JP2004168671A

JP2004168671A - Insect repellent material

Info

Publication number: JP2004168671A
Application number: JP2002333222A
Authority: JP
Inventors: Masaya Okada; 賢哉岡田; Tadakatsu Matsunaga; 忠功松永
Original assignee: Mishima Paper Manufacturing Co Ltd; Sumitomo Chemical Co Ltd; Osaka Pharmaceutical Co Ltd
Current assignee: Mishima Paper Manufacturing Co Ltd; Sumitomo Chemical Co Ltd; Osaka Pharmaceutical Co Ltd
Priority date: 2002-11-18
Filing date: 2002-11-18
Publication date: 2004-06-17
Anticipated expiration: 2022-11-18
Also published as: JP4340761B2

Abstract

<P>PROBLEM TO BE SOLVED: To simply provide an insect repellent material effectively exhibiting insect repellent performances essentially possessed by an active ingredient and suitable for clothes uses at a low cost, in the insect repellent material comprising an insect repellent composition using an ester compound (1) contained in a frame body composed of an olefinic resin. <P>SOLUTION: The insect repellent composition comprises the ester compound represented by formula (1) and triethyl citrate in (1:0.5)-(1:10) weight ratio. The insect repellent material comprises the insect repellent composition contained in the frame body composed of the olefinic resin as a substrate. <P>COPYRIGHT: (C)2004,JPO

Description

【０００１】
【発明の属する技術分野】
本発明は、防虫材、とりわけ洋服ダンス、衣装ケース等の衣料収納容器内における衣料害虫防除に適した防虫材に関する。
【０００２】
【従来の技術】
いわゆるピレスロイド系化合物の一種であるエムペントリンを有効成分として、これをマットや紙に含浸させた薬剤含浸体を、プラスチック製の枠体に収納した防虫材は、パラジクロロベンゼン、ショウノウ等を用いる防虫材に比し、衣料に対する高い防虫性能のみならず、無臭性の点で優れており、また、高い安全性や手頃な価格等とも相俟って、家庭における洋服ダンス、衣装ケース等の衣料用防虫材として広く普及し、もはや汎用日用品と言われるまでに至っている。また一般に、前記した衣料用防虫材におけるプラスチック製の枠体は加工性、価格等の点から汎用樹脂であるポリプロピレン等のオレフィン系樹脂が使用されているが、該オレフィン系樹脂製の枠体を用いると有効成分の一部が該枠体に吸着されることが知られている。
【０００３】
一方近年、エムペントリンに比し、より防虫性能の高い有効成分として同じピレスロイド系化合物の一種である下記一般式（１）

