JP2006036759A - Insect repellent and insect-repelling device and method using the same - Google Patents

Insect repellent and insect-repelling device and method using the same Download PDF

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JP2006036759A
JP2006036759A JP2005181375A JP2005181375A JP2006036759A JP 2006036759 A JP2006036759 A JP 2006036759A JP 2005181375 A JP2005181375 A JP 2005181375A JP 2005181375 A JP2005181375 A JP 2005181375A JP 2006036759 A JP2006036759 A JP 2006036759A
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insect repellent
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JP4890798B2 (en
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Kazuyoshi Funabashi
一良 船橋
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ST Chemical Co Ltd
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Abstract

<P>PROBLEM TO BE SOLVED: To provide an insect repellent which is highly effective to repel harmful insects, is quite safe for human health, is highly stable, and is capable of being simply used even at home. <P>SOLUTION: The insect repellent contains a silicone compound as an active ingredient. The insect repellent is embodied by one wherein the silicone compound is volatile. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

本発明は、防虫剤、防虫器及び防虫方法に関し、さらに詳細には、例えばイガ、コイガ等の繊維害虫やノシメマダラメイガ等の穀物害虫等の害虫等による被害を防ぐ防虫剤、防虫器及び防虫方法に関する。   The present invention relates to an insect repellent, an insect repellent, and an insect repellent method, and more specifically, an insect repellent, an insect repellent, and an insect repellent that prevent damage caused by pests such as fiber pests such as moths and moths, and grain pests such as scallop Regarding the method.

従来より、様々な害虫に対する防虫剤は種々提案されており、近年ではピレスロイド系化合物等が防虫剤として知られ、広く使用されている(例えば特許文献1)。しかしながら、これらのピレスロイド系防虫剤は、安全性や安定性の点で、十分に満足のいくものではなかった。   Conventionally, various insect repellents against various pests have been proposed. In recent years, pyrethroid compounds and the like are known and widely used as insect repellents (for example, Patent Document 1). However, these pyrethroid insect repellents were not fully satisfactory in terms of safety and stability.

また、安全性の高い天然成分や食品成分が、防虫剤として使用されることも公知である。例えば、わさび、カラシ、ショウガ、トウガラシ、ニンニク等を使用した米用の防虫剤(特許文献2)や、シネオールを有効成分として含有する繊維製品の防虫剤(特許文献3)、l―カルボン又はl−カルボンを含む精油及びリナロール及び/又はアネトールを有効成分として含有する芳香性防虫剤(特許文献4)が知られている。   It is also known that highly safe natural ingredients and food ingredients are used as insect repellents. For example, an insect repellent for rice using horseradish, mustard, ginger, pepper, garlic, etc. (Patent Document 2), an insect repellent for fiber products containing cineol as an active ingredient (Patent Document 3), l-carvone or l -An aromatic insect repellent (Patent Document 4) containing an essential oil containing carvone and linalool and / or anethole as active ingredients is known.

しかしながら、これらの防虫剤は、天然物又は食品に用いられている薬剤を使用しているため、安全性については問題ないが、害虫に対しての防虫効果が弱く、十分な防虫効力が得られないという問題を有していた。   However, since these insect repellents use chemicals used in natural products or foods, there is no problem with safety, but the insect repellent effect against pests is weak and sufficient insect repellent effect is obtained. Had no problem.

一方、シリコーン系化合物を防虫剤中に配合することも知られている。しかしながら、防虫剤中にシリコーン系化合物を配合する理由は、特定の揮散性薬剤成分の揮散を抑制して、防虫効果の長期持続性を目的としたものであったり(特許文献5、6)、人体用害虫忌避剤において、皮膚からの揮散防止、擦過及び汗水による流れだしを防止して、持続性と使用感を向上させたもの(特許文献7)や、特定の薬剤の変色・変質防止を目的としたもの(特許文献8)であり、これらは何れもシリコーン系化合物自身の防虫効果を利用したものではなかった。
特開昭63−203649号公報 特開平 6−038678号公報 特開昭57―062204号公報 特開昭55―129204号公報 特開昭53−107418号公報 特開昭63−316706号公報 特開平 4―244001号公報 特開平 7―206615号公報
On the other hand, it is also known to blend a silicone compound in an insect repellent. However, the reason why the silicone compound is blended in the insect repellent is to suppress the volatilization of a specific volatilizing drug component and aim at long-term sustainability of the insect repellent effect (Patent Documents 5 and 6). In the pest repellent for human body, prevention of volatilization from the skin, prevention of chafing and run-out due to sweat, improved durability and feeling of use (Patent Document 7), and prevention of discoloration and alteration of specific drugs These were intended (Patent Document 8), and none of them utilized the insecticidal effect of the silicone compound itself.
JP-A-63-203649 Japanese Patent Laid-Open No. 6-038678 JP-A-57-062024 JP-A-55-129204 JP-A-53-107418 JP-A-63-3316706 JP-A-4-244001 JP-A-7-206615

従って、害虫に対して十分な防虫効力を有するとともに、人体に対して安全性が高いとともに安定性も高く、一般家庭でも手軽に使用できる防虫剤の開発が望まれており、このような防虫剤の提供が本発明の課題である。   Accordingly, it is desired to develop an insect repellent that has a sufficient insect repellent effect against pests, is highly safe and stable to the human body, and can be easily used in general households. Is the subject of the present invention.

本発明者は、上記課題を解決するために鋭意研究を行ったところ、従来より種々の化粧品や工業製品に利用されているシリコーン系化合物の中に優れた防虫効力を有するものが存在することを見いだし本発明に至った。   The present inventor has conducted intensive research to solve the above-mentioned problems. As a result, it has been found that some silicone compounds that have been used in various cosmetics and industrial products have an excellent insecticidal effect. As a result, the present invention has been achieved.

すなわち、本発明は、シリコーン系化合物を有効成分として含有することを特徴とする防虫剤を提供するものである。   That is, the present invention provides an insect repellent comprising a silicone compound as an active ingredient.

また本発明は、上記防虫剤を、常温自然蒸散、加熱蒸散、送風蒸散、薫蒸又は噴霧により環境中に放出させる構造を有する防虫器を提供するものである。   Moreover, this invention provides the insect repellent which has the structure which discharge | releases the said insect repellent in an environment by normal temperature natural transpiration, heating transpiration, ventilation transpiration, fumigation, or spraying.

本発明防虫剤の有効成分であるシリコーン系化合物は、害虫や害虫の卵に対して優れた防虫効果を発揮するものであり、しかも従来より化粧品等に使用されているものであるため、人体に対して安全であり、安定性も高いものである。従って、本発明防虫剤は、一般家庭においても手軽に使用できるものである。   The silicone compound, which is an active ingredient of the insect repellent of the present invention, exhibits an excellent insect repellent effect against pests and pest eggs, and has been conventionally used in cosmetics and the like. It is safe and highly stable. Therefore, the insect repellent of the present invention can be easily used in general households.

本発明において、「防虫」とは、下記の作用を含む概念である。
(1)害虫の卵の孵化を抑制する孵化抑制作用
(2)孵化した若齢幼虫を死滅させる若齢幼虫の殺虫作用
(3)害虫を忌避する忌避作用
(4)害虫を死滅させる殺虫作用
(5)害虫の増殖を抑制する増殖抑制作用
In the present invention, “insect protection” is a concept including the following actions.
(1) Inhibitory action to suppress hatching of pest eggs (2) Insecticidal action of young larvae to kill young larvae hatched (3) Repellent action to repel pests (4) Insecticidal action to kill pests ( 5) Growth inhibitory action that suppresses the growth of pests

本発明の防虫剤は、その有効成分としてシリコーン系化合物の1種又は2種以上を含有するものである。   The insect repellent of this invention contains the 1 type (s) or 2 or more types of a silicone type compound as the active ingredient.

本発明の防虫剤において、有効成分として使用されるシリコーン系化合物は、上記した意味での防虫作用を有するものであれば特に限定されず、環境中に放出して使用する場合は揮散性が高いものが好ましく、液体又は固体状態で害虫又は害虫の卵に接触させて使用する場合は揮散性が低いものが好ましい。ここで揮散性とは、常温ないしある程度の加熱条件下で気化する性質を意味する。環境中に放出して使用する場合は、揮散性が高いもの、すなわち常圧における沸点が350℃以下のものが好ましく、300℃以下のものが更に好ましく、250℃以下のものが特に好ましい。逆に液体又は固体状態で害虫又は害虫の卵に接触させて使用する場合は、揮散性が低いもの、すなわち常圧における沸点が250℃以上のものが好ましく、300℃以上のものが更に好ましく、350℃以上のものが特に好ましい。   In the insect repellent of the present invention, the silicone compound used as an active ingredient is not particularly limited as long as it has an insect repellent effect in the above sense, and has high volatility when used by being released into the environment. Those having low volatility are preferred when used in contact with a pest or a pest egg in a liquid or solid state. Here, the volatility means a property of vaporizing under normal temperature or a certain heating condition. When released into the environment and used, those having high volatility, that is, those having a boiling point of 350 ° C. or less at normal pressure, more preferably 300 ° C. or less, and particularly preferably 250 ° C. or less are preferred. Conversely, when used in contact with a pest or a pest egg in a liquid or solid state, those having low volatility, that is, those having a boiling point of 250 ° C. or higher at normal pressure, more preferably those of 300 ° C. or higher, A temperature of 350 ° C. or higher is particularly preferable.

