JP6823225B2 - Flying pest repellent products and flying pest repellent methods - Google Patents
Flying pest repellent products and flying pest repellent methods Download PDFInfo
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- JP6823225B2 JP6823225B2 JP2020513231A JP2020513231A JP6823225B2 JP 6823225 B2 JP6823225 B2 JP 6823225B2 JP 2020513231 A JP2020513231 A JP 2020513231A JP 2020513231 A JP2020513231 A JP 2020513231A JP 6823225 B2 JP6823225 B2 JP 6823225B2
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- pest repellent
- flying pest
- rubber molded
- flying
- product
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Images
Classifications
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- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
- A01N25/10—Macromolecular compounds
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/18—Vapour or smoke emitting compositions with delayed or sustained release
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N27/00—Biocides, pest repellants or attractants, or plant growth regulators containing hydrocarbons
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N31/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic oxygen or sulfur compounds
- A01N31/04—Oxygen or sulfur attached to an aliphatic side-chain of a carbocyclic ring system
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N31/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic oxygen or sulfur compounds
- A01N31/06—Oxygen or sulfur directly attached to a cycloaliphatic ring system
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N35/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical
- A01N35/06—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical containing keto or thioketo groups as part of a ring, e.g. cyclohexanone, quinone; Derivatives thereof, e.g. ketals
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/02—Saturated carboxylic acids or thio analogues thereof; Derivatives thereof
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/10—Aromatic or araliphatic carboxylic acids, or thio analogues thereof; Derivatives thereof
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
Landscapes
- Life Sciences & Earth Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Plant Pathology (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- Agronomy & Crop Science (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Toxicology (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Catching Or Destruction (AREA)
Description
本発明は、硬度50度以下のシリコーンゴム成形体において、飛翔害虫忌避香料成分を含有する飛翔害虫忌避香料組成物が、シリコーンゴム成形体を構成するゴムの分子構造の隙間に入り込んだ状態で保持されている飛翔害虫忌避製品、及び当該飛翔害虫忌避製品を用いた飛翔害虫忌避方法に関する。 In the present invention, in a silicone rubber molded body having a hardness of 50 degrees or less, a flying pest repellent fragrance composition containing a flying pest repellent fragrance component is held in a state of being inserted into a gap in the molecular structure of the rubber constituting the silicone rubber molded body. The present invention relates to a flying pest repellent product and a flying pest repellent method using the flying pest repellent product.
従来、蚊、蚋、ユスリカ、ハエ類などの飛翔害虫に対して、ディート(N,N−ジエチルトルアミド)を含む忌避剤を皮膚表面に塗布する方法が汎用されている。しかし、ディートは通常の香料成分と比べると揮散性が幾分低いために空間的な忌避効果は期待できない。一方、常温揮散性の殺虫成分、例えば、ピレスロイド系のエムペントリン等を空間に揮散させて飛翔害虫に対する忌避効果を実現することはできるが、常温揮散性の殺虫成分の使用が敬遠される場面が少なからず存在する。 Conventionally, a method of applying a repellent containing DEET (N, N-diethyltoluamide) to the skin surface against flying pests such as mosquitoes, silkworms, chironomids, and flies has been widely used. However, DEET cannot be expected to have a spatial repellent effect because it is somewhat less volatile than ordinary fragrance components. On the other hand, it is possible to volatilize a room temperature volatilizing insecticidal component, for example, pyrethroid empentrin, into the space to realize a repellent effect against flying pests, but the use of a room temperature volatilizing insecticidal component is rarely avoided. Does exist.
