | suction suppression type insecticide composition characterized by containing a normal temperature volatile pyrethroid and a silicone compound.

  The present invention is also a method for suppressing adsorption of a room temperature volatile pyrethroid to a resin, characterized in that the room temperature volatile pyrethroid is mixed with a silicone compound.

  The insect repellent composition of the present invention is capable of suppressing the adsorption of a room temperature volatile pyrethroid, which is an active ingredient, to a general-purpose olefin-based resin container, so that the room temperature volatile pyrethroid is an active ingredient even when stored for a long period of time. Can be prevented, and as a result, the insect repellent effect lasts for a long time.

  Therefore, the insect repellent of the present invention has a high insect repellent for a long period of time against clothing pests such as squid, koiga, Himekatsuobushimushi, Himemarukatushimushi under the use environment such as clothes dance, drawer, closet, costume case, doll case, etc. An effect can be exhibited.

  The adsorption-suppressing insect repellent composition of the present invention comprises a room temperature volatile pyrethroid and a silicone compound as essential components.

  The room temperature volatile pyrethroid used in the present invention is not particularly limited as long as it is a pyrethroid compound that is volatilized at room temperature, which has been conventionally used. For example, empentrin, transfluthrin, 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-dimethylcyclopropa 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 those in which one or more of various isomers are mixed. Among these, in terms of volatility and insect repellency, empentrin, transfluthrin, 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 is preferably used.

Moreover, the silicone compound used for this invention is although it does not specifically limit, For example, the compound represented by following formula (1) is mentioned.

[Wherein, R ₁ represents a methyl group or a phenyl group, R ₂ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a group —0—Si (CH ₃ ) ₃ , and n represents a natural number of 0 to 100 Show]

  Specific examples of the compound represented by the formula (1) include hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, dimethylpolysiloxane, methylphenylpolysiloxane, and the like. Specific product names of these include SH200C-1CS, SH200C-1.5CS, SH200C-2CS, SH200C-5CS, SH200C-6CS, SH200C-10CS, SH200C-20CS, SH200C-30CS, SH200C-50CS, SH200C- 100CS, SH200C-200CS, SH200C-500CS, SH556, FZ-3196, SS-3408, etc. (all are manufactured by Toray Dow Corning Silicone Co., Ltd.).

  Specific examples of the silicone compound used in the present invention include 3,3-diphenylpolysiloxane, polyoxyethylenemethylpolysiloxane copolymer, poly (oxyethylene) in addition to the silicone compound represented by the above formula (1). -Oxypropylene) methylpolysiloxane copolymer, laurylmethicone copolyol, aminomethylaminopropylsiloxane dimethylsiloxane copolymer, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, 1,3,5 , 7-tetramethyltetravinylcyclotetrasiloxane, 1,3,5,7,9-pentamethylpentavinylcyclopentasiloxane, 1,3,5,7,9-pentamethylpentaphenylcyclopentasiloxane, trimethylpenta It can be mentioned E sulfonyl trisiloxane like.

  Of these silicone compounds, the compound represented by the above formula (1) is preferably used from the viewpoint of compatibility with the room temperature volatile pyrethroid compound.

  Among the compounds represented by the general formula (1), it is more preferable to use a non-volatile or hardly volatile silicone compound at room temperature, and if a non-volatile or hardly volatile silicone compound is used at room temperature, It can prevent that the silicone compound itself volatilizes and the adsorption | suction suppression effect to the resin of a room temperature volatility pyrethroid compound falls. Examples of such room temperature non-volatile or hardly volatile silicone compounds include dimethylpolysiloxane, methylphenylpolysiloxane, and the like, and specific product names include SH200C-5CS, SH200C-6CS, SH200C- 10CS, SH200C-20CS, SH200C-30CS, SH200C-50CS, SH200C-100CS, SH200C-200CS, SH200C-500CS, SH556, etc. (all manufactured by Toray Dow Corning Silicone Co., Ltd.).

Here, the non-volatile property or the non-volatile property of the silicone compound means that a vertical length of 320 mm, a width of 430 mm, a height of 180 mm, an aluminum foil is laid on the bottom, and 1.0 g of the silicone compound is impregnated thereon. Volatilization amount after 2 weeks when 125 mm, 55 mm wide, 1.05 mm thick filter paper (pulp 100%, basis weight 600 g / m ² ) was capped and volatilized from one side of the filter paper at 40 ° C. Is 0.20 g or less.

  The mixing ratio of the room temperature volatile pyrethroid and the silicone compound used in the insect repellent composition of the present invention is not particularly limited, but room temperature volatile pyrethroid: silicone compound is preferably 20: 1 to 1: 9, more preferably 9: 1-1: 1. If the blending ratio of the silicone compound is less than this range, the adsorption preventing effect may not be exhibited. If the blending ratio of the silicone compound is greater than this range, the volatilization of the room temperature volatile pyrethroid compound is hindered and appropriate. May not be effective.