（式中、Ｒは水素原子、メチル基、メトキシ基またはメトキシメチル基を表し、Ｘ，Ｙはそれぞれ独立して塩素原子、水素原子またはメチル基を表す）
で示されるエステル化合物が見出されている。このエステル化合物（１）は極めて高い防虫性能を有するので、従来の防虫材と同等の防虫性能を発揮するために必要となる有効成分の使用量を、例えば従来の約１／３〜１／６程度と低減できることが期待されている。
【０００４】
しかしながら、エステル化合物（１）を前記した衣料用防虫材に適用したところ、衣料用防虫材への使用量を従来のものより低減させた場合には期待されるほどの性能が発揮できないことが判明した。
【０００５】
【発明が解決しようとする課題】
本発明の課題は、エステル化合物（１）を用いる防虫組成物がオレフィン系樹脂からなる枠体に収納されてなる防虫材において、本来有効成分が有する高い防虫性能を有効に発揮させることを可能とし得る衣料用途に適した防虫材を簡便かつ安価に提供することにある。
【０００６】
【課題を解決するための手段】
かかる状況下、本発明者らはエステル化合物（１）を用いる防虫材について検討した結果、エステル化合物（１）を含有する防虫組成物においてクエン酸トリエチルを併用することにより前記課題が解決されることを見出し、本発明を完成した。
【０００７】
すなわち本発明は、一般式（１）で示されるエステル化合物（以下、本化合物と記す。）及びクエン酸トリエチルを含有する防虫組成物がオレフィン系樹脂を基材とする枠体に収納されてなる衣料用防虫材（以下、本防虫材と記す。）に関するものである。
【０００８】
【発明の実施の形態】
本化合物は、例えば特開平１１−２２２４６３号公報、特開２０００−６３３２９号公報、特開２０００−５３５０８号公報、特開２０００−５３６１４号公報、特開２００１−１１０２２号公報、特開昭６３−２０３６４９号公報等に記載の化合物であり、これらの公報に記載の方法または該方法に準じた方法により得ることができる。
【０００９】
本化合物の具体例としては、例えば２，３，５，６−テトラフルオロ−４−メチルベンジル３−（１−プロペニル）−２，２−ジメチルシクロプロパンカルボキシラート（以下、化合物１と記す。）、２，３，５，６−テトラフルオロ−４−メトキシメチルベンジル３−（１−プロペニル）−２，２−ジメチルシクロプロパンカルボキシラート、２，３，５，６−テトラフルオロベンジル３−（２，２−ジクロロビニル）−２，２−ジメチルシクロプロパンカルボキシラート、２，３，５，６−テトラフルオロ−４−メトキシベンジル３−（１−プロペニル）−２，２−ジメチルシクロプロパンカルボキシラートなどが挙げられ、これらは単独でまたは２種以上の混合物で用いることができる。また、光学異性体あるいは幾何異性体が存在する場合は、各異性体の単独、あるいは２種以上の混合物で有りえる。
【００１０】
クエン酸トリエチルは、僅かに特異臭のある無色の液体で、経口投与医薬品や化粧品の原料としても用いられる。アルコールやエステルと相溶性があり、本化合物とも容易に溶け合う。石油エーテルやパラフィン系溶剤には溶け難い。常温でも僅かづつ揮散する性質を有する。
【００１１】
本組成物における本化合物とクエン酸トリエチルとの重量割合は１：０．５〜１：１０であり、クエン酸トリエチルの割合が少なすぎるとオレフィン系樹脂を基材とする枠体への本化合物の吸着防止効果が満足でなくなり、多すぎると本組成物の防虫効果が低下する。好ましくは１：１〜１：５である。。
【００１２】
本組成物の実用的な形態としては、例えば、紙、織布、不織布、パルプ、リンター、木材等の薬液吸収性担体からなる例えばマット状物またはシート状物に、本化合物およびクエン酸トリエチルの混合物を１：０．５〜１：１０の重量割合で含浸させた薬液含浸体や、本化合物とクエン酸トリエチル（重量割合１：０．５〜１：１０）、石油系溶剤の混合物に金属石鹸等のゲル化剤を加えてゲル化させたものが挙げられる。
【００１３】
薬剤含浸体の場合は、本化合物とクエン酸トリエチルとの所定割合の混合物をそのまま、あるいは必要に応じて比較的低沸点のアルコール系やエステル系の溶剤に、本化合物とクエン酸トリエチルの合計量で５〜９０重量％の濃度で溶解させて前記マット状物またはシート状物に滴下することにより含浸させ、前記溶剤に溶解させた場合には、通常はさらに該溶剤を揮散除去する、通常の方法により製造することができる。