そこで、忌避成分として揮散性の天然精油や、その組成成分を用いる試みがいくつか提案されている。例えば、シトロネラ油やその主成分であるシトロネラールが蚊に対して忌避効果を示すことはよく知られており、アメリカではシトロネラ油を有効成分として含有するキャンドルが市販されている。しかしながら、キャンドルの熱を利用してシトロネラールを放散させる方法は、シトロネラールの揮散効率が悪く、実用的な忌避効果を奏し得ない。 Therefore, some attempts have been proposed to use volatile natural essential oils as repellent components and their composition components. For example, it is well known that citronella oil and its main component, citronellal, have a repellent effect on mosquitoes, and candles containing citronella oil as an active ingredient are commercially available in the United States. However, the method of dissipating citronellal using the heat of the candle has poor volatilization efficiency of citronellal and cannot produce a practical repellent effect.
また、特開2002−173407号公報(特許文献1)には、シトロネラ油の他、オレンジ油、カシア油などから選ばれた天然精油を有効成分とする飛翔害虫忌避剤が記載され、液剤に使用するための溶剤として、メチルアルコール、エチルアルコール等のアルコール類、フタル酸ジエチル、ミリスチン酸イソプロピル等のエステル類、ヘキサン、ケロシン、パラフィン等の脂肪族炭化水素類、芳香族炭化水素類、エーテル類等、多種が挙げられている。 Further, Japanese Patent Application Laid-Open No. 2002-173407 (Patent Document 1) describes a flying pest repellent containing a natural essential oil selected from orange oil, cassia oil and the like as an active ingredient in addition to citronella oil, and is used as a liquid preparation. As a solvent for this, alcohols such as methyl alcohol and ethyl alcohol, esters such as diethyl phthalate and isopropyl myristate, aliphatic hydrocarbons such as hexane, kerosine and paraffin, aromatic hydrocarbons, ethers and the like. , Various types are listed.
加えて、特開2003−201203号公報(特許文献2)は、害虫忌避成分として、シトロネラールと、ターピネオール、メントール、リモネン、ゲラニオール、シトロネロール、カンフェン等から選ばれる1種又は2種以上とを含み、害虫忌避成分中におけるシトロネラールの含有量が2〜10質量%である害虫忌避剤揮散組成物を開示している。しかしながら、これらの忌避剤は、天然産志向と安全性への配慮を謳っているものの、その忌避効果は持続性に劣っており、必ずしも満足のいくものではない。 In addition, Japanese Patent Application Laid-Open No. 2003-201003 (Patent Document 2) contains citronellal and one or more selected from tarpineol, menthol, limonene, geraniol, citronellol, camphene and the like as pest repellent components. Disclosed is a pest repellent volatilization composition in which the content of citronellal in the pest repellent component is 2 to 10% by mass. However, although these repellents claim to be naturally produced and give consideration to safety, their repellent effects are inferior in sustainability and are not always satisfactory.
更に、特開昭61−289002号公報(特許文献3)には、「グリコールエーテル類を有効成分とする節足動物類、軟体動物類並びに爬虫類用忌避剤」が提案されている。特許文献3には、グリコールエーテル類がゴキブリやダニ類に優れた忌避効果を示す旨が記載されているが、その効果は到底十分とは言い難く、しかも飛翔害虫に対する忌避効果は何ら言及されていない。 Further, Japanese Patent Application Laid-Open No. 61-289002 (Patent Document 3) proposes "a repellent for arthropods, mollusks and reptiles containing glycol ethers as an active ingredient". Patent Document 3 describes that glycol ethers have an excellent repellent effect on cockroaches and mites, but the effect is far from sufficient, and the repellent effect on flying pests is mentioned at all. Absent.
このように、飛翔害虫忌避効果、更にはこれに加えて芳香の持続性向上を目指した有用な飛翔害虫忌避香料組成物は未だ知られておらず、その開発が求められている。 As described above, a useful flying pest repellent fragrance composition aiming at the effect of repelling flying pests and further improving the persistence of fragrance is not yet known, and its development is required.
