JP5858663B2 - Aromatic insect repellent - Google Patents
Aromatic insect repellent Download PDFInfo
- Publication number
- JP5858663B2 JP5858663B2 JP2011147028A JP2011147028A JP5858663B2 JP 5858663 B2 JP5858663 B2 JP 5858663B2 JP 2011147028 A JP2011147028 A JP 2011147028A JP 2011147028 A JP2011147028 A JP 2011147028A JP 5858663 B2 JP5858663 B2 JP 5858663B2
- Authority
- JP
- Japan
- Prior art keywords
- insect repellent
- liquid
- fragrance
- activity
- aromatic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000000077 insect repellent Substances 0.000 title claims description 89
- 125000003118 aryl group Chemical group 0.000 title claims description 34
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- 239000003205 fragrance Substances 0.000 claims description 73
- 239000003795 chemical substances by application Substances 0.000 claims description 46
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Landscapes
- Catching Or Destruction (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Description
本発明は、衣料害虫に対する液体式芳香性防虫剤に関するものである。 The present invention relates to a liquid aromatic insect repellent against clothing pests.
従来、イガ類、カツオブシムシ類やシミ類等の衣料害虫から繊維製品を保護するため、主に、タンス、引き出し、クロ−ゼットや衣料収納箱用として、様々な防虫剤が提案、実用化されている。その有効成分としては、古くはパラジクロロベンゼンやナフタレン等の昇華性防虫剤成分が使用されたが、強い刺激性や安全性の問題が指摘され、近年、エムペントリンやプロフルトリン等の常温揮散性ピレスロイド系殺虫成分が主流となっている。後者のピレスロイド系殺虫成分は、衣料害虫に対して微量で高い殺虫効果を示し、無臭で、しかも安全性に優れ、有用性の高い有効成分であるが、処理空間に充分に拡散するまでに幾分時間がかかり、初期効果の改善が望まれている。また、最近の消費者ニ−ズの多様化に伴い、無臭よりも若干の香りを有する防虫剤を使用して、処理空間や衣類への賦香を積極的に行う傾向もみられるようになった。 In the past, various insect repellents have been proposed and put into practical use mainly for chiffons, drawers, closets and clothing storage boxes in order to protect textile products from clothing pests such as moths, cutworms and stains. Yes. In the past, sublimable insecticides such as paradichlorobenzene and naphthalene were used as active ingredients, but strong irritancy and safety problems were pointed out. Recently, room temperature volatile pyrethroid insecticides such as empentrin and profluthrin have been pointed out. Ingredients are mainstream. The latter pyrethroid-based insecticidal component is a highly effective active ingredient that shows a high insecticidal effect against clothing pests and is odorless, excellent in safety, and highly useful. Minute time is required and improvement of the initial effect is desired. In addition, with the recent diversification of consumer needs, there has also been a tendency to aggressively perfume treatment spaces and clothing using insect repellents that have a slight scent rather than odorless. .
このような状況を背景として、防虫効果と芳香性を兼ね備える天然産の精油由来成分を防虫成分として用いる提案がいくつかなされている。
例えば特開平９−２７８６２１号公報は、ハッカ油、レモン油、オレンジ油、シトロネロ−ル、ケシ油から選ばれる揮発性防虫剤と、ヒバ油、ヒノキ油、カンファ−、ピネンから選ばれる低揮発性防虫剤を組み合わせた防虫剤に関するものである。また、特許第４３１１７７３号公報では、衣料害虫の孵化抑制剤に着目し、卵から幼虫への移行を抑制すれば衣料害虫による食害を防止できると考え、卵孵化抑制剤として、リナロ−ル、ゲラニオ−ル、シトロネラ−ル、ヘプタン酸アリル、酢酸ネリル等、数多くのテルペン化合物が提案されている。しかしながら、これらについても、衣料害虫に対する効果は十分とは言えず、防虫効果と芳香性を兼ね備える天然産の精油由来成分や香料成分を有効成分とする衣料害虫用防虫剤の開発に当たっては、有効成分の選抜、他の剤や溶剤との組み合わせと供に、防虫剤の形態の検討が不可欠な状況であった。
Against this backdrop, several proposals have been made to use a natural essential oil-derived component having an insect repellent effect and aromaticity as an insect repellent component.
For example, JP-A-9-278621 discloses a volatile insect repellent selected from peppermint oil, lemon oil, orange oil, citronellol and poppy oil, and low volatility selected from hiba oil, cypress oil, camphor and pinene. The present invention relates to an insect repellent combined with an insect repellent. In addition, in Japanese Patent No. 4311773, attention is paid to a hatching inhibitor of clothing pests, and it is considered that if the migration from eggs to larvae is suppressed, food damage caused by clothing pests can be prevented, and linalol and geranio are used as egg hatching inhibitors. Numerous terpene compounds have been proposed, such as thiol, citronellal, allyl heptanoate and neryl acetate. However, these are also not effective against clothing pests, and are effective ingredients for the development of insect pests for clothing pests that contain natural essential oil-derived ingredients and fragrance ingredients that have both insect repellent effect and fragrance. It was indispensable to examine the form of insect repellents together with the selection of these and combinations with other agents and solvents.
防虫剤の形態としては、前述の常温昇華性固体である樟脳、ナフタリン、パラジクロロベンゼン等を有効成分とした固形の防虫剤が知られている。またこの固形防虫剤に代わるものとして、有効成分であるエムペントリンやプロフルトリン等の常温揮散性ピレスロイド系殺虫剤を有機溶剤で溶解した薬液を、パルプ製の台紙や不織布製シ−トなどに含浸させた防虫剤や、薬液をゲル化させたゲル状の防虫剤などが商品化されている。
固形タイプの防虫剤は、使用とともに経時的に小さくなっていくため薬剤の交換の時期がわかりやすいという利点があるが、その一方で独特の臭気があり、人によっては敬遠される向きがある。また含浸タイプの防虫剤は、防虫剤が揮散して消費されても、含浸担体そのものの外観形状には変化がなく、防虫効果の終点が明確でないという欠点がある。一方、ゲル状の防虫剤においては、使用とともに経時的に収縮していくため、ある程度の使用経過の判断はできるが、ゲルが完全に消滅するわけでなく、依然として防虫効果の終点が明確でないという欠点が残る。また、収縮したゲルの美観に問題が残る場合もある。
これらの問題を克服するものとして、液体の芳香剤をベースにした防虫機能を兼ね備えた芳香剤が提案されている（特許文献３）。これらの多くは、薬液の入ったボトルに差し込まれた吸液芯と呼ばれる吸液芯の毛細管現象により吸い上げられた薬液が、上面に位置するフェルトやパルプ素材の揮散面に染み出し、その面から薬液成分が揮散していくというシステムである。このシステムは薬液の減りが容易に目視でき、薬剤の交換時期がわかりやすいというメリットがある反面、ボトルを倒した際に薬液が周囲にこぼれ出すという心配があった。このことから、薬剤の減りが容易に確認でき、尚且つ、倒してもこぼれない液体タイプの防虫剤の開発が望まれていた。
As a form of insect repellents, solid insect repellents containing camphor, naphthalene, paradichlorobenzene, etc., which are the above-mentioned normal temperature sublimable solids, as active ingredients are known. As an alternative to this solid insect repellent, pulp mounts and non-woven sheets are impregnated with chemicals in which room temperature volatile pyrethroid insecticides such as empentrin and profluthrin, which are active ingredients, are dissolved in an organic solvent. Insect repellents and gel-like repellents obtained by gelling chemicals are commercialized.