また、揮発性でないシリコーン系化合物であっても、害虫又は害虫の卵にこのシリコーン系化合物を接触させることができれば防虫効果を発揮させることができ、防虫剤として使用できる。   Moreover, even if it is a non-volatile silicone type compound, if this silicone type compound can be made to contact a pest or a pest egg, an insecticidal effect can be exhibited and it can be used as an insecticide.

本発明の防虫剤において、有効成分として好ましく使用されるシリコーン系化合物としは、次の式(1)で表されるものを挙げることができる。

Figure 2006036759
[式中、R、R及びRは異なっていてもよい水素原子、フェニル基又は式(2)

−X−R' ・・・・・(2)
(式中、Xは炭素数1〜10のアルキレン基又は酸素原子を示し、R'は水素原子、フェニル基、エポキシ基、アミノ基、カルボキシル基、水酸基、トリフルオロメチル基、トリメチルシリル基、−(OC−(OCOR''(a及びbは異なっていてもよい0〜10の自然数であり、R''は炭素数1〜10のアルキル基である)又は−NH−(CH−NH(cは1〜10の自然数である)を示す)を示し、m、n及びoは異なっていてもよい0〜100の自然数を示す] In the insect repellent of the present invention, examples of the silicone compound preferably used as an active ingredient include those represented by the following formula (1).
Figure 2006036759
[Wherein R 1 , R 2 and R 3 may be different from each other, a hydrogen atom, a phenyl group or formula (2)

-XR '(2)
(In the formula, X represents an alkylene group having 1 to 10 carbon atoms or an oxygen atom, and R ′ represents a hydrogen atom, phenyl group, epoxy group, amino group, carboxyl group, hydroxyl group, trifluoromethyl group, trimethylsilyl group, — ( OC 2 H 4 ) a- (OC 3 H 6 ) b OR ″ (a and b are natural numbers of 0 to 10 which may be different, and R ″ is an alkyl group having 1 to 10 carbon atoms) Or —NH— (CH 2 ) c —NH 2 (where c is a natural number of 1 to 10), and m, n, and o are 0 to 100, which may be different.]

この式(1)で表されるシリコーン系化合物のうち、特に好ましいものは、下記式(5)又は式(6)で表されるものである。

Figure 2006036759
(式中、Rは水素原子、炭素数1〜10のアルキル基又はフェニル基を示し、sは0〜100の自然数を示す) Of the silicone compounds represented by the formula (1), particularly preferred are those represented by the following formula (5) or formula (6).
Figure 2006036759
(In the formula, R represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a phenyl group, and s represents a natural number of 0 to 100)

Figure 2006036759
(式中、tは1〜100の自然数を示す)
Figure 2006036759
(Wherein t represents a natural number of 1 to 100)

このうちでも、式(5)において、Rがメチル基であるものが更に好ましい。これらのものは特に限定されないが、防虫剤の調製のしやすさの点から、25℃での運動粘度が500mm/sec以下のものを用いることが好ましく、10mm/sec以下の物を用いることが特に好ましい。 Among these, in formula (5), it is more preferable that R is a methyl group. These are not particularly limited, but from the viewpoint of easy preparation of insect repellents, it is preferable to use those having a kinematic viscosity at 25 ° C. of 500 mm 2 / sec or less, and those having 10 mm 2 / sec or less are used. It is particularly preferred.

また、下記式(3)で表されるシリコーン系化合物も本発明防虫剤の有効成分として好ましい。

Figure 2006036759
[式中、Y及びZは異なっていてもよい炭素数1〜10のアルキレン基、フェニレン基又は単結合を示し、Rはメチル基又は水酸基を示し、Rはメチル基又は−(CH−NH−(CH−NH(d及びeは異なっていてもよい1〜10の自然数である)を示し、p及びqは異なっていてもよい0〜100の自然数を示す] Moreover, the silicone type compound represented by following formula (3) is also preferable as an active ingredient of this invention insect repellent.
Figure 2006036759
[Wherein, Y and Z each represent an optionally substituted alkylene group having 1 to 10 carbon atoms, a phenylene group or a single bond, R 4 represents a methyl group or a hydroxyl group, and R 5 represents a methyl group or — (CH 2 ) D -NH- (CH 2 ) e -NH 2 (d and e are natural numbers of 1 to 10 which may be different), and p and q represent natural numbers of 0 to 100 which may be different. ]

更にまた、下記式(4)で表されるシリコーン系化合物も本発明防虫剤の有効成分として好ましい。

Figure 2006036759
(式中、Rはメチル基又はフェニル基を示し、Rはメチル基、フェニル基又はビニル基を示し、rは3〜20の自然数を示す) Furthermore, a silicone compound represented by the following formula (4) is also preferable as an active ingredient of the insect repellent of the present invention.
Figure 2006036759
(In the formula, R 6 represents a methyl group or a phenyl group, R 7 represents a methyl group, a phenyl group, or a vinyl group, and r represents a natural number of 3 to 20)

式(4)で表される化合物のうち、特に好ましいものは、rが4〜6の自然数である化合物である。また、R及びRが共にメチル基であるものが特に好ましい。 Of the compounds represented by formula (4), particularly preferred are compounds in which r is a natural number of 4-6. Moreover, it is particularly preferable that both R 6 and R 7 are methyl groups.

上記シリコーン系化合物のうち、式(1)で表されるものの具体例としては、例えば、ヘキサメチルジシロキサン、オクタメチルトリシロキサン、デカメチルテトラシロキサン、ジメチルポリシロキサン、メチルハイドロジェンポリシロキサン、メチルフェニルポリシロキサン、3,3−ジフェニルヘキサメチルポリシロキサン、ポリオキシエチレンメチルポリシロキサン共重合体、ポリ(オキシエチレン−オキシプロピレン)メチルポリシロキサン共重合体、ラウリルメチコンコポリオール等を挙げることができる。これらの具体的商品名としては、SF8411、SF8413、SF8416、SF8417、SF8418、SF8428、SF8419、SF8421、SF8410、SF8451、SF8452、FS1265、SH200、SH203、SH556、SH3746、SH230、SH3749、SH3771、SH8400、SH8700、SH3772M、SH3771M、SH3773M、SH3775M、SH1107(何れも東レ・ダウコーニング・シリコーン(株)社製)等を挙げることができる。   Among the silicone compounds, specific examples of those represented by the formula (1) include, for example, hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, dimethylpolysiloxane, methylhydrogenpolysiloxane, and methylphenyl. Examples thereof include polysiloxane, 3,3-diphenylhexamethylpolysiloxane, polyoxyethylenemethylpolysiloxane copolymer, poly (oxyethylene-oxypropylene) methylpolysiloxane copolymer, and laurylmethicone copolyol. These specific product names include SF8411, SF8413, SF8416, SF8417, SF8418, SF8428, SF8419, SF8421, SF8410, SF8451, SF8452, FS1265, SH200, SH203, SH556, SH3746, SH230, H37S, H8S SH3772M, SH3771M, SH3773M, SH3775M, and SH1107 (all manufactured by Toray Dow Corning Silicone Co., Ltd.).

また、式(3)で表されるシリコーン系化合物の具体例としては、例えば、アミノメチルアミノプロピルシロキサンジメチルシロキサン共重合体等を挙げることができ、これらの具体的な商品名としては、SF8427、SM8704C(何れも東レ・ダウコーニング・シリコーン(株)製)等を挙げることができる。   Specific examples of the silicone compound represented by the formula (3) include, for example, aminomethylaminopropylsiloxane dimethylsiloxane copolymer and the like. Specific examples of these product names include SF8427, SM8704C (both manufactured by Toray Dow Corning Silicone Co., Ltd.).