ところで、シリコーンゴムは、吸着性及び気体透過性に優れ、かつ物性的に安定であり、香料の発散性に優れることが知られている。このような性質を利用し、香料をシリコーンゴムに含有させた芳香剤が市販されている。香料をシリコーンゴムに含有させるにあたっては、通常、(I)シリコーンコンパウンドを含むミラブル型シリコーンゴム組成物、又は(II)液状シリコーンポリマーを含む液状シリコーンゴム組成物と香料とを混合し、イオウ等の反応助剤、添加剤等を用いて加硫(架橋)を行う。ところが、混練時に香料とシリコーンゴムポリマー又は添加剤との分離が発生し易く、さらには、成形時の熱と反応助剤による香料の分解、変性等の化学変化を生じる結果、芳香性を有しかつ物性の安定した成形体が得られ難かった。 By the way, it is known that silicone rubber is excellent in adsorptivity and gas permeability, is physically stable, and is excellent in fragrance divergence. Taking advantage of these properties, air fresheners containing a fragrance in silicone rubber are commercially available. When the fragrance is contained in the silicone rubber, usually, (I) a miraculous silicone rubber composition containing a silicone compound or (II) a liquid silicone rubber composition containing a liquid silicone polymer and the fragrance are mixed and mixed with sulfur or the like. Vulcanization (crosslinking) is performed using a reaction aid, an additive, or the like. However, separation of the fragrance and the silicone rubber polymer or the additive is likely to occur during kneading, and further, as a result of causing chemical changes such as decomposition and modification of the fragrance by the heat during molding and the reaction aid, the fragrance has aroma. Moreover, it was difficult to obtain a molded product having stable physical properties.
そこで、かかる問題を解決する手段として、特開平8−311216号公報(特許文献4)や特開2011−26462号公報(特許文献5)では、シリコーンゴム成形前に香料を混練するのではなく、シリコーンゴム成形後に香料を添加する方法が採用されている。しかしながら、これらの文献は、香料組成物の性状とシリコーンゴムとの適合性について全く言及しておらず、機能的に異なる飛翔害虫忌避香料組成物に当てはまるとは限らない。 Therefore, as a means for solving such a problem, in JP-A-8-31216 (Patent Document 4) and JP-A-2011-26462 (Patent Document 5), the fragrance is not kneaded before the silicone rubber molding. A method of adding a fragrance after molding silicone rubber is adopted. However, these documents make no mention of the properties of the fragrance composition and its compatibility with silicone rubber, and do not necessarily apply to functionally different flying pest repellent fragrance compositions.
上記のようにシリコーンゴム成形体は、(I)シリコーンコンパウンドを含むミラブル型シリコーンゴム組成物、又は(II)液状シリコーンゴム組成物を硬化、成形して調製される。また、(II)液状シリコーンゴム組成物には付加型と縮合型の二種類が存在する。本発明者らは、シリコーンゴムを利用した有用な飛翔害虫忌避製品を開発するにあたり、(I)ミラブル型シリコーンゴム組成物、又は(II)液状シリコーンゴム組成物の硬化物であるシリコーンゴム成形体を用い、これと各種飛翔害虫忌避香料組成物との適合性を検討した。その結果、忌避組成物として(m)特定の酢酸エステル化合物と(n)モノテルペン系アルコール及び/又は炭素数10の芳香族アルコールを含有する混合物を採用することによって、飛翔害虫忌避香料成分がシリコーンゴム成形体から良好に揮散し、所定期間に亘って優れた飛翔害虫忌避効果を奏することを知見した(特許文献6)。 As described above, the silicone rubber molded body is prepared by curing and molding (I) a miraculous silicone rubber composition containing a silicone compound or (II) a liquid silicone rubber composition. Further, there are two types of (II) liquid silicone rubber compositions, an addition type and a condensation type. In developing a useful flying insect repellent product using silicone rubber, the present inventors have (I) a miraculous silicone rubber composition or (II) a cured product of a liquid silicone rubber composition, which is a silicone rubber molded product. Was used to examine the compatibility of this with various flying pest repellent fragrance compositions. As a result, by adopting a mixture containing (m) a specific acetic acid ester compound and (n) a monoterpene alcohol and / or an aromatic alcohol having 10 carbon atoms as the repellent composition, the flying pest repellent fragrance component is made of silicone. It has been found that it volatilizes well from the rubber molded body and exerts an excellent effect of repelling flying insects over a predetermined period (Patent Document 6).