Solid type insect repellents have the advantage of being easy to understand when to replace a drug because it becomes smaller over time, but on the other hand, it has a unique odor and tends to be avoided by some people. In addition, the impregnation type insect repellent has the disadvantage that even if the insect repellent is volatilized and consumed, the appearance shape of the impregnated carrier itself does not change and the end point of the insect repellent effect is not clear. On the other hand, gel-like insect repellents shrink over time with use, so a certain degree of use can be judged, but the gel does not completely disappear, and the end point of the insect repellent effect is still unclear The fault remains. There may also be a problem with the aesthetics of the contracted gel.
In order to overcome these problems, a fragrance having an insect repellent function based on a liquid fragrance has been proposed (Patent Document 3). In many of these, the chemical liquid sucked up by the capillary phenomenon of the liquid absorption core called the liquid absorption core inserted into the bottle containing the chemical liquid oozes out to the volatilization surface of the felt or pulp material located on the upper surface. It is a system in which chemical components are volatilized. This system has the merit that the decrease of the chemical solution can be easily seen and it is easy to understand the replacement time of the drug, but there is a concern that the chemical solution spills out when the bottle is knocked down. For this reason, it has been desired to develop a liquid type insect repellent that can easily confirm the decrease of the drug and that does not spill even when it is killed.
本発明は、天然産又は合成の香料成分を有効成分とする液体タイプの衣料害虫用防除剤であって、高い防虫効果を発揮する一方で、人やペットに対する安全性にも優れ、しかも、ほのかな芳香性が効果の立ち上がりを知らしめると共に使用感を高め、更には消費者に対して、使用末期における薬剤の取替え時期もわかりやすい、実用性の高い衣料害虫の芳香性防虫剤を提供することを目的とする。 The present invention is a liquid-type insect pest control agent comprising a natural or synthetic fragrance ingredient as an active ingredient, and exhibits a high insecticidal effect, while also being excellent in safety for humans and pets. To provide consumers with a highly practical fragrance repellent for clothing pests that not only gives notice of the rise of the effect, but also enhances the feeling of use, and also makes it easy for consumers to know when to replace drugs at the end of use. Objective.
そこで本発明は、衣料害虫に対して防虫効果のある香料成分を、液体香料剤透過性フィルムを通して適度な揮散速度で揮散させるために、防虫効果のある香料成分と液体香料剤透過性フィルムの種類を検討し、次いでその揮散を調整するための揮散助剤の組み合わせを鋭意検討した。
検討中の知見として、防虫効果のある香料成分単独だけではなく、香料成分に適当な揮散助剤の添加が必要であることがわかった。しかし、その組み合わせは極めて多種多様であったが、試行錯誤を繰り返した結果、ある特定の防虫剤香料成分と、ある特定の揮散助剤を組み合わせた液体香料剤は、適度な揮散速度を持って液体香料剤透過性フィルムを通して揮散し、衣料害虫に対し適度の防虫効果を発現できることがわかった。そしてこの方式による液体香料剤の揮散は、薬液の減少が経時的に明瞭に目視でき、さらには薬液の揮散後も容器内に残渣による汚れが残らず良好であることを見出した。本発明は、このような知見に基づいて更に改良を重ねることにより、完成したものである。
即ち、本発明は、以下の構成の芳香性防虫剤である。
（１）液体香料剤透過性フィルムを通して、防虫性香料と揮散助剤からなる液体香料剤を揮散させる芳香性防虫剤において、
前記揮散助剤が、パラフィン系炭化水素とグリコールエーテルの混合物であり、かつ、前記パラフィン系炭化水素が炭素数１２から１４のノルマルパラフィン系炭化水素であり、前記グリコールエーテルがプロピレングリコールモノブチルエーテルであることを特徴とする芳香性防虫剤。
（２）前記パラフィン系炭化水素とグリコールエーテルの重量混合比が、１：３から１：５の範囲であることを特徴とする（１）に記載の芳香性防虫剤。
（３）前記防虫性香料が、
エステル基を有し、その分子量が１３０から２１０の範囲にある化合物群のうちのいずれか一つ、又は二つ以上を含有することを特徴とする（１）又は（２）に記載の芳香性防虫剤。
（４）前記防虫性香料が、
安息香酸メチル、酢酸シス−3−ヘキセニル、酢酸ベンジル、ヘキサン酸アリル、酢酸フェニルエチル、ヘプタン酸アリル、酢酸シンナミル、オクタン酸アリル、イソアミルオキシ酢酸アリル、酢酸トリシクロデセニル、シクロヘキシルプロピオン酸アリル、酢酸２−ターシャリーブチルシクロヘキシル、酢酸４−ターシャリーブチルシクロヘキシル、シクロヘキシルオキシ酢酸アリル、フルーテート
のいずれか一つ、または二つ以上を含有することを特徴とする（１）から（３）のいずれかに記載の芳香性防虫剤。
（５）前記防虫性香料が、衣料害虫の生育および生存に対して阻害となる活性を有する香料群から選ばれた一種、または二種以上の混合物であることを特徴とする（１）から（４）のいずれかに記載の芳香性防虫剤。
（６）前記衣料害虫の生育および生存に対して阻害となる活性が、
衣類害虫の卵孵化抑制活性、殺幼虫活性、幼虫摂食阻害活性、幼虫忌避活性、成虫忌避活性、殺成虫活性のうちの一種、又は二種の混合活性であることを特徴とする（５）に記載の芳香性防虫剤。
（７）前記衣料害虫の生育および生存に対して阻害となる活性が、
衣類害虫の殺幼虫活性、幼虫摂食阻害活性のうちの一種、または二種以上の混合物であることを特徴とする（５）に記載の芳香性防虫剤。
（８）前記液体香料剤を、
該液体香料剤が透過しない素材からなり、その一部が開放した形状の容器に液体状態で、収め、且つ、容器の開放部に蓋材として液体香料剤透過性フィルムを貼り付け、このフィルムを通して該液体香料剤を揮散させることを特徴とする（１）から（７）いずれかに記載の芳香性防虫剤。
（９）前記蓋材が、液体香料剤透過性フィルムと液体香料剤非透過性フィルムとを剥離可能なように積層成形したものであり、使用前に、外層に位置する液体香料剤非透過性フィルムのみを剥離して取り除き、液体香料剤透過性フィルムを露出させることにより使用を開始することを特徴とする（８）に記載の芳香性防虫剤。
（１０）前記液体香料剤透過性フィルムが、ポリエチレン素材からなるフィルムであることを特徴とする（１）から（９）のいずれかに記載の芳香性防虫剤。
（１１）前記液体香料剤透過性フィルムが、直鎖状低密度ポリエチレン樹脂フィルムであることを特徴とする（１）から（１０）のいずれかに記載の芳香性防虫剤。
（１２）前記液体香料剤に、その視認性を高めるために着色剤を添加して着色したことを特徴とする（１）から（１１）のいずれかに記載の芳香性防虫剤。
Therefore, the present invention provides an insecticidal fragrance component and a liquid fragrance agent permeable film, in order to volatilize a fragrance component having an insecticidal effect against clothing pests at an appropriate volatilization rate through the liquid fragrance agent permeable film. Then, the combination of volatilization aids for adjusting the volatilization was studied earnestly.
As a finding under investigation, it was found that it is necessary to add an appropriate volatilization aid to the fragrance component as well as the fragrance component having an insect-repellent effect alone. However, the combination was extremely diverse, but as a result of repeated trial and error, liquid fragrances that combine a specific insect repellent fragrance component and a specific volatilization aid have an appropriate volatilization rate. It was found that it can volatilize through the liquid fragrance agent permeable film and can exhibit an appropriate insect repellent effect against clothing pests. Further, it has been found that the liquid fragrance agent volatilization by this method can be clearly observed over time with a decrease in the chemical solution, and further, no contamination due to residue remains in the container even after the chemical solution is volatilized. The present invention has been completed by making further improvements based on such findings.
That is, the present invention is an aromatic insect repellent having the following constitution.