更に、式(4)で表されるシリコーン系化合物の具体例としては、例えば、ヘキサメチルシクロトリシロキサン、オクタメチルシクロテトラシロキサン、デカメチルシクロペンタシロキサン、1,3,5,7―テトラメチルテトラビニルシクロテトラシロキサン、1,3,5,7,9―ペンタメチルペンタビニルシクロペンタシロキサン、オクタフェニルシクロテトラシロキサン、1,3,5,7,9―ペンタメチルペンタフェニルシクロペンタシロキサン等を挙げることができ、これらの具体的な商品名としては、SH244、SH245、SH344、DC345、DC246(何れも東レ・ダウコーニング・シリコーン(株)製)等を挙げることができる。   Furthermore, specific examples of the silicone compound represented by the formula (4) include, for example, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, 1,3,5,7-tetramethyltetra List vinylcyclotetrasiloxane, 1,3,5,7,9-pentamethylpentavinylcyclopentasiloxane, octaphenylcyclotetrasiloxane, 1,3,5,7,9-pentamethylpentaphenylcyclopentasiloxane, etc. Specific examples of these trade names include SH244, SH245, SH344, DC345, and DC246 (all manufactured by Toray Dow Corning Silicone Co., Ltd.).

上記シリコーン系化合物は、その濃度が、防虫剤全体に対して、0.1〜100質量%(以下「%」と略記する)となるように配合することが好ましく、1〜100%となるように配合することが特に好ましい。更に好ましくは、10〜100%である。   The silicone compound is preferably blended so that the concentration thereof is 0.1 to 100% by mass (hereinafter abbreviated as “%”) with respect to the whole insect repellent, and 1 to 100%. It is particularly preferable to blend in More preferably, it is 10 to 100%.

本発明の防虫剤は、有効成分として上記シリコーン系化合物の1種又は2種以上を組み合わせて使用し、常法により製剤化することにより製造される。本発明の防虫剤において使用するシリコーン系化合物は、適用する害虫、用途、剤の形態、使用方法等によって種々選択することができる。   The insect repellent of the present invention is produced by using one or two or more of the above silicone compounds as active ingredients in combination and formulating them by a conventional method. The silicone compound used in the insect repellent of the present invention can be variously selected depending on the pest to be applied, the purpose, the form of the agent, the method of use and the like.

また、本発明の防虫剤は、上記シリコーン系化合物を単独の有効成分として製剤化してもよいが、更に適当な物質を配合させて常法により製剤化することにより調製することが好ましい。本発明の防虫剤の剤型としては、特に限定はなく、液剤、ゲル剤、固形剤等の形態にすることができる。   In addition, the insect repellent of the present invention may be formulated as the above-mentioned silicone compound as a single active ingredient, but is preferably prepared by blending an appropriate substance and formulating it by a conventional method. There is no limitation in particular as a dosage form of the insect repellent of this invention, It can be set as forms, such as a liquid agent, a gel agent, and a solid agent.

液剤の剤形である本発明の防虫剤としては、シリコーン系化合物単独若しくはこれと他の防虫成分を組み合わせた混合液の形態であっても、シリコーン系化合物単独若しくはこれに他の防虫成分を加え、適当な溶媒に溶解した形態であっても良い。   The insect repellent of the present invention, which is a liquid dosage form, includes a silicone compound alone or a mixture of other insect repellent ingredients in combination with a silicone compound alone or other insect repellent ingredients added thereto. A form dissolved in an appropriate solvent may be used.

液剤を調製するために使用できる溶媒としては、特に限定されずに従来より公知の液状担体を用いることができるが、身体に対して安全性の高い物を使用することが好ましい。具体的には、水;ヘキサン、パラフィン等の炭化水素系化合物;メタノール、エタノール、1−プロパノール、2−プロパノール、1−ブタノール、2−ブタノール、2−メチル−1−プロパノール、2−メチル−2−プロパノール、ペンタノール、ヘキサノール、ヘプタノール、オクタノール、ノナノール、デカノール等のアルキルアルコール類;アリルアルコール等のアルケニルアルコール類;ベンジルアルコール等の芳香族環含有アルコール類;オイゲノール等のフェノール類;クロロホルム等のハロゲン化炭化水素化合物;ジエチルエーテル、ジエチレングリコールジエチルエーテル等のエーテル系化合物;アセトン等のケトン系化合物;酢酸、オレイン酸等の脂肪酸系化合物;酢酸エステル、プロピオン酸エステル、安息香酸エステル等のエステル系化合物;エチレングリコール、プロピレングリコール等のグリコール系化合物;2−フェノキシエタノール、3−メチル−3−メトキシブタノール等のグリコールエーテル系化合物;ごま油、リノール油、サラダ油等の植物油等が挙げられ、これらの1種又は2種以上を混合して用いられる。   The solvent that can be used to prepare the liquid agent is not particularly limited, and a conventionally known liquid carrier can be used, but it is preferable to use a substance that is highly safe for the body. Specifically, water; hydrocarbon compounds such as hexane and paraffin; methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-methyl-2 Alkyl alcohols such as propanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol; alkenyl alcohols such as allyl alcohol; aromatic ring-containing alcohols such as benzyl alcohol; phenols such as eugenol; halogens such as chloroform Hydrocarbon compounds; ether compounds such as diethyl ether and diethylene glycol diethyl ether; ketone compounds such as acetone; fatty acid compounds such as acetic acid and oleic acid; acetates, propionates, benzoates Ester compounds such as ethylene; glycol compounds such as ethylene glycol and propylene glycol; glycol ether compounds such as 2-phenoxyethanol and 3-methyl-3-methoxybutanol; vegetable oils such as sesame oil, linoleic oil and salad oil These 1 type or 2 types or more are mixed and used.

これらの溶媒は、防虫剤全体に対して、0.1〜99.9%となるように配合することが好ましく、1〜99%となるように配合することが特に好ましい。更に好ましくは、10〜90%である。   These solvents are preferably blended in an amount of 0.1 to 99.9%, particularly preferably 1 to 99%, based on the whole insect repellent. More preferably, it is 10 to 90%.

この液剤の調製に当たっては、必要により界面活性剤を添加することもできる。使用できる界面活性剤としては、陽イオン系界面活性剤、陰イオン系界面活性剤、両性界面活性剤、非イオン系界面活性剤等の従来公知の界面活性剤が挙げられ、これらの1種を単独で、又は2種以上を組み合わせて使用することができる。   In preparing this solution, a surfactant can be added as necessary. Examples of the surfactant that can be used include conventionally known surfactants such as cationic surfactants, anionic surfactants, amphoteric surfactants, and nonionic surfactants. It can be used alone or in combination of two or more.

また本発明の防虫剤は、上記した液剤を適当な担体に含浸、担持させて、固形状又はシート状の固形剤とすることができる。担持させる担体としては特に限定されないが、例えば、木、紙、織布、不織布、シリカ、タルク、活性炭、シリカゲル、ゼオライト、セルロースビーズ、活性炭、セラミック等を挙げることができる。   In addition, the insect repellent of the present invention can be made into a solid or sheet-like solid agent by impregnating and supporting the above liquid agent on a suitable carrier. The carrier to be supported is not particularly limited, and examples thereof include wood, paper, woven fabric, non-woven fabric, silica, talc, activated carbon, silica gel, zeolite, cellulose beads, activated carbon, ceramic and the like.

更に本発明の防虫剤は、上記した液剤をゲル化剤でゲル化させたゲル剤とすることができる。このゲル化剤としては、従来公知のものが挙げられ、例えば、カラギーナン、ジェランガム、寒天、ゼラチン、グアーガム、ペクチン、ローカストビーンガム、キサンタンガム、アルギン酸ソーダ、セルロース誘導体、ジベンジリデン−D−ソルビトール、ヒドロキシプロピル化多糖類、ステアリン酸イヌリン、アクリル酸ナトリウム等の高吸水性樹脂等が挙げられ、これらは1種又は2種以上を混合して使用することができる。   Furthermore, the insect repellent of this invention can be made into the gel agent which gelatinized the above-mentioned liquid agent with the gelatinizer. Examples of the gelling agent include conventionally known ones such as carrageenan, gellan gum, agar, gelatin, guar gum, pectin, locust bean gum, xanthan gum, sodium alginate, cellulose derivative, dibenzylidene-D-sorbitol, hydroxypropyl. Superabsorbent polysaccharides such as modified polysaccharides, inulin stearate, sodium acrylate and the like can be used, and these can be used alone or in combination of two or more.