特許文献6の飛翔害虫忌避製品は、飛翔害虫を忌避する性能的に優れたものであったが、(I)ミラブル型シリコーンゴム組成物を原料として用いた場合には、飛翔害虫忌避製品の複雑な形状に起因して成形時にバリが発生したり離型性が悪かったりするなど、成形作業性や機械特性について課題を有していた。そこで、本発明者らは、シリコーンゴム成形体の原料として(II)液状シリコーンゴム組成物のうち付加型について更に詳細に検討を進めることとした。なお、特許第5053114号明細書(特許文献7)には、縮合型の一種であるオキシム型液状シリコーンゴム組成物にアクリナトリンを配合した忌避性シリコーンゴム組成物が開示されているが、縮合型は副生物の生成が避けられないこと、またアクリナトリンは非揮散性で飛翔害虫忌避香料成分とは性状が全く異なることから参考となるに至らなかった。 The flying pest repellent product of Patent Document 6 was excellent in performance of repelling flying pests, but (I) when a miraculous silicone rubber composition was used as a raw material, the flying pest repellent product was complicated. Due to the shape, burrs are generated during molding and the mold releasability is poor, and there are problems in molding workability and mechanical properties. Therefore, the present inventors have decided to proceed with a more detailed study on the addition type of the (II) liquid silicone rubber composition as a raw material for the silicone rubber molded product. Japanese Patent No. 5053114 (Patent Document 7) discloses a repellent silicone rubber composition obtained by blending acrinathrin with an oxime type liquid silicone rubber composition which is a kind of condensation type. The formation of by-products is unavoidable, and acrinathrin is non-volatile and has completely different properties from the flying pest repellent fragrance component, so it was not useful as a reference.
このように、付加型液状シリコーンゴム組成物の硬化物であるシリコーンゴム成形体を用いて、その成形作業性や機械特性を改良するとともに、これとの適合性が高い飛翔害虫忌避香料組成物を見出した上で、より一層優れた飛翔害虫忌避効果を奏する飛翔害虫忌避製品を実現するには、各種試験の実施を不可欠とし、試行錯誤を繰り返さざるを得ない状況であった。 As described above, by using the silicone rubber molded product which is a cured product of the additive liquid silicone rubber composition, the molding workability and mechanical properties thereof are improved, and a flying pest repellent fragrance composition having high compatibility with the molded product is obtained. After finding out, in order to realize a flying pest repellent product that has an even better effect of repelling flying pests, it was indispensable to carry out various tests, and trial and error had to be repeated.
本発明は、上記問題点に鑑みてなされたものであり、シリコーンゴムの特性を生かしつつ、その成形作業性や機械特性等を改良するとともに、飛翔害虫忌避香料成分の揮散性能と飛翔害虫に対する忌避効果とに優れる飛翔害虫忌避製品、及び飛翔害虫忌避方法を提供することを目的とする。 The present invention has been made in view of the above problems, and while making the best use of the characteristics of silicone rubber, improving its molding workability, mechanical properties, etc., as well as the volatilization performance of flying pest repellent fragrance components and repelling against flying pests. An object of the present invention is to provide a flying pest repellent product having excellent effects and a flying pest repellent method.
本発明は、以下の構成が上記目的を達成するために優れた効果を奏することを見出したものである。 The present invention has found that the following configuration exerts an excellent effect in achieving the above object.