(1) In an aromatic insect repellent that volatilizes a liquid perfume agent comprising an insect repellent perfume and a volatilization aid through a liquid perfume agent permeable film,
The volatilization aid is a mixture of paraffinic hydrocarbon and glycol ether, the paraffinic hydrocarbon is normal paraffinic hydrocarbon having 12 to 14 carbon atoms, and the glycol ether is propylene glycol monobutyl ether. An aromatic insect repellent characterized by that.
(2) The aromatic insect repellent according to (1), wherein the weight mixing ratio of the paraffinic hydrocarbon and glycol ether is in the range of 1: 3 to 1: 5.
(3) The insect repellent fragrance is
The aromaticity according to (1) or (2), which contains any one or two or more of a group of compounds having an ester group and a molecular weight in the range of 130 to 210 Insect repellent.
(4) The insect repellent fragrance is
Methyl benzoate, cis-3-hexenyl acetate, benzyl acetate, allyl hexanoate, phenyl ethyl acetate, allyl heptanoate, cinnamyl acetate, allyl octanoate, allyl isoamyloxyacetate, tricyclodecenyl acetate, allyl cyclohexylpropionate, Any one of (1) to (3), characterized in that it contains any one or more of 2-tertiary butyl cyclohexyl acetate, 4-tertiary butyl cyclohexyl acetate, allyl cyclohexyloxyacetate, and fruteate. Aromatic insect repellents as described in 1.
(5) The insect repellent fragrance is one or a mixture of two or more selected from a fragrance group having an activity that inhibits the growth and survival of clothing pests (1) to ( The aromatic insect repellent according to any one of 4).
(6) the activity that inhibits the growth and survival of the clothing pest,
It is characterized in that it is an egg hatching inhibitory activity, larvicidal activity, larval feeding inhibitory activity, larval repellent activity, adult repellant activity, or one of the mixed insecticidal activities of clothing insect pests (5) Aromatic insect repellents as described in 1.
(7) Activity that inhibits the growth and survival of the clothing pests,
The aromatic insect repellent according to (5), which is one or a mixture of two or more kinds of larvicidal activity and larval feeding inhibitory activity of clothing pests.
(8) The liquid perfume agent,
The liquid fragrance agent is made of a material that does not permeate, and is stored in a liquid state in a partially opened container, and a liquid fragrance agent permeable film is attached to the open portion of the container as a lid, and through this film The aromatic insect repellent according to any one of (1) to (7), wherein the liquid perfume agent is volatilized.
(9) The lid material is formed by laminating the liquid fragrance agent permeable film and the liquid fragrance agent non-permeable film so as to be peelable, and before use, the liquid fragrance agent impermeable located in the outer layer removing only the release to a film, fragrant insect repellent according to to start using by exposing the liquid flavoring agent permeable film, characterized in Rukoto (8).
(10) The aromatic insect repellent according to any one of (1) to (9), wherein the liquid perfume permeable film is a film made of a polyethylene material .
(11) the liquid flavoring agent permeable film, aromatic insect repellent according to any one of and wherein linear low density polyethylene resin film der Rukoto (1) (10).
(12) The aromatic insect repellent according to any one of (1) to (11), wherein the liquid perfume is colored by adding a colorant in order to enhance the visibility.
本発明は、天然産の植物精油由来成分又は合成香料成分を有効成分とする液体タイプの衣料害虫用防除剤であって、高い防虫効果を発揮する一方で、人やペットに対する安全性にも優れている。しかも、ほのかな芳香性が効果の立ち上がりを知らしめると共に使用感を高め、薬液中の防虫剤香料成分と溶剤とがバランスよく揮散していくことから、使用後も容器内に残渣による汚れが残らず、使用末期における薬剤の取替え時期もわかりやすいので、その実用性は極めて高いといえる。 The present invention is a liquid type insect pest control agent comprising a natural plant essential oil-derived component or a synthetic fragrance component as an active ingredient, and exhibits a high insecticidal effect while also being excellent in safety for humans and pets ing. In addition, the subtle fragrance informs the rise of the effect and enhances the feeling of use, and the insecticide fragrance components in the chemical solution and the solvent are volatilized in a well-balanced manner. In addition, since it is easy to understand when to replace the drug at the end of use, its practicality is extremely high.
本発明の芳香性防虫剤の一般的な形態としては、防虫性香料と揮散助剤からなる液体香料剤６を適当な容器１に入れ、開口した容器の一部に貼り付けた液体香料剤透過性フィルム２から、液体香料剤６が揮散するように構成される。 As a general form of the aromatic insect repellent of the present invention, a liquid perfume agent permeated with a liquid perfume agent 6 composed of an insect repellent perfume and a volatilization aid is placed in a suitable container 1 and attached to a part of the opened container. The liquid perfume agent 6 is configured to evaporate from the conductive film 2.
本発明に用いられる防虫性香料としては、天然香料成分、合成香料成分、天然精油の中から選ばれ、イガ、コイガ、ヒメカツオブシムシ、ヒメマルカツオブシムシ、シミ等の衣料害虫に対して防虫効果があるものを用いる事ができる。本発明でいう防虫効果とは、殺幼虫、殺成虫活性はもちろんのこと、衣料害虫の生育ステ−ジにおいて、致命的な作用を与えるかあるいは、死に至らずとも、生育に阻害効果をもたらし、衣料への損害を防止することができるすべての効果を包含する。具体的には産卵抑制活性、卵孵化抑制活性、殺卵活性、殺幼虫活性、幼虫摂食阻害活性、幼虫営巣阻害活性、幼虫羽化阻害活性、幼虫忌避活性、成虫忌避活性、殺成虫活性、成虫交尾撹乱活性等をあげることができる。 The insect repellent fragrance used in the present invention is selected from natural fragrance ingredients, synthetic fragrance ingredients, and natural essential oils, and has an insect repellency effect against clothing pests such as squid, koiga, Himekatsuobushimushi, Hime Marukatsubushimushi, spot Can be used. The insecticidal effect referred to in the present invention is not only of larvicidal and adulterous activity, but also provides a lethal action in the growth stage of clothing pests, or brings an inhibitory effect on growth, even without dying, Includes all effects that can prevent damage to clothing. Specifically, egg-laying-inhibiting activity, egg-hatching-inhibiting activity, egg-killing activity, larvicidal activity, larval feeding inhibitory activity, larval nesting-inhibiting activity, larval emergence-inhibiting activity, larva-repellent activity, adult-repellent activity, adult-killing activity, adult worm Mating disturbance activity etc. can be raised.