【００１４】
また、ＭＧＫ２６４、ピペロニルブトキサイド、サイネピリン５００などのピレスロイド用共力剤、ＢＨＴなどの酸化防止剤、２−（２−ヒドロキシ５−ターシャリーオクチルフェニル）ベンゾトリアゾール（商品名：スミソーブ３４０）などの紫外線吸収剤、香料、チモールなどの殺菌剤、忌避剤、揮散調節剤などの他の成分を必要に応じて本発明の目的を阻害しない範囲で適宜本組成物中に配合することもできる。配合方法としては、例えば本化合物およびクエン酸トリエチルの混合物中に該他の成分を溶解させて、前記と同様に含浸体に含浸させる方法を挙げることができる。
【００１５】
本組成物中の本化合物の量は、本防虫材が使用される空間の大きさ、使用期間等により適宜決めることができる。例えば本組成物が薬剤含浸体の形態の場合には、本防虫材の適用場所、使用期間などにより、必要とされる本化合物の量、そのために使用する含浸体の大きさ、材質等を適宜決められる。より具体的には例えば、５×１０×０．２５ｍｍ（縦×横×厚み）程度の不織布シートを本防虫材に用いたときには、本化合物を３０〜１００ｍｇ含浸させることにより、０．２５〜１ｍ^３程度のタンス内で６ヶ月以上防虫効果を発揮することができる。
【００１６】
上記のように調製した本組成物を、オレフィン系樹脂を基材として成型した枠体に収納して、本防虫材として用いることができる。オレフィン系樹脂を基材とする枠体の形状、大きさは特に限定されるものではないが、例えば、実公昭６３−８２２３に記載のケースに準じた、重積あるいは二つ折りでき、内部に防虫マット収納用の空間を有しメッシュ状に多数の揮散孔を設けたものや、台板上に蓋板を重ねるようにして閉蓋可能とした台板に通気可能にして多数の突条を配列配置させ、かつ中央部には、防虫マット収納用空間を設けたものなど、例えばマット状やシート状の本組成物の略全面が枠体と当接しないような形状を例示することができる。具体的には、図１及び図２に示す枠体を挙げることができる。
【００１７】
該オレフィン系樹脂を基材とする枠体におけるオレフィン系樹脂としては、ポリエチレン、ポリプロピレン、ポリブテン−１、ポリ−４−メチルペンテン−１、エチレン−プロピレン共重合体等のポリオレフィンのみならず、該ポリオレフィンに少量の相溶性を有する他の樹脂、例えばポリ酢酸ビニル、ポリ塩化ビニル等を混合した樹脂ブレンドや、プロピレン−酢酸ビニル共重合体、エチレン−アクリル酸共重合体等を挙げることができる。中でもポリプロピレンが、価格、加工性等の点で広く使用されている。
【００１８】
本防虫材は衣料防虫用途等に使用するまでは、通常、プラスチックフィルム、アルミラミネートフィルムなどに密封保存されるが、高温苛酷条件下においても有効成分の枠体への移行が少なく、使用時に開封取り出し後、タンス、引出し、収納箱などの衣料収納容器内に置くだけで、有効成分を効率的に徐放し、イガ、コイガ、ヒメマルカツオブシムシなどの衣料害虫に対し高い防虫効果を発揮する。
【００１９】
収納容器１ｍ^３あたり本化合物に換算して４０〜２００ｍｇ程度含有する本防虫剤を設置することにより、６ヶ月以上防虫効果を発揮することができる。
【００２０】
【実施例】
次に実施例をあげて本発明を詳細に説明するが、本発明はこれらのみに限定されるものではない。
実施例１
化合物１とクエン酸トリエチルを１：４の比率で混合し、２×５．５ｃｍ、厚さ０．２５ｍｍの不織布に５０ｍｇ（化合物１として１０ｍｇ）滴下した薬液含浸体を図２に記載のポリプロピレン製枠体（外寸６．５×３×０．６５ｃｍ）に収納して本防虫材１を得る。
【００２１】
実施例２
化合物１とクエン酸トリエチルを１：１の比率で混合したものを２０ｍｇ（化合物１として１０ｍｇ）滴下する以外は実施例１と同様に調製し、本防虫材２を得る。
【００２２】
比較例１
化合物１のみを１０ｍｇ滴下する以外は実施例１と同様に調製し、比較用防虫材を得る。
【００２３】
試験例１
直径１２ｃｍ、高さ１０ｃｍのカップ３個に、衣料害虫であるコイガの幼虫を１０匹ずつと、餌用のウール布を入れる。本防虫剤１、本防虫剤２と比較用防虫剤を包装フィルムで密封して６０℃保存庫で２週間保存したものからフィルムを除き、ナイロン網を介して各カップの上に載せ、その上から別のカップで密閉した状態で、１日間放置する。１日後の虫の死亡または苦悶率を観察したところ、結果は以下のとおりであった。
【００２４】
【表１】