(1)硬度50度以下のシリコーンゴム成形体において、飛翔害虫忌避香料成分を含有する飛翔害虫忌避香料組成物が、前記シリコーンゴム成形体を構成するゴムの分子構造の隙間に入り込んだ状態で保持されている飛翔害虫忌避製品であって、
前記シリコーンゴム成形体は、(A)メチルビニルポリシロキサン、(B)架橋シリコーンポリマーとしてのメチルハイドロジェンポリシロキサン、(C)反応触媒としての白金化合物、(D)補強性充填剤、及び(E)反応抑制剤を含む付加型液状シリコーンゴム組成物の硬化物であり、
前記飛翔害虫忌避香料組成物は、前記飛翔害虫忌避香料成分として、以下の(a)、(b)、及び(c):
(a)リモネン、ピネン、カンフェン、及びテルピネンからなる群より選ばれる少なくとも一種のテルペン系炭化水素化合物、及び/又はカルボン、プレゴン、メントン、カンファー、及びピペリトンからなる群より選ばれる少なくとも一種のテルペン系ケトン化合物、
(b)ベンジルアセテート、p−t−ブチルシクロヘキシルアセテート、メンチルアセテート、リナリルアセテート、ベンジルベンゾエート、アリルヘキサノエート、アリルヘプタノエート、及びアリルオクタノエートからなる群より選ばれる少なくとも一種のエステル化合物、
(c)リナロール、テルピネオール、メントール、ジヒドロミルセノール、シトロネロール、及びゲラニオールからなる群より選ばれる少なくとも一種のテルペン系アルコール化合物
を含有し、
前記飛翔害虫忌避香料組成物における(a)テルペン系炭化水素化合物及び/又はテルペン系ケトン化合物の配合量Xと(b)エステル化合物の配合量Yとの合計と、(c)テルペン系アルコール化合物の配合量Zとの配合比率{(X+Y)/Z}が、0.2〜4.0に設定されている飛翔害虫忌避製品。(1) In a silicone rubber molded body having a hardness of 50 degrees or less, the flying pest repellent fragrance composition containing a flying pest repellent fragrance component is held in a state of being inserted into a gap in the molecular structure of the rubber constituting the silicone rubber molded body. It is a flying pest repellent product that has been used.
The silicone rubber molded product includes (A) methylvinylpolysiloxane, (B) methylhydrogenpolysiloxane as a crosslinked silicone polymer, (C) a platinum compound as a reaction catalyst, (D) a reinforcing filler, and (E). ) A cured product of an additive-type liquid silicone rubber composition containing a reaction inhibitor.
The flying pest repellent fragrance composition contains the following (a), (b), and (c) as the flying pest repellent fragrance component.
(A) At least one terpene hydrocarbon compound selected from the group consisting of limonene, pinene, camphene, and terpinene, and / or at least one terpene compound selected from the group consisting of carboxylic, pregon, menthone, camphor, and piperiten. Ketone compound,
(B) At least one ester compound selected from the group consisting of benzyl acetate, pt-butylcyclohexyl acetate, menthyl acetate, linalyl acetate, benzyl benzoate, allyl hexanoate, allyl heptanoate, and allyl octanoate.
(C) Containing at least one terpene alcohol compound selected from the group consisting of linalool, terpineol, menthol, dihydromilsenol, citronellol, and geraniol.
The total of (a) the total amount X of the terpene hydrocarbon compound and / or the terpene ketone compound and (b) the amount Y of the ester compound in the flying pest repellent fragrance composition, and (c) the terpene alcohol compound. A flying pest repellent product in which the compounding ratio {(X + Y) / Z} with the compounding amount Z is set to 0.2 to 4.0.
(2)前記シリコーンゴム成形体は、低分子シロキサンを低減した二次加硫物である(1)に記載の飛翔害虫忌避製品。 (2) The flying pest repellent product according to (1), wherein the silicone rubber molded product is a secondary vulcanized product in which low molecular weight siloxane is reduced.
(3)前記補強性充填剤は、シロキサン改質シリカを含む(1)又は(2)に記載の飛翔害虫忌避製品。 (3) The flying pest repellent product according to (1) or (2), wherein the reinforcing filler contains siloxane-modified silica.