防虫性香料として具体的には、テルピネオ−ル、シトロネラ−ル、シトラ−ル、ノナナ−ル、ゲラニオ−ル、ネロ−ル、ボルネオ−ル、デカノ−ル、リナロ−ル、ジヒドロリナロ−ル、テトラヒドロリナロ−ル、ジヒドロミルセノ−ル、ロジノ−ル、メント−ル、ｐ−メンタン−３，８−ジオ−ル、チモ−ル、エバノ−ル、メンタン、カンフェン、ピネン、リモネン、β−ヨノン、セドリルメチルエ−テル、アネト−ル、シンナミルアルデヒド、クミンアルデヒド、安息香酸メチル、酢酸シス−３−ヘキセニル、酢酸ベンジル、ヘプタン酸エチル、酢酸フェニルエチル、ヘキサン酸ブチル、ヘキサンイソ酸ブチル、酢酸シンナミル、酢酸アニシル、酢酸トリシクロデセニル、酢酸２−ターシャリーブチルシクロヘキシル（ベルドックス）、酢酸４−ターシャリーブチルシクロヘキシル（ベルテネックス）、フル−テ−ト、ヘキサン酸アリル、ヘプタン酸アリル、蟻酸ゲラニル、蟻酸シトロネリル、酢酸ゲラニル、酢酸シトロネリル、酢酸ネリル、メチルサリシレ−ト、イソブチルオキシ酢酸アリル、ｎ−アミルオキシ酢酸アリル、イソアミルオキシ酢酸アリル（アリルアミルグリコレート）、イソヘキシルオキシ酢酸アリル、３−エチルアミルオキシ酢酸アリル、シクロペンチルオキシ酢酸アリル、シクロヘキシルオキシ酢酸アリル（シクロガルバネート）、フェノキシ酢酸アリル、オクタン酸アリル、シクロヘキシルプロピオン酸アリル、安息香酸ベンジル、サリチル酸ベンジル、クエン酸トリエチル、δダマスコン、カルボン、シトロネラ油、シナモン油、ユ−カリ油、レモンユーカリ油、ヒバ油、ラベンダー油、オレンジ油、グレープフルーツ油、シダーウッド油、ゼラニウム油、タイムホワイト油、ハッカ油などから選ばれた１種又は２種以上を配合することができる。 Specific examples of insect repellents include terpineol, citronellal, citral, nonanal, geraniol, nerol, borneol, decanol, linalol, dihydrolinalol, tetrahydro Linalol, dihydromyrcenol, rosinol, menthol, p-menthane-3,8-diol, thymol, evanol, menthane, camphene, pinene, limonene, β-ionone, Cedrylmethyl ether, anetole, cinnamylaldehyde, cuminaldehyde, methyl benzoate, cis-3-hexenyl acetate, benzyl acetate, ethyl heptanoate, phenylethyl acetate, butyl hexanoate, butyl hexaneisoate, cinnamyl acetate, anisyl acetate , Tricyclodecenyl acetate, 2-tertiarybutylcyclohexyl acetate (Beldex), vinegar 4-tertiarybutylcyclohexyl (Vertenex), full tate, allyl hexanoate, allyl heptanoate, geranyl formate, citronellyl formate, geranyl acetate, citronellyl acetate, neryl acetate, methyl salicylate, allyl isobutyloxyacetate, n Allyl amyloxyacetate, allyl isoamyloxyacetate (allylamyl glycolate), allyl isohexyloxyacetate, allyl 3-ethylamyloxyacetate, allyl cyclopentyloxyacetate, allyl cyclohexyloxyacetate (cyclogalvanate), allyl phenoxyacetate, octane Acid allyl, cyclohexyl propionate, benzyl benzoate, benzyl salicylate, triethyl citrate, δ damascone, carvone, citronella oil, cinnamon oil, eucalyptus oil, lemon yu Cali oil can be blended cedarwood oil, lavender oil, orange oil, grapefruit oil, cedarwood oil, geranium oil, thyme white oil, one or more selected from such peppermint oil.
これらの中では、エステル基を有し、その分子量が１３０から２１０の範囲にある化合物が好ましく、安息香酸メチル、酢酸シス−３−ヘキセニル、酢酸ベンジル、ヘキサン酸アリル、酢酸フェニルエチル、ヘプタン酸アリル、酢酸シンナミル、オクタン酸アリル、イソアミルオキシ酢酸アリル、酢酸トリシクロデセニル、シクロヘキシルプロピオン酸アリル、酢酸２−ターシャリーブチルシクロヘキシル、酢酸４−ターシャリーブチルシクロヘキシル、シクロヘキシルオキシ酢酸アリル、フルーテートから選ばれた１種又は２種以上を配合するのがより好ましく、特に衣料害虫であるイガ、コイガの幼虫に対して優れた食害防止効果や殺虫活性を発揮する。 Among these, a compound having an ester group and having a molecular weight in the range of 130 to 210 is preferable. Methyl benzoate, cis-3-hexenyl acetate, benzyl acetate, allyl hexanoate, phenylethyl acetate, allyl heptanoate , Cinnamyl acetate, allyl octanoate, allyl isoamyloxyacetate, tricyclodecenyl acetate, allyl cyclohexylpropionate, 2-tert-butylcyclohexyl acetate, 4-tert-butylcyclohexyl acetate, allyl cyclohexyloxyacetate, and flutate It is more preferable to add 1 type or 2 types or more, and it exhibits an excellent food damage prevention effect and insecticidal activity especially against the larvae of garments and moths which are clothing pests.
また、衣料害虫の卵孵化抑制効果を発揮させたいのであれば、特許第４３１１７７３号および特許第４３３２３０１号公報に示された、テトラヒドロリナロール、シトロネラール、シトラール、ゲラニオール、リナロール、ヘキサン酸アリル、ヘプタン酸アリル、カンフェン、β−ヨノン、クミンアルデヒド、ダマスコン、シトロネラ油、シナモン油、ユーカリ油、レモンユーカリ油、ヒバ油などを配合するのが好ましい。さらに、衣料害虫の交尾、産卵、卵孵化等の増殖行為の阻害活性を付与するのであれば、特許第４１４８５５２号公報に示されたように、カルボン、アネトール、リナロール等を配合するのが好ましい。 Further, if it is desired to exert the effect of inhibiting egg hatching of clothing pests, tetrahydrolinalol, citronellal, citral, geraniol, linalool, allyl hexanoate, allyl heptanoate, as disclosed in Japanese Patent Nos. 4311773 and 4332301. , Camphene, β-ionone, cuminaldehyde, damascon, citronella oil, cinnamon oil, eucalyptus oil, lemon eucalyptus oil, hiba oil and the like are preferably blended. Furthermore, as long as the inhibitory activity of breeding acts such as clothing mating, egg laying, egg hatching, etc. is imparted, it is preferable to add carvone, anethole, linalool or the like as disclosed in Japanese Patent No. 4148552.
本発明において、前述の防虫剤香料成分とともに用いられる、揮散助剤としては、
水のほか、エタノール、イソプロパノールのような低級アルコール、
プロピレングリコールのようなグリコール、
ジエチレングリコールモノブチルエーテル、ジエチレングリコールモノヘキシルエーテル、エチレングリコールモノアリルエーテルのようなエチレングリコールエーテル、
ジプロピレングリコールモノメチルエーテル、プロピレングリコールモノプロピルエーテル、プロピレングリコールモノブチルエーテルのようなプロピレングリコールエーテル、
エチレングリコールジメチルエーテル、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテルのようなジアルキルグリコールエーテル、
各種炭素数のノルマルパラフィン系炭化水素やイソパラフィン系炭化水素もしくは芳香族炭化水素や、界面活性剤、可溶化剤、分散剤が適宜用いられる。
In the present invention, as a volatilization aid used together with the aforementioned insect repellent fragrance components,
In addition to water, lower alcohols such as ethanol and isopropanol,
Glycols such as propylene glycol,
Ethylene glycol ethers such as diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, ethylene glycol monoallyl ether,
Propylene glycol ethers such as dipropylene glycol monomethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether,
Dialkyl glycol ethers such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether,
Normal paraffin hydrocarbons, isoparaffin hydrocarbons or aromatic hydrocarbons having various carbon numbers, surfactants, solubilizers, and dispersants are appropriately used.
本発明においては、これらの中でも、パラフィン系炭化水素とグリコールエーテルの混合物が本発明においては好適である。
パラフィン系炭化水素は炭素数１２から１４のノルマルパラフィン系炭化水素がより好適である。炭素数１１以下の物では、自身の揮散が早すぎて本防虫剤用途では不適である。また炭素数１５以上では揮散補助効果が小さく、本用途では使用できない。
また、グリコ−ルエーテルではプロピレングリコールモノブチルエーテル、ジエチレングリコールジメチルエーテル、ジプロピレングリコールジメチルエーテルが好適であるが、中でもプロピレングリコールモノブチルエーテルがより好ましい。
Among these, in the present invention, a mixture of paraffinic hydrocarbon and glycol ether is preferable in the present invention.