【００２５】
【発明の効果】
本発明によれば、本来本化合物が有する高い防虫性能を有効に発揮させ得ることが可能で衣料用途に適した防虫材を簡便かつ安価に提供することができる。
【図面の簡単な説明】
【図１】本防虫材に使用される枠体の一例（洋タンス用）を示す説明図である。
【図２】本防虫材に使用される枠体の別の例（引き出し用）を示す説明図である。[0001]
TECHNICAL FIELD OF THE INVENTION
TECHNICAL FIELD The present invention relates to an insect repellent material, particularly an insect repellent material suitable for controlling insect pests in a clothing storage container such as a clothes dance and a costume case.
[0002]
[Prior art]
Insect repellent material containing empentrin, a kind of so-called pyrethroid compound, as an active ingredient, and impregnated with this in a mat or paper, and contained in a plastic frame, is used as an insect repellent material using paradichlorobenzene, camphor, etc. On the other hand, it is not only excellent in insect repellent performance against clothing, but also excellent in odorlessness, and combined with high safety and affordable price, etc., it is an insect repellent material for clothes such as clothes dance at home and clothes case. It has become so popular that it is no longer widely used. Generally, an olefin resin such as polypropylene, which is a general-purpose resin, is used as the plastic frame in the insect repellent for clothing from the viewpoints of workability, price, and the like. It is known that when used, a part of the active ingredient is adsorbed on the frame.
[0003]
On the other hand, in recent years, the following general formula (1) which is a kind of the same pyrethroid-based compound as an active ingredient having higher insect repellent performance than empentrin