(4)前記飛翔害虫忌避香料組成物は、前記飛翔害虫忌避香料成分として、(d)スチラリルアセテート、o−t−ブチルシクロヘキシルアセテート、シトロネリルアセテート、フェネチルアセテート、ゲラニルアセテート、シンナミルアセテート、トリシクロデセニルアセテート、アニシルアセテート、アリルシクロヘキシルアセテート、アリルシクロヘキシルプロピオネート、アリルイソブチルオキシアセテート、アリルn−アミルオキシアセテート、アリルシクロヘキシルオキシアセテート、アリルフェノキシアセテート、フェネチルアルコール、ボルネオール、オイゲノール、ネロール、エチルリナロール、チモール、p−メンタン−3,8−ジオール、1,8−シネオール、ジフェニルオキサイド、シトロネラール、ダマスコン、シス−ジャスモン、及びジヒドロジャスモンからなる群より選ばれる少なくとも一種の香料をさらに含有する(1)〜(3)の何れか一つに記載の飛翔害虫忌避製品。 (4) The flying pest repellent fragrance composition contains (d) styralyl acetate, ot-butylcyclohexyl acetate, citronellyl acetate, phenethyl acetate, geranyl acetate, cinnamyl acetate, and tri as the flying pest repellent fragrance component. Cyclodecenyl acetate, anisyl acetate, allylcyclohexyl acetate, allylcyclohexylpropionate, allylisobutyloxyacetate, allyl n-amyloxyacetate, allylcyclohexyloxyacetate, allylphenoxyacetate, phenethyl alcohol, borneol, eugenol, nerol, It further contains at least one fragrance selected from the group consisting of ethyllinalol, timol, p-menthan-3,8-diol, 1,8-cineol, diphenyloxide, citronellal, damascon, cis-jasmon, and dihydrojasmon ( The flying pest repellent product according to any one of 1) to (3).
(5)前記飛翔害虫忌避香料組成物は、シトラールを実質的に含有しない(1)〜(4)の何れか一つに記載の飛翔害虫忌避製品。 (5) The flying pest repellent product according to any one of (1) to (4), wherein the flying pest repellent fragrance composition does not substantially contain citral.
(6)前記シリコーンゴム成形体の表面からの前記飛翔害虫忌避香料成分の平均揮散量は、0.04〜0.9mg/cm2・hである(1)〜(5)の何れか一つに記載の飛翔害虫忌避製品。(6) The average amount of volatilization of the flying pest repellent fragrance component from the surface of the silicone rubber molded product is 0.04 to 0.9 mg / cm 2 · h, any one of (1) to (5). Flying pest repellent products described in.
(7)前記シリコーンゴム成形体は、人体の一部若しくは物体が挿入又は装着される伸縮可能な環部を備えた環状ゴム成形体、或いは端部どうしを結合若しくは近接させて人体の一部若しくは物体が挿入又は装着される伸縮可能な環部を形成し得る帯状ゴム成形体である(6)に記載の飛翔害虫忌避製品。 (7) The silicone rubber molded body is an annular rubber molded body having a stretchable ring portion into which a part of the human body or an object is inserted or mounted, or a part of the human body or a part of the human body in which ends are bonded or brought close to each other. The flying pest repellent product according to (6), which is a strip-shaped rubber molded body capable of forming a stretchable ring portion into which an object is inserted or mounted.
(8)前記環部に前記人体の一部若しくは前記物体を挿入又は装着した状態で、前記飛翔害虫忌避香料成分が5〜15時間に亘って揮散する(7)に記載の飛翔害虫忌避製品。 (8) The flying pest repellent product according to (7), wherein the flying pest repellent fragrance component volatilizes over 5 to 15 hours with a part of the human body or the object inserted or attached to the ring portion.
(9)前記環部は、図形又はキャラクターの輪郭を備える(7)又は(8)に記載の飛翔害虫忌避製品。 (9) The flying pest repellent product according to (7) or (8), wherein the ring portion has a graphic or character contour.