The paraffinic hydrocarbon is more preferably a normal paraffinic hydrocarbon having 12 to 14 carbon atoms. Those having 11 or less carbon atoms are too early to volatilize and are not suitable for this insect repellent application. Further, if the carbon number is 15 or more, the volatilization assisting effect is small and cannot be used in this application.
As glycol ethers, propylene glycol monobutyl ether, diethylene glycol dimethyl ether, and dipropylene glycol dimethyl ether are preferred, with propylene glycol monobutyl ether being more preferred.
パラフィン系炭化水素とグリコールエーテルの混合比率に関しては、
パラフィン系炭化水素とグリコールエーテルの混合比が１：３から１：５の範囲であることが好ましい。グリコールエーテルの比率がこれより低ければ揮散が早すぎたり、保管中にフィルムに浸出したりすることがあり、逆にグリコールエーテルの比率がこれより高ければ揮散性が低く、残渣として残ってしまうことになる。
Regarding the mixing ratio of paraffinic hydrocarbon and glycol ether,
The mixing ratio of paraffinic hydrocarbon and glycol ether is preferably in the range of 1: 3 to 1: 5. If the ratio of glycol ether is lower than this, volatilization may be too early, or it may be leached into the film during storage. Conversely, if the ratio of glycol ether is higher than this, volatilization will be low and it will remain as a residue. become.
揮散助剤は自身の揮散の際に香料成分も牽引して揮散する役目を持つと予想され、揮散助剤の比率が低いと揮散効率は改善されない。防虫性香料と揮散助剤との配合比は本発明においては揮散助剤の比率が高いことが望ましく、防虫性香料：揮散助剤は重量比で２：３から２：５、なかでもおよそ１：２がより好ましい。 The volatilization aid is expected to have the role of volatilizing the fragrance component during its volatilization, and the volatilization efficiency is not improved if the ratio of the volatilization aid is low. In the present invention, the mixing ratio of the insect-repellent fragrance and the volatilization aid is preferably a high ratio of the volatilization aid, and the insect-repellent perfume: volatilization aid is in a weight ratio of 2: 3 to 2: 5, especially about 1 : 2 is more preferable.
本発明の芳香性防虫剤は、衣料害虫に対する防虫効果と人やペットに対する安全性に支障を来たさない限りにおいて、各種消臭剤成分や、香調の調整のために他の芳香成分、香料成分を配合してもよい。例えば、「緑の香り」と呼ばれる青葉アルコ−ルや青葉アルデヒド等を添加して、リラックス効果を付与することができる。
また、常温揮散性のピレスロイド系殺虫成分、例えば、エムペントリン、２，３，５，６−テトラフルオロベンジル−２，２−ジメチル−３−（２，２−ジクロロビニル）シクロプロパンカルボキシレ−ト［トランスフルトリン］、４−メチル−２，３，５，６−テトラフルオロベンジル−２，２−ジメチル−３−（１−プロペニル）シクロプロパンカルボキシレ−ト［プロフルトリン］、４−メトキシメチル−２，３，５，６−テトラフルオロベンジル−２，２−ジメチル−３−（１−プロペニル）シクロプロパンカルボキシレ−ト［メトフルトリン］などを添加すれば防虫効果の向上を図ることが可能となる。
As long as the aromatic insect repellent of the present invention does not interfere with the insect repellent effect against clothing pests and safety for humans and pets, various deodorant components, other aromatic components for adjusting the fragrance, A perfume ingredient may be blended. For example, green leaf alcohol or green leaf aldehyde called “green fragrance” can be added to give a relaxing effect.
Also, room temperature volatile pyrethroid insecticides such as empentrin, 2,3,5,6-tetrafluorobenzyl-2,2-dimethyl-3- (2,2-dichlorovinyl) cyclopropanecarboxylate [ Transfluthrin], 4-methyl-2,3,5,6-tetrafluorobenzyl-2,2-dimethyl-3- (1-propenyl) cyclopropanecarboxylate [profluthrin], 4-methoxymethyl-2 1,3,5,6-tetrafluorobenzyl-2,2-dimethyl-3- (1-propenyl) cyclopropanecarboxylate [methfluthrin] and the like can improve the insect-repellent effect.
その他、本発明の芳香性防虫剤に添加できる成分としては、
消臭剤として、揮発性のヒバ油、ヒノキ油、竹エキス、ヨモギエキス、キリ油やピルビン酸エチル、ピルビン酸フェニルエチル等のピルビン酸エステルなどが、
防黴剤としては、２−ｎ−オクチル−４−イソチアゾリン−３−オン、イソプロピルメチルフェノ−ル、オルソフェニールフェノールなどが、
抗菌剤としては、ヒノキチオ−ル、テトラヒドロリナロール、オイゲノール、シトロネラール、アリルイソチオシアネートなどが挙げられる。
In addition, as a component that can be added to the aromatic insect repellent of the present invention,
As a deodorant, volatile Hiba oil, cypress oil, bamboo extract, mugwort extract, drill oil, pyruvate such as ethyl pyruvate, phenylethyl pyruvate, etc.
Antifungal agents include 2-n-octyl-4-isothiazolin-3-one, isopropylmethylphenol, orthophenylphenol, etc.
Antibacterial agents include hinokitiol, tetrahydrolinalol, eugenol, citronellal, allyl isothiocyanate and the like.
本発明において用いられる液体香料剤透過性フィルム２とは、液体香料剤６を、液体ではなく気体の状態でフィルムから透過、放散させるものである。本液体香料剤透過性フィルム２としては、耐薬品性があり、液体香料剤を液体として滲出させることなく、気体として容器外へ揮散透過するものであれば特に限定されない。
一例としては、ポリエチレン、低密度ポリエチレン樹脂フィルム、直鎖状低密度ポリエチレン樹脂フィルムといったポリエチレン素材からなるフィルムや、ポリプロピレン、エチレン−酢酸共重合樹脂フィルム等が挙げられる。中でも本発明においては、直鎖状低密度ポリエチレン樹脂フィルムが最も好ましい。また、これ以外の素材でも、微小多孔化処理をして透過性を付与したポリプロピレンやポリエチレンテレフタレート、ポリアミド等の他のプラスティック樹脂フィルムも用いることができる。
The liquid fragrance agent permeable film 2 used in the present invention is a film in which the liquid fragrance agent 6 is transmitted and dissipated from the film in a gas state instead of a liquid. The liquid fragrance agent permeable film 2 is not particularly limited as long as it has chemical resistance and does not exude the liquid fragrance agent as a liquid and can be vaporized and transmitted outside the container as a gas.
As an example, a film made of a polyethylene material such as polyethylene, a low density polyethylene resin film, a linear low density polyethylene resin film, a polypropylene, an ethylene-acetic acid copolymer resin film, and the like can be given. Among these, in the present invention, a linear low density polyethylene resin film is most preferable. In addition, other plastic resin films such as polypropylene, polyethylene terephthalate, and polyamide that have been subjected to microporosity treatment to impart permeability can also be used.
また、本発明では、使用前に液体香料剤が揮散するのを防止するために、容器の蓋剤５としての素材が、上記液体香料剤透過性フィルム２の外気と接触する面である表面を、取り除き可能なガスバリア性の液体香料剤非透過性フィルム３で覆った多層体フィルムであることが望ましい。
具体的には、蓋材５が、液体香料剤透過性フィルム２と液体香料剤非透過性フィルム３とが接着層４を介した積層体であり、外層に位置する液体香料剤非透過性フィルム３を、接着層４と共に剥離、取り除くことにより、液体香料剤透過性フィルム２を露出させ、使用開始することができる。
この液体香料剤非透過性フィルム３部材については、使用する防虫性香料の種類に応じて適宜選択されるが、ポリエチレンテレフタレート、ナイロン、アルミ箔等が例示される。上記液体香料剤非透過性フィルム３は、１種の部材からなる単層のフィルムであってもよく、また２種以上の素材を積層したフィルムであってもよい。
Moreover, in this invention, in order to prevent that a liquid perfume agent volatilizes before use, the surface which is a surface where the raw material as the lid | cover 5 of a container contacts the external air of the said liquid perfume agent permeable film 2 is used. A multilayer film covered with a removable gas barrier liquid perfume non-permeable film 3 is desirable.