上記のようにして得られる本発明防虫剤の好ましい使用方法としては、本発明の防虫剤に有効成分として含まれるシリコーン系化合物を環境中に放出させて使用する方法が挙げられる。環境中に放出させる方法としては、液剤、固型剤、ゲル剤等の本発明防虫剤を、常温で自然に蒸散させる方法や、強制的に蒸散させる方法が挙げられる。強制的に蒸散させる方法としては、加熱による蒸散、送風による蒸散、薫蒸による蒸散等が挙げられる。また、環境中に放出させる方法として噴霧による方法等を使用しても良い。   A preferred method of using the insect repellent of the present invention obtained as described above includes a method in which a silicone compound contained as an active ingredient in the insect repellent of the present invention is released into the environment. Examples of the method for releasing into the environment include a method of spontaneously evaporating the insect repellent of the present invention such as a liquid agent, a solid agent and a gel agent, and a method of forcibly evaporating. Examples of the method of forcibly evaporating include transpiration by heating, transpiration by air blowing, and transpiration by fumigation. Moreover, you may use the method by spraying, etc. as a method of releasing in an environment.

上記の強制的蒸散方法のうち、加熱による蒸散は、例えば、実開平2-78077号等に開示されているような、薬液ボトル内に収納した防虫剤を吸い上げ芯で吸い上げ、吸い上げ芯の上部等を加熱ヒーターで加熱することにより蒸散させるようにした加熱蒸散器や、実開平1−116072号等に開示されているようなマット状の含浸体に防虫剤を含浸し、このマットを加熱ヒーター上に載置することにより蒸散させるようにした加熱蒸散器等を用いて行うことができる。   Among the above-mentioned forced transpiration methods, transpiration by heating, for example, as disclosed in Japanese Utility Model Publication No. 2-78077 etc., sucks up an insect repellent housed in a chemical solution bottle with a suction core, the upper part of the suction core, etc. An insecticide is impregnated into a heating evaporator that is evaporated by heating with a heater, or a mat-like impregnated body as disclosed in Japanese Utility Model Laid-Open No. 1-116072, and the mat is placed on the heater. It can be carried out using a heating transpiration device or the like adapted to evaporate by being placed on.

また、送風による蒸散は、例えば、特開平11―308955号公報等に開示されているような薬剤保持体と送風機を備え、その薬剤保持体に送風機により発生する気流を接触させることで、防虫剤を放出口から環境中に放出するファン式防虫装置等を用いて行うことができる。   In addition, transpiration by blowing is provided with a medicine holder and a blower as disclosed in, for example, JP-A-11-308955, and an insect repellent is brought into contact with the air current generated by the blower. Can be carried out using a fan-type insect repellent device or the like that discharges water into the environment from the discharge port.

更に、燻蒸による蒸散は、例えば、実開昭54−148267等に開示されているような、上部開口の容器に、アゾジカルボンアミド等のアゾ化合物、ニトロソ化合物、ヒドラジド化合物等の有機発泡剤と防虫剤を収納した収納室を形成させ、収納室の底部を加熱手段により加熱することで発泡剤が分解して発生する窒素ガス、炭酸ガス等により、防虫剤を蒸散させる燻蒸装置等を用いて行うことができる。   Further, the transpiration by fumigation is, for example, an organic foaming agent such as an azo compound such as azodicarbonamide, a nitroso compound, a hydrazide compound and an insect repellent in a container having an upper opening as disclosed in Japanese Utility Model Publication No. 54-148267. A storage chamber containing the agent is formed, and the bottom of the storage chamber is heated by a heating means, using a fumigation device that evaporates the insect repellent using nitrogen gas, carbon dioxide gas, etc. generated by decomposition of the foaming agent. be able to.

噴霧による蒸散は、噴霧器を用い、液剤をスプレーする方法や、適当な噴射剤を用いたエアゾールを使用して行うことができる。   The transpiration by spraying can be performed by using a sprayer and spraying a liquid or using an aerosol using an appropriate propellant.

本発明の防虫剤は、これを、タンス、押入、クローゼット、キッチン、トイレ、居間、玄関等の空間に設置、適用することにより、有効成分であるシリコーン系化合物が上記環境中に放出され、好適に防虫することができる。   The insect repellent of the present invention is preferably used by installing and applying it to a space such as a chiffon, closet, closet, kitchen, toilet, living room, entrance, etc., so that the silicone compound as an active ingredient is released into the environment. Can be insect-proof.

なお、本発明の防虫剤を、効果的に環境中に放出させるために使用する防虫器としては、上記したように本発明防虫剤を常温自然蒸散、加熱蒸散、送風蒸散、薫蒸又は噴霧により環境中に放出させる構造を有する防虫器が好ましい。そのような防虫器の例としては、放出口を有する構造体、当該構造体内に設けられた防虫剤を保持する保持部、当該保持部に近接して設置された加熱ヒーター若しくは送風機を具備する防虫器が挙げられる。   As described above, the insect repellent used to effectively release the insect repellent of the present invention into the environment, as described above, the natural repellent of the present invention by natural transpiration, heat transpiration, air transpiration, fumigation or spraying. Insect repellents having a structure for release into the environment are preferred. Examples of such insect repellents include a structure having a discharge port, a holding part for holding an insect repellent provided in the structure, a heater or a blower installed in the vicinity of the holding part. Vessel.

また、本発明の防虫剤の好ましい他の使用方法としては、シリコーン系化合物を、液体又は固体状態で、害虫又は害虫の卵に接触させて使用する方法が挙げられる。この場合、設置された防虫剤のシリコーン系化合物に、害虫等が接触することによって防虫効果を発揮させることができる。   Another preferred method of using the insect repellent of the present invention includes a method in which a silicone compound is used in contact with a pest or a pest egg in a liquid or solid state. In this case, the insect repellent effect can be exerted by the contact of a pest and the like with the installed insect repellent silicone compound.

上記使用方法として具体的には、シリコーン化合物を含有する上記液剤で処理した処理製品に、害虫又は害虫の卵を接触させる方法が挙げられる。ここで処理される製品としては、繊維製品、プラスティックフィルム製品等が挙げられ、具体的には例えば、衣類、カーテン、シーツ、衣類防虫カバー等が挙げられる。また、処理の方法としては、該製品の基材にシリコーン化合物を練り込んだり、それらの基材に塗布、含浸、印刷、スプレー等により付着させる方法等が挙げられる。   Specific examples of the method of use include a method in which a pest or a pest egg is brought into contact with a treated product treated with the above-described liquid preparation containing a silicone compound. Examples of products to be treated here include fiber products, plastic film products, and the like. Specific examples include clothes, curtains, sheets, clothing insect repellent covers, and the like. Examples of the treatment method include a method in which a silicone compound is kneaded into the base material of the product, or a method of adhering to the base material by coating, impregnation, printing, spraying, or the like.

上記方法は、本発明の防虫剤の有効成分であるシリコーン系化合物が、孵化抑制又は若齢幼虫の殺虫として作用するので好ましい。   The above method is preferable because the silicone compound, which is an active ingredient of the insect repellent of the present invention, acts as a hatching inhibitor or an insecticide for young larvae.

なお本発明の防虫剤には、前記したようにシリコーン系化合物以外に、他の従来公知の防虫成分を配合しても良く、これによりさらに優れた防虫効果を発揮することができる。これらの他の防虫成分としては、例えば、エンペントリン、トランスフルスリン、アレスリン、フェノトリン、プロフルトリン、エミネンス等のピレスロイド系化合物;パラジクロロベンゼン、ナフタリン、2−フェノキシエタノール等の化合物;樟脳、トウガラシ、ワサビ、シソ、カルダモン、ナツメグ、クローブ、コリアンダー、セージ、ローズマリー、バジル、キャラウェー、タイム、ユーカリ、ローレル、シトロネラ、アニス、オレンジ、ラベンダー、精油、アリシン、カプサイシン、ペリラアルデヒド、ティートリーオイル、パインオイル等の植物抽出物等が挙げられ、これらの1種を単独で使用しても良く、2種類以上を組み合わせて使用することもできる。   In addition to the silicone compound as described above, other conventionally known insect repellent components may be blended with the insect repellent of the present invention, whereby a further excellent insect repellent effect can be exhibited. Examples of these other insect repellent components include pyrethroid compounds such as empentrin, transfluthrin, allethrin, phenothrin, profluthrin, and eminence; compounds such as paradichlorobenzene, naphthalene, 2-phenoxyethanol; camphor, pepper, horseradish, perilla, Plant extracts such as cardamom, nutmeg, clove, coriander, sage, rosemary, basil, caraway, thyme, eucalyptus, laurel, citronella, anise, orange, lavender, essential oil, allicin, capsaicin, perilaldehyde, tea tree oil, pine oil A thing etc. are mentioned, These 1 type may be used independently and can also be used in combination of 2 or more type.