  In addition to the above room temperature volatile pyrethroid and silicone compound, the insect repellent composition of the present invention includes, as necessary, an antioxidant, an ultraviolet absorber, a fungicide, a fungicide, a dye, a deodorant, a fragrance, a metal Inert agents, efficacy enhancers, other insect repellents and the like can be blended.

  Further, the insect repellent composition of the present invention can be obtained by mixing the above-mentioned room temperature volatile pyrethroid and silicone compound with the above optional components according to a conventional method, if necessary, and further using these components in a suitable solvent. It may be dissolved.

  The solvent is not particularly limited, and a conventionally known solvent can be used. Specifically, water; 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; 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 acetate, ethylene glycol, propylene glycol, etc. Glycol compounds; glycol ether compounds such as 2-phenoxyethanol and 3-methyl-3-methoxy-1-butanol; vegetable oils such as linoleic oil, and the like. These may be used alone or in combination. it can. When mixing with a solvent, a surfactant may be used as necessary. The surfactant that can be used may be one or a mixture of two or more of an anionic surfactant, a cationic surfactant, an amphoteric surfactant, a nonionic surfactant, and the like.

  The insect repellent composition of the present invention thus obtained can be used as a solution as it is, but can also be used by impregnating a suitable impregnated body. The impregnated body is not particularly limited as long as it can be impregnated with a room temperature volatile pyrethroid, and specifically, pulp, paper, wood chips, silica gel, woven fabric, non-woven fabric, etc. are granular, spherical, plate-shaped, mat-shaped. And those formed into a film.

  Moreover, the insect repellent composition of the present invention can also be used as a gel obtained by gelling with a known gelling agent. Examples of the gelling agent include carrageenan, gellan gum, agar, and gelatin.

  The insect repellent composition of the present invention prepared in the form of a liquid agent, an impregnated body, a gel or the like as described above can be stored in a container to obtain the insect repellent composition of the present invention. The material used for this container is not particularly limited, but an olefin resin is preferably used. Examples of the olefin resin include polyethylene, polypropylene, polybutene-1, poly-4-methylpentene polymer, homopolymers such as an ethylene-propylene copolymer, block copolymers, random copolymers, alternating copolymers, graft copolymers, and the like. These may contain a small amount of additives. Among these, it is preferable to use polypropylene in terms of formability, workability, hinge characteristics, and impact resistance.

  Moreover, the shape of this container can use a conventionally well-known shape, but it is not specifically limited, It is preferable to provide opening parts, such as a volatilization hole.

  The insect repellent of the present invention is hermetically preserved and stored in a barrier film before the start of use, and when used, it is opened and taken out, and then placed in a storage container such as a clothes dance, drawer, clothes case, etc. Is effectively volatilized and exhibits an insect-repellent effect in the storage container against clothing pests such as moths, koiga, himemekaobushimushi, himemarukatsuobushimushi.

  Since the insect repellent of the present invention can suppress adsorption of a room temperature volatile pyrethroid to a container even if it is hermetically sealed for a long period of time, its effectiveness can be maintained for a long period of time.

  EXAMPLES Next, although an Example is given and this invention is demonstrated in detail, this invention is not limited to these.

Example 1
(Adsorption test)
A room temperature volatile pyrethroid having a composition shown in Table 1 below and a silicone compound were mixed to obtain an insect repellent composition (Products 1 to 3 of the present invention). 1.0 g of this insect repellent composition was impregnated into pulp-impregnated paper (12.5 × 5.5 cm) to prepare an insect repellent housed in a polypropylene container as shown in FIG. 1 having volatilization holes. This insect repellent is stored in a polyethylene terephthalate barrier bag, sealed, placed in a constant temperature bath at 40 ° C., and the remaining amount of impentrin in the impregnated paper is measured every certain period. Asked. As Comparative Product 1, a product impregnated with only 0.5 g of empentrin was used. The results are shown in Table 2.
Residual rate (%) = (Remaining amount of impregnated body (g) / Initial impregnation amount (g)) × 100

  As is apparent from these results, the product of the present invention using both empentrin and a silicone compound showed an effect of inhibiting the adsorption of empentrin on the container as compared with the comparative product 1 of the empentrin alone.

Example 2
A room temperature volatile pyrethroid having a composition shown in Table 3 below and a silicone compound were mixed to obtain an insect repellent composition (products 4 to 6 of the present invention). In the same manner as in Example 1, the residual rate of room temperature volatile pyrethroid was determined. As a comparative product, a product impregnated only with 0.2 g of empentrin was used. The results are shown in Table 4.

  As is apparent from the results, the products of the present invention in which empentrin and a silicone compound were used in combination showed an effect of suppressing the adsorption of enpentrin on the container as compared with the comparative product 2 containing only empentrin.