(10)(1)〜(9)の何れか一つに記載の飛翔害虫忌避製品を用いた飛翔害虫忌避方法であって、
前記ゴム成形体の表面から前記飛翔害虫忌避香料成分を揮散させる飛翔害虫忌避方法。(10) A method for repelling flying pests using the flying pest repellent product according to any one of (1) to (9).
A method for repelling flying pests by volatilizing the flying pest repellent fragrance component from the surface of the rubber molded body.
本発明の飛翔害虫忌避製品、及び飛翔害虫忌避方法によれば、付加型液状シリコーンゴム組成物の硬化物であるシリコーンゴム成形体に、特定の飛翔害虫忌避香料成分を含む飛翔害虫忌避香料組成物を保持させるため、当該シリコーンゴム成形体の成形作業性や機械特性等が改良されるとともに、飛翔害虫忌避香料成分の揮散性能と飛翔害虫に対する忌避効果が従来品に較べてより一層優れるので、その有用性は極めて高い。 According to the flying pest repellent product and the flying pest repellent method of the present invention, a flying pest repellent fragrance composition containing a specific flying pest repellent fragrance component in a silicone rubber molded product which is a cured product of the additive liquid silicone rubber composition. In addition to improving the molding workability and mechanical properties of the silicone rubber molded product, the volatilization performance of the flying pest repellent fragrance component and the repellent effect against flying pests are even better than those of conventional products. The usefulness is extremely high.
以下、本発明の飛翔害虫忌避製品について説明する。本発明の飛翔害虫忌避方法については、飛翔害虫忌避製品の説明中で併せて説明する。ただし、本発明は、以下に説明する実施形態に記載される構成に限定されることを意図しない。 Hereinafter, the flying pest repellent product of the present invention will be described. The flying pest repellent method of the present invention will also be described in the description of the flying pest repellent product. However, the present invention is not intended to be limited to the configurations described in the embodiments described below.
本発明の飛翔害虫忌避製品は、付加型液状シリコーンゴム組成物の硬化物であって硬度50度以下のシリコーンゴム成形体(以下、「ゴム成形体」と省略する場合がある。)に、飛翔害虫忌避香料成分を含有する飛翔害虫忌避香料組成物を保持させたものである。飛翔害虫忌避香料成分は、ゴム成形体に適した特定の種類のものが使用される。飛翔害虫忌避香料成分の詳細については後述する。 The flying pest repellent product of the present invention is a cured product of an add-on liquid silicone rubber composition and flies to a silicone rubber molded product having a hardness of 50 degrees or less (hereinafter, may be abbreviated as "rubber molded product"). A flying pest repellent fragrance composition containing a pest repellent fragrance component is retained. As the flying pest repellent fragrance component, a specific type suitable for the rubber molded product is used. Details of the flying pest repellent fragrance component will be described later.
付加型液状シリコーンゴム組成物は、(A)メチルビニルポリシロキサン、(B)架橋シリコーンポリマーとしてのメチルハイドロジェンポリシロキサン、(C)反応触媒としての白金化合物、(D)補強性充填剤、及び(E)反応抑制剤を含む。付加型液状シリコーンゴム組成物には一液性のものと、シリコーンゴム硬化・成形時に二剤を混ぜ合わせる二液性のものがあるが、何れも使用することができる。 The additive liquid silicone rubber composition includes (A) methylvinylpolysiloxane, (B) methylhydrogenpolysiloxane as a crosslinked silicone polymer, (C) a platinum compound as a reaction catalyst, (D) a reinforcing filler, and (E) Contains a reaction inhibitor. The addition-type liquid silicone rubber composition includes a one-component type and a two-component type in which two agents are mixed at the time of curing and molding the silicone rubber, and any of them can be used.