本発明の防虫剤のうち好ましいものの例の一つとしては、安全性が特に高い点から、シリコーン系化合物と上記植物抽出物を組み合わせた防虫剤を挙げることができる。また、本発明の防虫剤を液体又は固体状態で、害虫又は害虫の卵に接触させて使用したり、孵化抑制又は若齢幼虫の殺虫として作用させる場合には、シリコーン系化合物にピレスロイド系化合物等の上記他の公知の防虫成分を配合させることも好ましいが、本発明の防虫剤を環境中に放出させて使用する場合には、安全性の点からピレスロイド系化合物等を含有させず、シリコーン系化合物のみを単独の防虫有効成分とする防虫剤が好ましい。   As an example of a preferable thing among the insect repellents of this invention, the insect repellent which combined the silicone type compound and the said plant extract from the point with especially high safety | security can be mentioned. In addition, when the insect repellent of the present invention is used in contact with a pest or a pest egg in a liquid or solid state, or acts as a hatching inhibitor or a young larvae insecticide, a pyrethroid compound, etc. It is also preferable to add the above-mentioned other known insect repellent ingredients, but when the insect repellent of the present invention is used after being released into the environment, it does not contain a pyrethroid compound or the like from the viewpoint of safety. Insect repellents comprising only the compound as the sole insect repellent active ingredient are preferred.

以上説明した本発明の防虫剤は、家庭内で発生する種々の害虫、特に昆虫に対して防虫効果を有するものである。本発明防虫剤が有効な害虫としては、特に限定はないが、その具体例としては、コクヌストモドキ、ノコギリコクヌスト、オオコクヌスト、コクゾウムシ、ココクゾウムシ、グラナリヤコクゾウムシ、ヒメカツオブシムシ、ヒメマル、カツオブシムシ等の鞘翅目の害虫;ノシメコクガ、バクガ、ノシメマダラメイガ、スジコナマダラメイガ、ハチミツガ、ガイマイツヅリガ、ユメマダラメイガ、カクムネコクヌスト、イガ、コイガ等の鱗翅目の害虫;レピスマ・サッカリナ等のシミ目の害虫;コバネゴキブリ、ワモンゴキブリ、レウコフェア・マデラエ、チャバネゴキブリ、アケータ・ドメスチクス等の直翅目の害虫;ホルフィクラ・アウリクラリス等のハサミムシ目の害虫;レチクリテルメス等のシロアリ目の害虫;ヒトジラミ等のシラミ目の害虫;ナンキンムシ、ロドニウス・プロリクスス、トリアトマ・インフェスタンス等の半翅目の害虫;イエヒメアリ、ラシウス・ニゲル、スズメバチ等の膜翅目の害虫;アエデス・エギプティ、ハマダラカ、アカイエカ、イエバエ、ヒメイエバエ、オオクロバエ、キンバエ、オビキンバエ、サシバエ、アブ等の双翅目の害虫;ネズミノミ、ナガノミ等のノミ目の害虫の成虫、蛹、幼虫、卵等が挙げられる。   The insect repellent of the present invention described above has an insect repellent effect against various pests generated in the home, particularly insects. The pests for which the present insect repellent is effective are not particularly limited, but specific examples thereof include pods such as wolfberry, sawtooth moth, wolfberry, weevil, weevil, granary weevil, scorpion worm, himemaru, katobushimushi, etc. Pests of the eyes; Pests of the Lepidoptera such as Noshimekoga, Bakuga, Nomemadarameiga, Suikomamadarameiga, Hachimitsuga, Gaimitsuna Riga, Yumemadarameiga, Kakumnekokunusu, Iga, Koiga; Pests such as cockroach, reucofair maderae, chaban cockroach, aceta domestics, etc .; pests of insects such as Horficula auricularis; termite pests such as reticulitermes; lice such as human lice Pests such as bed bugs, rhodonius prolixus, triatoma infestans, etc .; Hymenoptera pests such as house spiders, Lasius nigel, hornets, etc .; Examples include dipteran pests such as the butterflies, lobsters, fly flies, and flies; adults, fleas, larvae, and eggs of fleas such as the murine flea and the chironomid.

次に実施例を挙げて本発明を更に詳しく説明するが、本発明はこれら実施例に何ら制約されるものではない。   EXAMPLES Next, although an Example is given and this invention is demonstrated in more detail, this invention is not restrict | limited at all by these Examples.

実 施 例 1
直径4cmの金属製のかごの中に、表1に示した試験物質10mgをそれぞれ含浸させた濾紙を入れ、これを内容積0.5リットルのガラス製ふたつき容器のほぼ中央に置き、その底部に産卵後1日の衣類害虫であるイガの卵20個を載せた1辺2.5cmの正方形のサージを置いた。温度25℃、相対湿度60%RHの条件下に14日間保存した後、容器の蓋を開け、孵化した卵の数を数え、孵化していた場合には、孵化直後の若齢幼虫の生死を判別した。Nを生存していた若齢幼虫の数とすると、「孵化しなかった卵の数+死んでいた若齢幼虫の数」の全体数に対する百分率(以下、「防虫率」という)は、
防虫率(%)=100×(20−N)/20
で表されるが、各試験物質についてのその値を表2に示す。なおブランクとして、試験物質を何も入れないものを用いた。
Example 1
A filter paper impregnated with 10 mg of the test substance shown in Table 1 is placed in a metal cage having a diameter of 4 cm, and this is placed at the center of a glass lidded container having an internal volume of 0.5 liter. A 2.5-cm square surge with 20 iga eggs, which are clothing pests one day after egg laying, was placed on. 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. When N is the number of young larvae that survived, the percentage of the total number of “number of eggs that did not hatch + number of young larvae that died” (hereinafter referred to as “insect repellent rate”) is:
Insect repellent rate (%) = 100 × (20−N) / 20
The values for each test substance are shown in Table 2. In addition, the blank which did not put any test substance was used.

Figure 2006036759
Figure 2006036759

Figure 2006036759
Figure 2006036759

実 施 例 2
卵を穀物害虫であるメイガの卵に代えた以外は、実施例1と同様の試験方法により、防虫率を算出した。結果を表3に示す。
Example 2
The insect repellent rate was calculated by the same test method as in Example 1 except that the eggs were replaced with the eggs of maiga, a grain pest. The results are shown in Table 3.

Figure 2006036759
Figure 2006036759

実 施 例 3
1辺2.0cmの正方形のサージに、サージ質量に対して5質量%の量の試験物質を含浸させたものを、直径4.5cmのシャーレの中に入れ、その上に産卵後1日のヒメカツオブシムシの卵30個を載せた。25℃、60%RHの条件下に7日間保存した後、実施例1と同様の方法で生存していた若齢幼虫の数(N)を求め、下記の計算式を用いて防虫率を算出した。結果を表4に示す。
防虫率(%)=100×(30−N)/30
Example 3
Place a 2.0 cm square surge impregnated with 5% by mass of the test substance in a square surge into a petri dish with a diameter of 4.5 cm. 30 eggs of Himekatsuobushimushi were placed. After storage for 7 days under conditions of 25 ° C. and 60% RH, the number of young larvae (N) that survived in the same manner as in Example 1 was determined, and the insect control rate was calculated using the following formula: did. The results are shown in Table 4.
Insect control rate (%) = 100 × (30−N) / 30

Figure 2006036759
Figure 2006036759

実 施 例 4
上記実施例3の対象害虫の卵を、ヒメマルカツオブシムシの卵からノシメマダラメイガの卵に、試験物質の含浸量をサージ質量に対して15質量%にした以外は、実施例3と同様にして試験を行った。結果を表5に示す。
Example 4
The target pest eggs of Example 3 were tested in the same manner as in Example 3 except that the eggs of the pine beetle were changed to eggs of Nomadamearaga and the impregnation amount of the test substance was 15% by mass with respect to the surge mass. Went. The results are shown in Table 5.

Figure 2006036759
Figure 2006036759

実 施 例 5
(アカイエカの成虫に対する殺虫試験)
アカイエカの雌成虫(羽化後3〜4日)50匹をジエチルエーテルで麻酔し厚紙上にうつぶせ状態で並べ、その胸部背板に各試料5μg滴下した。その後、供試虫を清潔な腰高シャーレに移し、シロップ綿を添えて金網蓋をし、25℃の温度下に保存した。24時間後の供試虫の生死について判別し、致死率を死亡虫数の全体数に対する百分率として算出した。結果を表6に示す。
Example 5
(Insecticidal tests against adult mosquitoes)
Fifty female adult mosquitoes (3 to 4 days after emergence) were anesthetized with diethyl ether and lined up on cardboard, and 5 μg of each sample was dropped on the chest back plate. Thereafter, the test insects were transferred to a clean waist-high petri dish, covered with syrup cotton, covered with a wire mesh, and stored at a temperature of 25 ° C. The life and death of the test insects after 24 hours were determined, and the lethality was calculated as a percentage of the total number of dead insects. The results are shown in Table 6.