Example 3
(Insect repellent test)
A polypropylene container shown in FIG. 1 having a volatilized hole, impregnated with 1.0 g of an insect repellent composition of the present invention products 1 to 3 obtained in Example 1 in a pulp impregnated paper (12.5 × 5.5 cm). 1 to 3 were prepared. FIG. 1 is a front view of the container 1, and FIG. 2 is a cross-sectional view taken along line AA ′ of FIG. This insect repellent was stored in a polyethylene terephthalate barrier bag, sealed, and placed in a constant temperature bath at 40 ° C. After 60 days, the barrier bag was opened and an insect repellent test was conducted by the following method. For comparison, a product impregnated with 0.5 g of the insect repellent composition of Comparative Product 1 was used. The results are shown in Table 5.

(Insect repellent test method)
The pulp-impregnated paper was cut into 1 cm × 1 cm and placed in a metal basket having a diameter of 4 cm. Place this in the center of a container with a glass lid with a volume of 0.5 liters, and place a 2.5 cm square surge on one side with 20 eggs of moths that are clothing pests one day after laying on the bottom. It was. After storage for 14 days under conditions of temperature 25 ° C and relative humidity 60% RH, open the container lid, count the number of hatched eggs, and if hatched, the young larvae immediately after hatching Determined. The insect repellent rate was calculated by the following formula as a percentage of the total number of eggs of “number of eggs not hatched + number of young larvae dead”.
Insect repellent rate (%) = 100 × (20−N) / 20
N: Number of young larvae that survived

  As is clear from the above results, it was shown that the insect repellent of the present invention exerts an insect repellent effect for a long period even after long-term storage, as compared with a comparative product.

Example 4
(Examples for Western dance)
The insect repellent container 2 (made of polypropylene) with a hook shown in FIG. 3 was prepared, and 2,3,5,6-tetrafluoro-4-methoxymethylbenzyl-3- (1) was placed on a 12 cm × 5.5 cm filter paper. -Propenyl) -2,2-dimethylcyclopropanecarboxylate 500 mg and methylphenylpolysiloxane ^{* 3} 500 mg were impregnated and stored in a container to prepare the insect repellent of the present invention. 3 is a front view of the container 2, and FIG. 4 is a view in which the container is opened. The container was placed in a PET / CP packaging bag and stored at 40 ° C. for 1 month, then opened and placed in a clothes dance. This had an insect repellent effect for about 6 months.

  Since the insect repellent composition of the present invention can suppress adsorption of a room-temperature volatile pyrethroid, which is an active ingredient, onto a container, its effectiveness can be sustained for a long period even when stored for a long period of time, and can be advantageously used.

It is a front view of the container 1 which comprises the insect repellent of this invention. It is sectional drawing of the A-A 'direction of the container 1 of FIG. It is a front view of the container 2 which comprises the insect repellent of this invention. It is a figure of the state which opened the main body of the container 2 of FIG.

Explanation of symbols

1 insect repellent 2 container
2a Right container body 2b Left container body 2c Upper container body 2d Lower container body 3 Volatilization hole 4 Drug impregnation body 5 Hinge part 6 Hook part 6a Hook part of right container body 6b Hook part of left container body 7 Support pin 8 Container inner surface part 9 Mating hole 10 Mating pin

Claims (10)

  An adsorption-inhibiting insect repellent composition comprising a room temperature volatile pyrethroid and a silicone compound. The silicone compound is represented by the following formula (1)

[Wherein, R ₁ represents a methyl group or a phenyl group, R ₂ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a group —0—Si (CH ₃ ) ₃ , and n represents 0 to 100. Show natural number]
The adsorption-inhibiting insect repellent composition according to claim 1, which is a compound represented by the formula:   The adsorption-suppressing insecticide composition according to claim 1 or 2, wherein the silicone compound is non-volatile at room temperature or hardly volatile at room temperature.   The adsorption-inhibiting insect repellent composition according to any one of claims 1 to 3, wherein a mixing ratio of the room temperature volatile pyrethroid and the silicone compound is 20: 1 to 1: 9.   An insect repellent, wherein the adsorption-suppressing insect repellent composition according to any one of claims 1 to 4 is housed in a container composed of an olefin resin.   The insect repellent according to claim 5, wherein the container has a volatilization hole.   A method for suppressing adsorption of a room temperature volatile pyrethroid to a resin, comprising mixing the room temperature volatile pyrethroid with a silicone compound.   The method for suppressing adsorption of a room temperature volatile pyrethroid to a resin according to claim 7, wherein the silicone compound is a compound represented by the formula (1).   The method for suppressing adsorption of a room temperature volatile pyrethroid to a resin according to claim 7 or 8, wherein the silicone compound is a room temperature non-volatile or a room temperature hardly volatile. The method for suppressing adsorption of a room temperature volatile pyrethroid to a resin according to any one of claims 7 to 9, wherein the ratio of mixing the room temperature volatile pyrethroid and the silicone compound is 20: 1 to 1: 9.

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