Specifically, the lid 5 is a laminate in which the liquid fragrance permeable film 2 and the liquid fragrance non-permeable film 3 are interposed via the adhesive layer 4, and the liquid fragrance non-permeable film located in the outer layer. By peeling and removing 3 together with the adhesive layer 4, the liquid perfume permeable film 2 can be exposed and the use can be started.
The liquid fragrance agent non-permeable film 3 member is appropriately selected according to the type of insect-proof fragrance used, and examples thereof include polyethylene terephthalate, nylon, and aluminum foil. The liquid perfume non-permeable film 3 may be a single-layer film made of one kind of member, or may be a film in which two or more kinds of materials are laminated.
なお、上記のように、液体香料剤透過性フィルム２を、取り除き可能な液体香料剤非透過性フィルム３で覆わない場合には、本発明の芳香性防虫剤は、使用前に香料が揮散するのを防止するために、容器１全体を、液体香料剤非透過性部材からなる包装体に密閉した状態で収容しておくことが望ましい。 In addition, as mentioned above, when the liquid fragrance agent permeable film 2 is not covered with the removable liquid fragrance agent non-permeable film 3, the aromatic insect repellent of the present invention volatilizes the fragrance before use. In order to prevent this, it is desirable to store the entire container 1 in a sealed state in a package made of a liquid perfume non-permeable member.
容器本体１としてはプラスチック製の物を用いるのが実用上適当である。このプラスチックの材質として、液体香料剤が透過しない素材であることが必要であり、耐内容物性を考慮して、基材にポリエチレンフタレート、ポリカーボネート、ポリプロピレン、ポリアミドなどが使用できる。 容器の形状は液体が収納でき、一部に開口部を有する形状であればよく、真空成形法や圧空成形法などの熱成形法や、インジェクション成形法など公知慣用の成形方法で作製される。
この容器本体の開口部周辺には平坦な面やフランジ部７を設け、液体香料剤透過性フィルムを接着剤や、あるいは超音波溶着などにより熱シールして、容器内に液体香料剤を封じることができる。この際、液体自体の減りを確認できるように、吸液性の含浸体等に担持させることなく、液体香料剤を液体のまま容器に添加することが望ましい。
It is practically appropriate to use a plastic object as the container body 1. The plastic material needs to be a material that does not allow liquid perfume to permeate, and polyethylene phthalate, polycarbonate, polypropylene, polyamide, or the like can be used for the base material in consideration of resistance to contents. The shape of the container may be any shape that can store liquid and has an opening in a part thereof, and is produced by a known and commonly used molding method such as a vacuum molding method or a pressure molding method, or an injection molding method.
A flat surface or flange portion 7 is provided around the opening of the container body, and the liquid fragrance agent permeable film is heat-sealed by an adhesive or ultrasonic welding to seal the liquid fragrance agent in the container. Can do. At this time, it is desirable to add the liquid fragrance agent to the container as it is without being supported on a liquid-absorbing impregnated body or the like so that the decrease of the liquid itself can be confirmed.
芳香性防虫剤は、薬液の減り具合が観察しやすいように、必要に応じて染料で着色することができる。染料は、本発明で使用する防虫性香料と揮散助剤に溶けるものであれば特に限定されず、橙色４０３号のようなアゾ染料、緑色２０２号のようなアントラキノン染料、その他、タール色素、インジゴ系色素等が提示できる。 The aromatic insect repellent can be colored with a dye as necessary so that the decrease in the chemical solution can be easily observed. The dye is not particularly limited as long as it is soluble in the insect repellent and the volatilization aid used in the present invention, and is an azo dye such as orange 403, an anthraquinone dye such as green 202, other tar pigments, indigo System dyes can be presented.
次に具体的な実施等を挙げて、本発明を説明するが、本発明はこれらの実施例に限定されるものではない。
（試験例１：防虫性香料基礎効力試験）
Next, the present invention will be described with specific implementations, but the present invention is not limited to these examples.
(Test Example 1: Insect repellent perfume basic efficacy test)
１０×１０ｃｍの濾紙に、表１記載の各種香料成分１００ｍｇをエタノールで１０倍希釈したものを１ml分注して含浸させ、エタノールは風乾して供試濾紙とした。
容量約６Ｌのガラス瓶の底に供試濾紙を置き、その５ｃｍ上方に、３０日令、平均体重３０〜３５ｍｇ／頭のイガ幼虫１０頭と、羊毛試験布（２ｃｍ×２ｃｍ、４０〜４５ｍｇ）を入れたカゴを固定した。次に、ガラス瓶を密閉し、２７℃、湿度６５％の恒温恒湿室内に７日間放置したのち、羊毛試験布を取り出して食害率（食害量／元の重量×１００）を測定するとともに、死虫率を求めた。
食害率、死虫率と総合評価を表１に示す。
総合評価は以下の基準で示した。 ◎：食害がなく、死虫率が１００％のもの。○：食害がなく、死虫率が５０〜９９％のもの。△：食害はないものの、死虫率が１〜５０％のもの。×：食害があるもの、あるいは食害がないものの死虫率が０％のもの。
A 10 × 10 cm filter paper, impregnated with 1 ml of 100-fold diluted 100-percent fragrance ingredients listed in Table 1 with ethanol, was impregnated, and ethanol was air-dried to obtain a test filter paper.
Place the test paper on the bottom of a glass bottle with a capacity of about 6L, and place 10 moth larvae with an average weight of 30 to 35 mg / head and a wool test cloth (2 cm x 2 cm, 40 to 45 mg) 5 cm above it. The basket that was put in was fixed. Next, after sealing the glass bottle and leaving it in a constant temperature and humidity room at 27 ° C. and a humidity of 65% for 7 days, the wool test cloth was taken out and the damage rate (damage amount / original weight × 100) was measured. The insect rate was determined.
Table 1 shows the feeding damage rate, dead insect rate and overall evaluation.
The overall evaluation is shown by the following criteria. A: There is no food damage and the death rate is 100%. ○: No damage to insects and a death rate of 50 to 99%. Δ: Although there is no food damage, the death rate is 1 to 50%. X: A thing with eating damage or a thing with no insect damage but a death rate of 0%.
試験の結果より、各種香料成分のうち、防虫性香料として効果の認められたものを選抜して、フィルム透過性の試験を行った。
（試験例２：フィルム透過性揮散試験）
From the results of the test, among the various fragrance components, those that were confirmed to be effective as insect repellent fragrances were selected and tested for film permeability.
(Test Example 2: Film permeability volatilization test)
５×１５ｃｍのサイズ（厚さ７０μｍ）のポリエチレンフィルムの長辺を二つ折りにして、長辺二方をヒートシールした後、表１記載の香料成分を１．５g（約２ｍｌ）分注し、さらに残りの一方もシールして香料入り簡易フィルム容器を作製した。
この香料入り簡易フィルム容器を２５℃恒温室にて吊り下げ設置し、３０日目まで定期的に重量の減少を測定し、初期との差から揮散率を求めた。
１５日および３０日目での揮散率と総合評価を表２に示す。
（総合評価は◎：３０日目で揮散率が７５％以上のもの。○：３０日目で揮散率が３０〜７４％のもの。△：３０日目で揮散率が１０〜２９％のもの。×：３０日目で揮散率が９％以下のもの。で示した。）
After folding the long side of a polyethylene film having a size of 5 × 15 cm (thickness 70 μm) in half and heat-sealing the two long sides, 1.5 g (about 2 ml) of the fragrance component described in Table 1 is dispensed, Further, the remaining one was sealed to prepare a simple film container containing a fragrance.