Figure 2006036759
Figure 2006036759

実 施 例 6
(アカイエカの幼虫に対する殺虫試験)
試料1及び4の10ppm水懸濁液を調製し、各200mlを腰高シャーレに入れた。この中に、アカイエカの終令幼虫25匹を投入し、約25℃の温度下に保存して24時間後の死亡虫数を測定した。なお、微動虫は死亡虫とし、蛹化したものは除いた。同様の試験を2連で行い、合計した死亡虫数を薬剤処理区の死亡虫数とした。薬剤を加えないものを対照として、薬剤処理区と同様に、対照区の死亡虫数を求め、下記の計算式を用いて致死率を算出した。結果を表7に示す。
致死率(%)=100×(Na−Nb)/(Nt−Nb)
Nt:各群の全虫数
Na:薬剤処理区の死亡虫数
Nb:対照区の死亡虫数
Example 6
(Insecticidal test against larvae of Culex pipiens)
A 10 ppm aqueous suspension of Samples 1 and 4 was prepared, and 200 ml of each was placed in a waist-high petri dish. Into this, 25 final larvae of Culex pipiens were introduced, stored at a temperature of about 25 ° C., and the number of dead worms after 24 hours was measured. The fine worms were dead and the hatched ones were excluded. Similar tests were performed in duplicate, and the total number of dead insects was taken as the number of dead insects in the drug-treated area. The number of dead insects in the control group was determined in the same manner as in the drug-treated group, with no drug added, and the mortality was calculated using the following formula. The results are shown in Table 7.
Lethality rate (%) = 100 × (Na−Nb) / (Nt−Nb)
Nt: Total number of insects in each group Na: Number of dead insects in the drug-treated group Nb: Number of dead insects in the control group

Figure 2006036759
Figure 2006036759

実 施 例 7
(イエバエの成虫に対する殺虫試験)
試料1及び4をノルマルヘキサンで10倍に希釈して調製し、イエバエの雌成虫(羽化後3〜4日)50匹をジエチルエーテルで麻酔し厚紙上にうつぶせ状態で並べ、その胸部背板に調製した各試料を1匹につき5μg滴下した。その後、供試虫を清潔な腰高シャーレに移し、シロップ綿を添えて金網蓋をし、約25℃の温度下に保存した。24時間後の供試虫の生死について判別し、薬剤処理区の死亡虫数を求めた。なお、薬剤を含まないノルマルヘキサンのみを滴下したものを対照とし、薬剤処理区と同様にして、対照区の死亡虫数を求め、下記の計算式を用いて致死率を算出した。結果を表8に示す。
致死率(%)=100×(Na−Nb)/(Nt−Nb)
Nt:各群の全虫数
Na:薬剤処理区の死亡虫数
Nb:対照区の死亡虫数
Example 7
(Insecticidal test against housefly adults)
Samples 1 and 4 were prepared by diluting 10-fold with normal hexane. 50 adult female flies (3-4 days after emergence) were anesthetized with diethyl ether and lined up on cardboard, and placed on the chest backplate. 5 μg of each prepared sample was dropped per animal. Thereafter, the test insects were transferred to a clean waist-high petri dish, covered with syrup cotton, covered with a wire mesh, and stored at a temperature of about 25 ° C. The life and death of the test insects after 24 hours were determined, and the number of dead insects in the drug-treated area was determined. In addition, the thing which dripped only the normal hexane which does not contain a chemical | medical agent was made into the control, the number of dead insects of the control group was calculated | required like the chemical treatment group, and the lethality was computed using the following formula. The results are shown in Table 8.
Lethality rate (%) = 100 × (Na−Nb) / (Nt−Nb)
Nt: Total number of insects in each group Na: Number of dead insects in the drug-treated group Nb: Number of dead insects in the control group

Figure 2006036759
Figure 2006036759

実 施 例 8
(イエバエの幼虫に対する殺虫試験)
試料1及び4の1000ppm水懸濁液を調製し、各200mlを腰高シャーレに入れた。この中に、イエバエの終令幼虫25匹を投入し、約25℃の温度下、相対湿度90%に保存して24時間後の死亡虫数を測定した。なお、微動虫は死亡虫とし、蛹化したものは除いた。同様の試験を2連で行い合計の死亡虫数を求め、これを薬剤処理区の死亡虫数とした。薬剤を加えないものを対照とし、薬剤処理区と同様にして死亡虫数を求め下記の計算式を用いて致死率を算出した。結果を表9に示す。
致死率(%)=100×(Na−Nb)/(Nt−Nb)
Nt:各群の全虫数
Na:薬剤処理区の死亡虫数
Nb:対照区の死亡虫数
Example 8
(Insecticidal test against housefly larvae)
A 1000 ppm water suspension of Samples 1 and 4 was prepared, and 200 ml of each was placed in a waist-high petri dish. Twenty-five housefly larvae were introduced into this, and the number of dead worms after 24 hours was measured at a temperature of about 25 ° C. and a relative humidity of 90%. The fine worms were dead and the hatched ones were excluded. A similar test was performed in duplicate to determine the total number of dead insects, which was used as the number of dead insects in the drug-treated area. The number of dead insects was determined in the same manner as in the drug-treated section, and the mortality rate was calculated using the following formula. The results are shown in Table 9.
Lethality rate (%) = 100 × (Na−Nb) / (Nt−Nb)
Nt: Total number of insects in each group Na: Number of dead insects in the drug-treated group Nb: Number of dead insects in the control group

Figure 2006036759
Figure 2006036759

実 施 例 9
(チャバネゴキブリ幼虫に対する殺虫試験)
幼虫の這い上がりを防ぐ為に、内壁上から約4cmバターを塗った直径9cm、高さ6cmの腰高シャーレ内に孵化後6日以内のチャバネゴキブリの幼虫10〜20匹を静かにはたき落とし供試虫とした。10cm角のベニヤ板に試料1及び試料1の30%ジエチルエーテル溶液0.5mlを均一に塗布し50〜60分間風乾させた試験板を、試料塗布面を下にして腰高シャーレ上に置き、これを反転させて薬剤塗布面に供試虫を接触させた。その後、時間経過に伴うノックダウンの状況を観察し、供試虫の50%がノックアウトした経過時間(KT50)及び供試虫の90%がノックアウトした経過時間(KT90)を測定した。また、24時間後の致死率を算出した。なお、試験は3連で実施し、ノックアウトした経過時間は平均をとり、致死率は合計数を用いて、死亡虫数の全体数に対する百分率として算出した。結果を表10に示す。
Example 9
(Insecticidal test against German cockroach larvae)
In order to prevent the larvae from creeping up, 10 to 20 cockroach larvae within 6 days after hatching were gently knocked out in a petri dish of 9 cm in diameter and 6 cm in height, coated with butter 4 cm from the inner wall. It was. Place a test plate that was uniformly coated with 0.5 ml of the 30% diethyl ether solution of Sample 1 and Sample 1 on a 10 cm square plywood plate and air-dried for 50 to 60 minutes. The test insect was brought into contact with the drug application surface by inverting it. Thereafter, the state of knockdown with the passage of time was observed, and the elapsed time (KT 50 ) when 50 % of the test insects were knocked out and the elapsed time (KT 90 ) when 90% of the test insects were knocked out were measured. In addition, the mortality after 24 hours was calculated. The test was performed in triplicate, the elapsed time of knockout was averaged, and the mortality was calculated as a percentage of the total number of dead insects using the total number. The results are shown in Table 10.

Figure 2006036759
Figure 2006036759

実 施 例 10
(チャバネゴキブリ成虫に対する殺虫試験)
供試虫の這い上がりを防ぐ為に、内壁上から約4cmバターを塗った直径9cm、高さ6cmの腰高シャーレ内に雌チャバネゴキブリの成虫30匹を入れ供試虫とした。10cm角のベニヤ板に試料1 0.5mlを均一に塗布した試験板を、試料塗布面を下にして腰高シャーレ上に置き、これを反転させて薬剤塗布面に供試虫を接触させた。24時間後の致死率を死亡虫数の全体数に対する百分率として算出した。結果を表11に示す。
Example 10
(Insecticidal test against adult German cockroaches)
In order to prevent the test insects from crawling, 30 adult female German cockroaches were placed in a petri dish with a diameter of 9 cm and a height of 6 cm coated with butter about 4 cm from the inner wall. A test plate in which 0.5 ml of Sample 1 was uniformly applied to a 10 cm square plywood plate was placed on a waist-high petri dish with the sample application surface down, and this was inverted to bring the test insect into contact with the drug application surface. The lethality after 24 hours was calculated as a percentage of the total number of dead insects. The results are shown in Table 11.