(Wherein, R represents a hydrogen atom, a methyl group, a methoxy group or a methoxymethyl group, and X and Y each independently represent a chlorine atom, a hydrogen atom or a methyl group)
Has been found. Since the ester compound (1) has an extremely high insect repellent performance, the amount of the active ingredient required to exhibit the same insect repellent performance as that of the conventional insect repellent material is reduced to, for example, about 1/3 to 1/6 of the conventional amount. It is expected that it can be reduced to a degree.
[0004]
However, when the ester compound (1) was applied to the insect repellent for clothing described above, it was found that when the amount used for the insect repellent for clothing was reduced from that of the conventional one, the performance as expected could not be exhibited. did.
[0005]
[Problems to be solved by the invention]
An object of the present invention is to make it possible to effectively exhibit the high insect repellent performance originally possessed by an active ingredient in an insect repellent material in which an insect repellent composition using an ester compound (1) is housed in a frame made of an olefin resin. An object of the present invention is to provide a simple and inexpensive insect repellent material suitable for use in clothing.
[0006]
[Means for Solving the Problems]
Under such circumstances, the present inventors have studied an insect repellent material using the ester compound (1). As a result, the problem can be solved by using triethyl citrate in combination with the insect repellent composition containing the ester compound (1). And completed the present invention.
[0007]
That is, the present invention provides an insect repellent composition containing an ester compound represented by the general formula (1) (hereinafter, referred to as the present compound) and triethyl citrate, which is housed in a frame having an olefin resin as a base material. The present invention relates to an insect repellent material for clothing (hereinafter referred to as the present insect repellent material).
[0008]
BEST MODE FOR CARRYING OUT THE INVENTION
The present compound is described in, for example, JP-A-11-222463, JP-A-2000-63329, JP-A-2000-53508, JP-A-2000-53614, JP-A-2001-11022, and JP-A-63-163. It is a compound described in JP-A-203649 or the like, and can be obtained by a method described in these publications or a method analogous to the method.
[0009]
As a specific example of the present compound, for example, 2,3,5,6-tetrafluoro-4-methylbenzyl 3- (1-propenyl) -2,2-dimethylcyclopropanecarboxylate (hereinafter, referred to as compound 1). 2,3,5,6-tetrafluoro-4-methoxymethylbenzyl 3- (1-propenyl) -2,2-dimethylcyclopropanecarboxylate, 2,3,5,6-tetrafluorobenzyl 3- (2 , 2-Dichlorovinyl) -2,2-dimethylcyclopropanecarboxylate, 2,3,5,6-tetrafluoro-4-methoxybenzyl 3- (1-propenyl) -2,2-dimethylcyclopropanecarboxylate and the like These can be used alone or in a mixture of two or more. When an optical isomer or a geometric isomer is present, each isomer may be used alone or a mixture of two or more thereof.
[0010]
Triethyl citrate is a colorless liquid with a slightly peculiar odor, and is also used as a raw material for orally administered drugs and cosmetics. It is compatible with alcohols and esters and easily dissolves with this compound. Insoluble in petroleum ether and paraffinic solvents. It has the property of evaporating little by little even at room temperature.
[0011]
The weight ratio of the present compound to triethyl citrate in the present composition is from 1: 0.5 to 1:10, and when the proportion of triethyl citrate is too small, the present compound to a frame based on an olefin resin is used. Is not satisfactory, and if too large, the insect repellent effect of the present composition decreases. Preferably it is 1: 1 to 1: 5. .
[0012]
Practical forms of the composition include, for example, paper, woven fabric, nonwoven fabric, pulp, linter, and a mat-like or sheet-like material composed of a drug-absorbing carrier such as wood. Chemical mixture impregnated with the mixture at a weight ratio of 1: 0.5 to 1:10, or a mixture of the present compound, triethyl citrate (weight ratio 1: 0.5 to 1:10), and a petroleum-based solvent Examples thereof include those gelled by adding a gelling agent such as soap.
[0013]
In the case of a drug-impregnated product, a mixture of the present compound and triethyl citrate in a predetermined ratio as it is or, if necessary, in a relatively low-boiling alcohol-based or ester-based solvent, is added to the total amount of the present compound and triethyl citrate. When dissolved in a concentration of 5 to 90% by weight and dropped into the mat-like material or sheet-like material to be impregnated and dissolved in the solvent, the solvent is usually further volatilized and removed. It can be manufactured by a method.
[0014]
In addition, synergists for pyrethroids such as MGK264, piperonyl butoxide, and sinepiline 500; antioxidants such as BHT; 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole (trade name: Sumisorb 340); Other components such as an ultraviolet absorber, a perfume, a bactericide such as thymol, a repellent, a volatilization regulator, and the like can be appropriately incorporated into the composition as needed within a range not to impair the purpose of the present invention. Examples of the compounding method include a method of dissolving the other components in a mixture of the present compound and triethyl citrate and impregnating the impregnated body in the same manner as described above.
[0015]
The amount of the present compound in the present composition can be appropriately determined according to the size of the space in which the present insect-controlling material is used, the period of use, and the like. For example, when the present composition is in the form of a drug impregnated body, the amount of the required compound, the size of the impregnated body used for the purpose, the material, etc. are appropriately determined depending on the application place of the insect repellent material, the period of use, and the like. I can decide. More specifically, for example, when a nonwoven fabric sheet of about 5 × 10 × 0.25 mm (length × width × thickness) is used as the insect repellent material, 30 to 100 mg of the present compound is impregnated to obtain 0.25 to 1 m ^The insect repellent effect can be exhibited for 6 months or more in a closet of about ³ or more.
[0016]
The present composition prepared as described above can be housed in a frame molded using an olefin-based resin as a base material and used as the present insect repellent material. The shape and size of the frame made of an olefin-based resin as a base material are not particularly limited. For example, according to the case described in Japanese Utility Model Publication No. 63-8223, the product can be stacked or folded in two, and an insect repellent is provided inside. Arrangement of a large number of ridges by allowing ventilation to be provided on a base plate that has a space for mat storage and has many volatile holes in a mesh shape and a lid plate that can be closed by stacking a lid plate on a base plate For example, a shape in which substantially the entire surface of the present composition in the form of a mat or a sheet does not come into contact with the frame, for example, one in which a space for accommodating insect repellent mats is provided in the center portion, and the like, can be exemplified. Specifically, the frame shown in FIGS. 1 and 2 can be mentioned.
[0017]
Examples of the olefin resin in the frame based on the olefin resin include not only polyolefins such as polyethylene, polypropylene, polybutene-1, poly-4-methylpentene-1, and ethylene-propylene copolymer, but also the polyolefins. And a resin blend in which a small amount of other resins having compatibility, for example, polyvinyl acetate, polyvinyl chloride, and the like are mixed, a propylene-vinyl acetate copolymer, an ethylene-acrylic acid copolymer, and the like. Among them, polypropylene is widely used in terms of price, processability, and the like.
[0018]
The insect repellent material is usually sealed and stored in a plastic film, aluminum laminated film, etc. until it is used for clothing insect repellent, etc., but the active ingredient does not easily transfer to the frame even under high temperature and severe conditions, and it is opened when used. After being taken out, the active ingredient is released slowly and efficiently by simply placing it in a clothing storage container such as a closet, drawer, or storage box, and exerts a high insect repellent effect on clothing pests such as iga, kiga and himemarukatsuobushimushi.
[0019]
By installing this insect repellent containing about 40~200mg in terms of the compound per container 1 m ^3, it is possible to exert insect repellent six months or more.
[0020]
【Example】
Next, the present invention will be described in detail with reference to examples, but the present invention is not limited thereto.
Example 1
Compound 1 and triethyl citrate were mixed at a ratio of 1: 4, and 50 mg (10 mg as compound 1) was dropped on a non-woven fabric having a size of 2 × 5.5 cm and a thickness of 0.25 mm. The insect repellent material 1 is obtained by being housed in a frame (external size 6.5 × 3 × 0.65 cm).
[0021]
Example 2
Except that 20 mg (10 mg as compound 1) of a mixture of compound 1 and triethyl citrate at a ratio of 1: 1 was dropped, the same preparation as in Example 1 was carried out to obtain the insect repellent material 2.
[0022]
Comparative Example 1
Except for dropping only 10 mg of compound 1, the same preparation as in Example 1 is performed to obtain a comparative insect repellent.
[0023]
Test example 1
Into three cups 12 cm in diameter and 10 cm in height, 10 larvae of kiga moth, which are clothing pests, and a wool cloth for feeding are put. The insect repellent 1, the insect repellent 2 and the comparative insect repellent were sealed with a packaging film and stored in a storage at 60 ° C. for 2 weeks. Then, the film was removed and placed on each cup via a nylon net. And leave it closed for another day in a sealed state with another cup. Observation of the mortality or agony rate of the insects one day later showed the following results.
[0024]
[Table 1]