This simple fragranced film container was suspended and installed in a constant temperature room at 25 ° C., and the decrease in weight was measured periodically until the 30th day, and the volatilization rate was determined from the difference from the initial stage.
Table 2 shows the volatilization rate and comprehensive evaluation on the 15th and 30th days.
(Overall evaluation is ◎: Volatilization rate is 75% or more on the 30th day. ○: Volatilization rate is 30 to 74% on the 30th day. Δ: Volatilization rate is 10 to 29% on the 30th day. X: The volatilization rate on the 30th day is 9% or less.)
試験の結果、アルコール系、エーテル系、ケトン系の香料に比べて、エステル系の防虫剤香料の揮散が比較的良好な傾向にあった。 ただし防虫性
香料のみでは揮散速度が緩慢なことから、防虫剤として実用性を高めるために、揮散を促進する揮散助剤の検討を行った。
（試験例３： 防虫性香料と揮散助剤の組合せ： 実施例１〜実施例６）
As a result of the test, the volatilization of the ester-based insect repellent fragrance tended to be relatively good compared to the alcohol-based, ether-based, and ketone-based fragrances. However, since the volatilization rate was slow only with insect-repellent fragrances, we investigated volatilization aids that promote volatilization in order to increase practicality as insect repellents.
(Test Example 3: Combination of insect repellent fragrance and volatilization aid: Examples 1 to 6)
試験例２で比較的良好であった防虫剤香料のうちから選んで調合して作製した表３記載の防虫性香料と揮散助剤と色素を、表４に示す処方で混ぜ合わせ、各種液体香料剤を作製した。この液体香料剤の薬液を、所定の容器（ポリエチレンでラミレートしたポリエチレンテレフタレート樹脂シ−トを、縦×横×厚みが３０×３０×６ｍｍであり、開口部周囲に８ｍｍのフランジを有するようトレ−状に真空成形したもの）に３ｇ分注し、フランジ部分を含む開口部を、蓋材フィルムで覆いヒートシールした。
蓋材フィルムは、液体香料剤透過性フィルム（直鎖状低密度ポリエチレンフィルム：厚さ７０μｍ）と非透過性フィルム（ポリエチレンテレフタレートフィルムとアルミニウムフィルムとポリプロピレンフィルム）とを接着層として溶融樹脂のポリエチレン層を介して張り合わせて積層成形したものであり、使用前に蓋材を容器から剥がすと、液体香料剤非透過性フィルムのみが剥離され、容器側に残った液体香料剤透過性フィルムが外気に露呈し、容器内の液体香料剤が揮散を始める。この液体香料剤非透過性フィルム剥離させた容器を、２５℃恒温室にて静置し、６０日目まで定期的に重量の減少を測定し、初期重量との差から液体香料剤の揮散率を測定した。 また蓋材フィルムを含む容器の安定性を見るために、蓋材における液体香料剤非透過性フィルムを剥離しない状態での容器も、同条件である２５℃恒温室にて６０日目まで静置した。 ２０日、４０日、６０日目での各揮散率と総合評価を表５に示した。
Insect repellents, volatilization aids and pigments listed in Table 3 prepared by selecting and preparing from insect repellent perfumes that were relatively good in Test Example 2 were mixed in the formulations shown in Table 4, and various liquid perfumes An agent was prepared. This liquid perfume chemical solution was transferred to a predetermined container (polyethylene terephthalate resin sheet laminated with polyethylene, length × width × thickness 30 × 30 × 6 mm, and with an 8 mm flange around the opening. 3 g), and the opening including the flange portion was covered with a lid material film and heat-sealed.
The cover material film is a polyethylene layer of a molten resin using a liquid perfume permeable film (linear low density polyethylene film: thickness 70 μm) and a non-permeable film (polyethylene terephthalate film, aluminum film and polypropylene film) as an adhesive layer. When the lid is peeled off from the container before use, only the liquid fragrance agent non-permeable film is peeled off, and the liquid fragrance agent permeable film remaining on the container side is exposed to the outside air. Then, the liquid flavoring agent in the container starts to volatilize. The container from which this liquid perfume agent-impermeable film was peeled was allowed to stand in a thermostatic chamber at 25 ° C., and the decrease in weight was measured periodically until the 60th day. Was measured. In addition, in order to check the stability of the container containing the lid material film, the container in the state where the liquid perfume non-permeable film in the lid material is not peeled is also allowed to stand in the same condition at 25 ° C. until the 60th day. did. Table 5 shows the volatilization rates and comprehensive evaluations on the 20th, 40th, and 60th days.
この試験の結果、防虫剤香料と、揮散助剤としてのパラフィン系炭化水素とグリコールエーテルの混合物からなる処方である実施例１から６において、使用開始から６０日目まで安定した揮散が認められた。その中においても、パラフィン系溶剤：グリコールエーテルの比が１：３から１：５の範囲にある実施例２、４，５，６が有効であった。この範囲外であって、グリコールエーテルの比率が小さいと揮散速度が速すぎる傾向にあり、グリコールエーテルの比率が大きいと揮散速度が遅すぎる傾向にあった。また、実施例２と６を比較して、着色剤にて薬液に着色を施すと、薬液の揮散による減少がわかり易く有効であった。
本発明では揮散助剤としてのパラフィン系炭化水素とグリコールエーテルの混合物であることが重要であり、揮散助剤としてパラフィン系炭化水素だけ（比較例２）や、グリコールエーテルだけ（比較例３）では良好な揮散が得られなかった。
As a result of this test, stable volatilization was recognized from the start of use to the 60th day in Examples 1 to 6, which are prescriptions composed of a mixture of an insect repellent fragrance, a paraffinic hydrocarbon as a volatilization aid, and a glycol ether. . Among them, Examples 2, 4, 5, and 6 in which the ratio of paraffinic solvent: glycol ether was in the range of 1: 3 to 1: 5 were effective. Outside this range, when the proportion of glycol ether is small, the volatilization rate tends to be too fast, and when the proportion of glycol ether is large, the volatilization rate tends to be too slow. Moreover, when Examples 2 and 6 were compared and the chemical was colored with a colorant, the decrease due to the volatilization of the chemical was easily understood and effective.
In the present invention, it is important that the mixture is a paraffinic hydrocarbon and a glycol ether as a volatilization aid, and only the paraffinic hydrocarbon (Comparative Example 2) or the glycol ether alone (Comparative Example 3) is used as the volatilization aid. Good volatilization was not obtained.
先の試験例３での実施例２に用いられた物と同一の薬液、容器、フィルムからなる防虫剤を、周囲に開口部を有するポリプロピレン製外容器（４５×４５×１５ｍｍ）に納めた。
本芳香性防虫剤を、衣類が８割ほど収納された縦５０ｃｍ×横４０ｃｍ×高さ２５ｃｍ（約５０リットル）の衣装ケース 内の衣類の隙間に２個設置したところ、約２ヶ月にわたり、イガ、コイガ、ヒメカツオブシムシ、ヒメマルカツオブシムシ等の衣類害虫に対して食害を受けることなく、さらに消臭効果も付与されて極めて実用的であった。
The same insecticide made of the same chemical solution, container and film as used in Example 2 in the previous Test Example 3 was placed in a polypropylene outer container (45 × 45 × 15 mm) having an opening around it.
When two of these aromatic insect repellents were installed in the gap between the clothes in a 50 cm long x 40 cm wide x 25 cm high (about 50 liters) clothes case containing about 80% of the clothes, It was extremely practical because it was not damaged by clothing pests such as koiga, Himekatsuobushimushi, Himemarukatsubushimushi, and was given a deodorizing effect.