Figure 2006036759
Figure 2006036759

実 施 例 11
以下の製剤例1〜6のようにして、防虫剤を調製した。
Example 11
Insect repellents were prepared as in Formulation Examples 1 to 6 below.

製剤例1
エアゾール剤:
以下の処方を、市販の200mlエアゾール缶に充填することによって、エアゾール剤を調製した。
有効成分:ドデカメチルシクロヘキサシロキサン 80.0ml
溶媒 :エタノール 40.0ml
噴射剤 :LPG 30.0ml
噴射剤 :イソペンタン 30.0ml
Formulation Example 1
Aerosol:
An aerosol was prepared by filling the following formulation into a commercially available 200 ml aerosol can.
Active ingredient: Dodecamethylcyclohexasiloxane 80.0ml
Solvent: Ethanol 40.0ml
Propellant: LPG 30.0ml
Propellant: Isopentane 30.0ml

製剤例2
固型防虫剤:
125mm×65mmmのパルプ製ろ紙に、500mgのデカメチルシクロペンタシロキサンを含浸させた。これを、通気性を有するプラスチックケースに収納して、衣類害虫用固型防虫剤を調製した。
Formulation Example 2
Solid insect repellent:
A 125 mm × 65 mm mm pulp filter paper was impregnated with 500 mg of decamethylcyclopentasiloxane. This was housed in a plastic case having air permeability to prepare a solid insect repellent for clothing pests.

製剤例3
スプレー剤:
以下の処方のスプレー剤を、市販の150mlトリガー製容器に収納してスプレー剤を調製した。
有効成分:ドデカメチルシクロヘキサシロキサン 20g
溶剤 :エタノール 80g
Formulation Example 3
Spray:
A spray having the following formulation was placed in a commercially available 150 ml trigger container to prepare a spray.
Active ingredient: 20 g dodecamethylcyclohexasiloxane
Solvent: Ethanol 80g

製剤例4
燻蒸剤:
メチルポリシロキサン10g、アゾジカルボンアミド55g及びタルク35gを混練し、造粒、乾燥して燻蒸剤を調製した。
Formulation Example 4
Fumigant:
10 g of methylpolysiloxane, 55 g of azodicarbonamide and 35 g of talc were kneaded, granulated and dried to prepare a fumigant.

製剤例5
加熱蒸散剤:
メチルポリシロキサン100mgを3cm×3cmのパルプ製マットに含浸させ加熱蒸散剤を得た。このものは、加熱ヒーターに接置させることにより有効成分を蒸散する。
Formulation Example 5
Heating transpiration agent:
A 3 cm × 3 cm pulp mat was impregnated with 100 mg of methylpolysiloxane to obtain a heat transpiration agent. This thing evaporates an active ingredient by making it contact with a heater.

製剤例6
送風蒸散剤
パルプ製の粒状含浸体(平均粒径5mm)50gに、ドデカメチルシクロヘキサシロキサン50mLを含浸させ、送風蒸散剤を得た。このものは、ファン式の防虫器により有効成分を蒸散する。
Formulation Example 6
Blowing transpiration agent 50 g of dodecamethylcyclohexasiloxane was impregnated into 50 g of a pulp impregnated product (average particle size 5 mm) to obtain a blasting transpiration agent. This product evaporates the active ingredient with a fan type insect repellent.

本発明の防虫剤の有効成分であるシリコーン系化合物は、害虫や害虫の卵に対して優れた防虫効果を発揮するものであり、しかも人体に対して安全であり、安定性も高いものである。従って、本発明防虫剤は、一般家庭においても手軽に使用できるものである。   The silicone compound which is an active ingredient of the insect repellent of the present invention exhibits an excellent insect repellent effect against pests and insect eggs, and is safe to the human body and has high stability. . Therefore, the insect repellent of the present invention can be easily used in general households.

また本発明の防虫剤を環境中に有効に放出させることのできる防虫器に用いることによって高い防虫効果を得ることができ、広く防虫用途に使用されるものである。
以 上
Further, by using the insect repellent of the present invention in an insect repellent that can be effectively released into the environment, a high insect repellent effect can be obtained, and it is widely used for insect repellent applications.
more than

Claims (18)

シリコーン系化合物を有効成分として含有することを特徴とする防虫剤。   An insect repellent comprising a silicone compound as an active ingredient. シリコーン系化合物が揮散性のものである請求項1記載の防虫剤。   The insect repellent according to claim 1, wherein the silicone compound is volatile. シリコーン系化合物が、式(1)で表されるものである請求項1又は請求項2記載の防虫剤。
Figure 2006036759
[式中、R、R及びRは異なっていてもよい水素原子、フェニル基又は式(2)

−X−R' ・・・・・(2)
(式中、Xは炭素数1〜10のアルキレン基又は酸素原子を示し、R'は水素原子、フェニル基、エポキシ基、アミノ基、カルボキシル基、水酸基、トリフルオロメチル基、トリメチルシリル基、−(OC−(OCOR''(a及びbは異なっていてもよい0〜10の自然数であり、R''は炭素数1〜10のアルキル基である)又は−NH−(CH−NH(cは1〜10の自然数である)を示す)を示し、m、n及びoは異なっていてもよい0〜100の自然数を示す]
The insect repellent according to claim 1 or 2, wherein the silicone compound is represented by the formula (1).
Figure 2006036759
[Wherein R 1 , R 2 and R 3 may be different from each other, a hydrogen atom, a phenyl group or formula (2)