[0025]
【The invention's effect】
ADVANTAGE OF THE INVENTION According to this invention, the high insect repellency which this compound originally has can be exhibited effectively, and the insect repellent material suitable for clothing use can be provided simply and inexpensively.
[Brief description of the drawings]
FIG. 1 is an explanatory view showing an example of a frame (for a Western chest) used in the present insect repellent material.
FIG. 2 is an explanatory view showing another example (for drawing) of a frame used for the insect repellent material.

Claims

General formula (1)

(Wherein, R represents a hydrogen atom, a methyl group, a methoxy group or a methoxymethyl group, and X and Y each independently represent a chlorine atom, a hydrogen atom or a methyl group)
An insect repellent material comprising an insect repellent composition containing the ester compound represented by the formula (1) and triethyl citrate at a weight ratio of 1: 0.5 to 1:10, which is housed in a frame made of an olefin resin.

When the ester compound (1) is 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 The compound according to claim 1, which is at least one selected from -dimethylcyclopropanecarboxylate and 2,3,5,6-tetrafluorobenzyl 3- (2,2-dichlorovinyl) -2,2-dimethylcyclopropanecarboxylate. Insect repellent material as described.

The insect repellent material according to claim 1 or 2, wherein the content ratio by weight of the ester compound (1) and triethyl citrate in the composition is from 1: 1 to 1: 5.

The insect repellent composition containing the ester compound (1) and triethyl citrate is a drug solution-impregnated body obtained by impregnating a mixture of the ester compound (1) and triethyl citrate into a drug solution-absorbing carrier. Insect repellent material described in Crab.

A method for controlling insect pests on clothing, comprising installing the insect repellent material according to any one of claims 1 to 4 in a clothing storage container.