先の試験例３での実施例３に用いられた物と同一の薬液、容器、フィルムからなる防虫剤を、吊り下げ部が付属し、周囲に開口部と薬液の減りが確認できる開口窓を有するポリプロピレン製外容器（１００×５０×１５ｍｍ）１個につき２個納めた。この外容器を２個、すなわち計４個の芳香性防虫剤を容積約５００Ｌの洋服タンスに吊るして２ヶ月間使用した。その結果、その間、衣料害虫から衣類を完全に保護することができ、また、２ヶ月後の時点で着色された薬液によって認められる残量は僅かで、終点表示機能を有することが認められた。また薬液の残量以外には容器内に色素や油分残渣の汚れは認められず極めて実用的であった。 Insect repellent consisting of the same chemical solution, container, and film as used in Example 3 in the previous Test Example 3 is attached with a hanging part, and an opening window can be confirmed around the opening and the chemical solution. Two pieces were put in one polypropylene outer container (100 × 50 × 15 mm). Two of these outer containers, that is, a total of four aromatic insect repellents were hung on a clothes chest having a volume of about 500 L and used for two months. As a result, it was confirmed that clothing could be completely protected from clothing pests during that period, and that the remaining amount recognized by the colored chemicals after 2 months was small and had an end point display function. In addition to the remaining amount of the chemical solution, no stain of pigment or oil residue was found in the container, which was extremely practical.
本発明は、衣料防虫剤だけでなく、害虫忌避分野においても広く利用可能であり、極めて有用である。 The present invention can be widely used not only in clothing insect repellents but also in the field of pest repellent and is extremely useful.
１ 容器
２ 液体香料剤透過性フィルム
３ 液体香料剤非透過性フィルム
４ 接着層
５ 蓋材
６ 液体香料剤
７ フランジ部
DESCRIPTION OF SYMBOLS 1 Container 2 Liquid perfume agent permeable film 3 Liquid perfume agent non-permeable film 4 Adhesive layer 5 Cover material 6 Liquid perfume agent 7 Flange part
Claims (12)
前記揮散助剤が、パラフィン系炭化水素とグリコールエーテルの混合物であり、かつ、前記パラフィン系炭化水素が炭素数１２から１４のノルマルパラフィン系炭化水素であり、前記グリコールエーテルがプロピレングリコールモノブチルエーテルであることを特徴とする芳香性防虫剤。 In an aromatic insect repellent that volatilizes a liquid perfume agent consisting of an insect repellent perfume and a volatilization aid through a liquid perfume agent permeable film,
The volatilization aid is a mixture of paraffinic hydrocarbon and glycol ether, the paraffinic hydrocarbon is normal paraffinic hydrocarbon having 12 to 14 carbon atoms, and the glycol ether is propylene glycol monobutyl ether. An aromatic insect repellent characterized by that.
エステル基を有し、その分子量が１３０から２１０の範囲にある化合物群のうちのいずれか一つ、又は二つ以上を含有することを特徴とする請求項１又は請求項２に記載の芳香性防虫剤。 The insect repellent fragrance is
3. The fragrance according to claim 1, comprising at least one of a compound group having an ester group and a molecular weight in the range of 130 to 210, or two or more. Insect repellent.
安息香酸メチル、酢酸シス−3−ヘキセニル、酢酸ベンジル、ヘキサン酸アリル、酢酸フェニルエチル、ヘプタン酸アリル、酢酸シンナミル、オクタン酸アリル、イソアミルオキシ酢酸アリル、酢酸トリシクロデセニル、シクロヘキシルプロピオン酸アリル、酢酸２−ターシャリーブチルシクロヘキシル、酢酸４−ターシャリーブチルシクロヘキシル、シクロヘキシルオキシ酢酸アリル、フルーテート
のいずれか一つ、または二つ以上を含有することを特徴とする請求項１から請求項３のいずれかに記載の芳香性防虫剤。 The insect repellent fragrance is
Methyl benzoate, cis-3-hexenyl acetate, benzyl acetate, allyl hexanoate, phenyl ethyl acetate, allyl heptanoate, cinnamyl acetate, allyl octanoate, allyl isoamyloxyacetate, tricyclodecenyl acetate, allyl cyclohexylpropionate, 4. Any one of 2-tertiary butyl cyclohexyl acetate, 4-tertiary butyl cyclohexyl acetate, cyclohexyl allyl oxyacetate, or fructate, or two or more thereof, Aromatic insect repellents as described in 1.
衣類害虫の卵孵化抑制活性、殺幼虫活性、幼虫摂食阻害活性、幼虫忌避活性、成虫忌避活性、殺成虫活性のうちの一種、又は二種の混合活性であることを特徴とする請求項５に記載の芳香性防虫剤。 Activity that inhibits the growth and survival of the clothing pests,
6. An insect hatching inhibitory activity, a larvicidal activity, a larval feeding inhibitory activity, a larval repellent activity, an adult repellant activity, and an insecticidal activity of clothing pests, or a mixed activity of the two types Aromatic insect repellents as described in 1.
衣類害虫の殺幼虫活性、幼虫摂食阻害活性のうちの一種、または二種以上の混合物であることを特徴とする請求項５に記載の芳香性防虫剤。 Activity that inhibits the growth and survival of the clothing pests,
6. The aromatic insect repellent according to claim 5, which is one or a mixture of two or more kinds of larvicidal activity and larval feeding inhibitory activity of clothing pests.
該液体香料剤が透過しない素材からなり、その一部が開放した形状の容器に液体状態で、収め、且つ、容器の開放部に蓋材として液体香料剤透過性フィルムを貼り付け、このフィルムを通して該液体香料剤を揮散させることを特徴とする請求項１から請求項７いずれかに記載の芳香性防虫剤。 The liquid perfume agent,
The liquid fragrance agent is made of a material that does not permeate, and is stored in a liquid state in a partially opened container, and a liquid fragrance agent permeable film is attached to the open portion of the container as a lid, and through this film The aromatic insect repellent according to any one of claims 1 to 7, wherein the liquid perfume agent is volatilized.
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| JP2011147028A JP5858663B2 (en) | 2011-07-01 | 2011-07-01 | Aromatic insect repellent |
| CN201210228425.9A CN102845416B (en) | 2011-07-01 | 2012-07-02 | Armaticity insecting driving insect agent |
| HK13102783.2A HK1175368A1 (en) | 2011-07-01 | 2013-03-06 | Aromatic insect-preventing repellent |
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| JP5840029B2 (en) * | 2012-02-28 | 2016-01-06 | 花王株式会社 | Insect control agent |
| JP6041720B2 (en) * | 2013-03-22 | 2016-12-14 | 大日本除蟲菊株式会社 | Invasion inhibitor and feeding inhibitor of clothing pests |
| JP6925098B2 (en) * | 2015-02-20 | 2021-08-25 | アース製薬株式会社 | Activity enhancer for pests of compounds with menthan skeleton |
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| JPS6059882B2 (en) * | 1978-11-13 | 1985-12-27 | 出光興産株式会社 | Insect repellent for clothing |
| US5711955A (en) * | 1993-09-28 | 1998-01-27 | Celaflor Gmbh | Insect combatant controlled/prolonged delivery device |
| JP4311773B2 (en) * | 1997-04-14 | 2009-08-12 | エステー株式会社 | Fiber insect pest egg hatching inhibitor and insect control method |
| JP3209962B2 (en) * | 1997-04-17 | 2001-09-17 | エステー化学株式会社 | Fiber pest egg hatching inhibitor, fiber pest egg hatching inhibitor composition, and insect repellent method using the same |
| JP4317349B2 (en) * | 2001-07-11 | 2009-08-19 | アース製薬株式会社 | Heating transpiration method and heating transpiration container used therefor |
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