-XR '(2)
(In the formula, X represents an alkylene group having 1 to 10 carbon atoms or an oxygen atom, and R ′ represents a hydrogen atom, phenyl group, epoxy group, amino group, carboxyl group, hydroxyl group, trifluoromethyl group, trimethylsilyl group, — ( OC 2 H 4 ) a- (OC 3 H 6 ) b OR ″ (a and b are natural numbers of 0 to 10 which may be different, and R ″ is an alkyl group having 1 to 10 carbon atoms) Or —NH— (CH 2 ) c —NH 2 (where c is a natural number of 1 to 10), and m, n, and o are 0 to 100, which may be different.]
シリコーン系化合物が、式(3)で表されるものである請求項1又は請求項2記載の防虫剤。
Figure 2006036759
[式中、Y及びZは異なっていてもよい炭素数1〜10のアルキレン基、フェニレン基又は単結合を示し、Rはメチル基又は水酸基を示し、Rはメチル基又は−(CH−NH−(CH−NH(d及びeは異なっていてもよい1〜10の自然数である)を示し、p及びqは異なっていてもよい0〜100の自然数を示す]
The insect repellent according to claim 1 or 2, wherein the silicone compound is represented by the formula (3).
Figure 2006036759
[Wherein, Y and Z each represent an optionally substituted alkylene group having 1 to 10 carbon atoms, a phenylene group or a single bond, R 4 represents a methyl group or a hydroxyl group, and R 5 represents a methyl group or — (CH 2 ) D -NH- (CH 2 ) e -NH 2 (d and e are natural numbers of 1 to 10 which may be different), and p and q represent natural numbers of 0 to 100 which may be different. ]
シリコーン系化合物が、式(4)で表されるものである請求項1又は請求項2記載の防虫剤。
Figure 2006036759
(式中、Rはメチル基又はフェニル基を示し、Rはメチル基、フェニル基又はビニル基を示し、rは3〜20の自然数を示す。)
The insect repellent according to claim 1 or 2, wherein the silicone compound is represented by the formula (4).
Figure 2006036759
(Wherein R 6 represents a methyl group or a phenyl group, R 7 represents a methyl group, a phenyl group or a vinyl group, and r represents a natural number of 3 to 20)
シリコーン系化合物を、環境中に放出させて使用するものである請求項1ないし請求項5の何れかの請求項記載の防虫剤。   The insect repellent according to any one of claims 1 to 5, wherein the silicone compound is used after being released into the environment. シリコーン系化合物を、液体又は固体状態で、害虫又は害虫の卵に接触させて使用するものである請求項1ないし請求項5の何れかの請求項記載の防虫剤。   6. The insect repellent according to any one of claims 1 to 5, wherein the silicone compound is used in contact with a pest or a pest egg in a liquid or solid state. 害虫の卵に対して使用されるものである請求項1ないし請求項7の何れかの請求項記載の防虫剤。   The insect repellent according to any one of claims 1 to 7, which is used for a pest egg. 害虫の幼虫に対して使用されるものである請求項1ないし請求項7の何れかの請求項記載の防虫剤。   The insect repellent according to any one of claims 1 to 7, which is used against pest larvae. 害虫の成虫に対して使用されるものである請求項1ないし請求項7の何れかの請求項記載の防虫剤。   The insect repellent according to any one of claims 1 to 7, which is used against adult insects. 害虫の孵化抑制又は若齢幼虫の殺虫を目的として使用されるものである請求項1ないし請求項7の何れかの請求項記載の防虫剤。   The insect repellent according to any one of claims 1 to 7, which is used for the purpose of inhibiting hatching of pests or killing young larvae. シリコーン系化合物のみが有効成分である請求項1ないし請求項11の何れかの請求項記載の防虫剤。   The insect repellent according to any one of claims 1 to 11, wherein only the silicone compound is an active ingredient. 更に、植物抽出物を含有する請求項1ないし請求項11記載の防虫剤。   Furthermore, the insect repellent of Claim 1 thru | or 11 containing a plant extract. 更に、ピレスロイド系化合物を含有する請求項7ないし請求項11記載の防虫剤。   Furthermore, the insect repellent of Claim 7 thru | or 11 containing a pyrethroid type compound. 請求項1ないし請求項14の何れかの請求項記載の防虫剤を、常温自然蒸散、加熱蒸散、送風蒸散、薫蒸又は噴霧により環境中に放出させる構造を有する防虫器。   An insect repellent having a structure in which the insect repellent according to any one of claims 1 to 14 is released into the environment by natural transpiration at room temperature, heat transpiration, air transpiration, fumigation or spraying. 放出口を有する構造体、当該構造体内に設けられた請求項1ないし請求項14の何れかの請求項記載の防虫剤を保持する保持部、当該保持部に近接して設置された加熱ヒーター若しくは送風機を具備してなる防虫器。   A structure having a discharge port, a holding part for holding the insect repellent according to any one of claims 1 to 14 provided in the structure, a heater installed in the vicinity of the holding part, or An insect repellent comprising a blower. 請求項1ないし請求項14の何れかの請求項記載の防虫剤を、害虫又は害虫の卵に適用させる防虫方法。   An insect repellent method comprising applying the insect repellent according to any one of claims 1 to 14 to a pest or a pest egg. 請求項1ないし請求項14の何れかの請求項記載の防虫剤を含有する繊維製品を、害虫又は害虫の卵に接触させる防虫方法。
An insect repellent method comprising bringing a fiber product containing the insect repellent according to any one of claims 1 to 14 into contact with a pest or a pest egg.
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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008056605A (en) * 2006-08-31 2008-03-13 St Kk Insecticide composition and method for preventing adsorption of pyrethroid volatile under normal temperature
JP2009167131A (en) * 2008-01-17 2009-07-30 Fumakilla Ltd Insect pest eclosion inhibitor
JP2017119643A (en) * 2015-12-28 2017-07-06 ライオン株式会社 Antifungal smoking agent composition
JP2019081752A (en) * 2017-10-30 2019-05-30 アース製薬株式会社 Method of inhibiting colonization by blood-sucking pests and colonization inhibitor against blood-sucking pests
WO2020137774A1 (en) * 2018-12-28 2020-07-02 花王株式会社 Pest repellent composition
WO2020137771A1 (en) * 2018-12-28 2020-07-02 花王株式会社 Oil-in-water type pest repellent composition

Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS53107418A (en) * 1977-02-26 1978-09-19 Dainippon Jochugiku Kk Sustaining for effect of volatile pesticide
JPS545027A (en) * 1977-05-31 1979-01-16 Block Drug Co Siloxane poison
JPS5939808A (en) * 1982-08-31 1984-03-05 Shin Etsu Chem Co Ltd Expellent for hygienic and agricultural vermin
JPS5939809A (en) * 1982-08-31 1984-03-05 Shin Etsu Chem Co Ltd Expellent for hygienic and agricultural vermin
EP0191543A1 (en) * 1985-01-15 1986-08-20 Ventec Laboratories, Inc. Silicone insect toxicants
JPS62212302A (en) * 1986-03-14 1987-09-18 Fukuvi Chem Ind Co Ltd Resin molded article for repelling insect pest, having durability
JPS63264506A (en) * 1987-04-22 1988-11-01 Toray Ind Inc Insecticidal material
JPS63316706A (en) * 1987-06-19 1988-12-26 Osaka Seiyaku:Kk Volatile solution in ambient temperature
JPH06179604A (en) * 1992-12-14 1994-06-28 Toyo Ink Mfg Co Ltd Hygienic vermin repellent or antibacterial mildew-proofing agent
JPH0733608A (en) * 1993-07-22 1995-02-03 Japan Tobacco Inc Insecticide using surfactant and insecticidal method
JPH07206612A (en) * 1994-01-27 1995-08-08 Sankyo Co Ltd Insecticidal and acaricidal composition enhanced in potency
JPH07206615A (en) * 1993-11-25 1995-08-08 Dainippon Jochugiku Co Ltd Insecticidal composition
JPH10195032A (en) * 1997-01-08 1998-07-28 Earth Chem Corp Ltd Modification of viscosity of quaternary ammonium salt aqueous solution and viscosity modifier of the same aqueous solution
JP2000501087A (en) * 1995-11-30 2000-02-02 バイエル・アクチエンゲゼルシヤフト Pest control agents based on cyclic polysiloxanes
WO2001067863A2 (en) * 2000-03-15 2001-09-20 Kidron Agrochem Ltd. Pesticidal compositions containing silicon compounds

Patent Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS53107418A (en) * 1977-02-26 1978-09-19 Dainippon Jochugiku Kk Sustaining for effect of volatile pesticide
JPS545027A (en) * 1977-05-31 1979-01-16 Block Drug Co Siloxane poison
JPS5939808A (en) * 1982-08-31 1984-03-05 Shin Etsu Chem Co Ltd Expellent for hygienic and agricultural vermin
JPS5939809A (en) * 1982-08-31 1984-03-05 Shin Etsu Chem Co Ltd Expellent for hygienic and agricultural vermin
EP0191543A1 (en) * 1985-01-15 1986-08-20 Ventec Laboratories, Inc. Silicone insect toxicants
JPS62212302A (en) * 1986-03-14 1987-09-18 Fukuvi Chem Ind Co Ltd Resin molded article for repelling insect pest, having durability
JPS63264506A (en) * 1987-04-22 1988-11-01 Toray Ind Inc Insecticidal material
JPS63316706A (en) * 1987-06-19 1988-12-26 Osaka Seiyaku:Kk Volatile solution in ambient temperature
JPH06179604A (en) * 1992-12-14 1994-06-28 Toyo Ink Mfg Co Ltd Hygienic vermin repellent or antibacterial mildew-proofing agent
JPH0733608A (en) * 1993-07-22 1995-02-03 Japan Tobacco Inc Insecticide using surfactant and insecticidal method
JPH07206615A (en) * 1993-11-25 1995-08-08 Dainippon Jochugiku Co Ltd Insecticidal composition
JPH07206612A (en) * 1994-01-27 1995-08-08 Sankyo Co Ltd Insecticidal and acaricidal composition enhanced in potency
JP2000501087A (en) * 1995-11-30 2000-02-02 バイエル・アクチエンゲゼルシヤフト Pest control agents based on cyclic polysiloxanes
JPH10195032A (en) * 1997-01-08 1998-07-28 Earth Chem Corp Ltd Modification of viscosity of quaternary ammonium salt aqueous solution and viscosity modifier of the same aqueous solution
WO2001067863A2 (en) * 2000-03-15 2001-09-20 Kidron Agrochem Ltd. Pesticidal compositions containing silicon compounds

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008056605A (en) * 2006-08-31 2008-03-13 St Kk Insecticide composition and method for preventing adsorption of pyrethroid volatile under normal temperature
JP2009167131A (en) * 2008-01-17 2009-07-30 Fumakilla Ltd Insect pest eclosion inhibitor
JP2017119643A (en) * 2015-12-28 2017-07-06 ライオン株式会社 Antifungal smoking agent composition
JP2019081752A (en) * 2017-10-30 2019-05-30 アース製薬株式会社 Method of inhibiting colonization by blood-sucking pests and colonization inhibitor against blood-sucking pests
WO2020137774A1 (en) * 2018-12-28 2020-07-02 花王株式会社 Pest repellent composition
WO2020137771A1 (en) * 2018-12-28 2020-07-02 花王株式会社 Oil-in-water type pest repellent composition
CN113226029A (en) * 2018-12-28 2021-08-06 花王株式会社 Pest repellent composition
CN113226028A (en) * 2018-12-28 2021-08-06 花王株式会社 Oil-in-water pest repellent composition

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