(A)メチルビニルポリシロキサンとしては、分子鎖両末端及び/又は分子鎖側鎖に架橋反応に関与するビニル基を有する下記の(A−1)〜(A−3)タイプのものが挙げられる。 Examples of the methyl vinyl polysiloxane (A) include the following types (A-1) to (A-3) having a vinyl group involved in the cross-linking reaction at both ends of the molecular chain and / or the side chain of the molecular chain. ..
(A−1)タイプ:分子鎖両末端がジメチルビニルシロキサン基で封鎖されたジメチルポリシロキサン、分子鎖両末端がジメチルビニルシロキサン基で封鎖されたメチルアルキルポリシロキサン、分子鎖両末端がジメチルビニルシロキサン基で封鎖されたジメチルシロキサン・メチルフェニルシロキサン共重合体、及び分子鎖両末端がジメチルビニルシロキサン基で封鎖されたジメチルシロキサン・メチルアルキルシロキサン共重合体等の分子鎖両末端にビニル基を有するもの。 (A-1) Type: Dimethylpolysiloxane having both ends of the molecular chain sealed with a dimethylvinylsiloxane group, methylalkylpolysiloxane having both ends of the molecular chain sealed with a dimethylvinylsiloxane group, and dimethylvinylsiloxane having both ends of the molecular chain. Dimethylsiloxane / methylphenylsiloxane copolymer sealed with a group, and dimethylsiloxane / methylalkylsiloxane copolymer having both ends of the molecular chain sealed with a dimethylvinylsiloxane group, etc. having vinyl groups at both ends of the molecular chain ..
(A−2)タイプ:分子鎖両末端がトリメチルシロキシ基で封鎖されたメチルビニルポリシロキサン、分子鎖両末端がトリメチルシロキシ基で封鎖されたメチルビニルシロキサン・ジメチルシロキサン共重合体、及び分子鎖両末端がトリメチルシロキシ基で封鎖されたメチルビニルシロキサン・メチルフェニルシロキサン共重合体等の分子鎖側鎖にビニル基を有し分子鎖両末端にビニル基を有さないもの。 (A-2) Type: Methylvinylpolysiloxane with both ends of the molecular chain sealed with a trimethylsiloxy group, a methylvinylsiloxane / dimethylsiloxane copolymer with both ends of the molecular chain sealed with a trimethylsiloxy group, and both molecular chains. A polymer having a vinyl group on the side chain of the molecular chain, such as a methylvinylsiloxane / methylphenylsiloxane copolymer whose ends are sealed with a trimethylsiloxy group, and no vinyl group at both ends of the molecular chain.
(A−3)タイプ:分子鎖両末端及び分子鎖側鎖の両方にビニル基を有するもの。 (A-3) Type: Those having vinyl groups at both ends of the molecular chain and side chains of the molecular chain.
付加型液状シリコーンゴム組成物において(A)メチルビニルポリシロキサンには、(A−1)タイプ、又は(A−3)タイプが一般的に使用されるが、金型離型性を向上させるという観点から、(A−1)タイプと(A−2)タイプとを併用することがより好ましい。付加型液状シリコーンゴム組成物における(A)メチルビニルポリシロキサンの配合量は、50〜80質量%であることが好ましい。 In the addition type liquid silicone rubber composition, the (A-1) type or the (A-3) type is generally used for the (A) methyl vinyl polysiloxane, but it is said that the mold releasability is improved. From the viewpoint, it is more preferable to use the (A-1) type and the (A-2) type together. The blending amount of (A) methyl vinyl polysiloxane in the addition type liquid silicone rubber composition is preferably 50 to 80% by mass.
(B)メチルハイドロジェンポリシロキサンは、(A)メチルビニルポリシロキサンの架橋剤として作用する。すなわち、(B)メチルハイドロジェンポリシロキサン中のケイ素原子結合水素原子が、(A)メチルビニルポリシロキサン中のビニル基とヒドロシリル化反応し、架橋により付加型液状シリコーンゴム組成物を硬化させる。このような(B)メチルハイドロジェンポリシロキサンとしては、例えば、分子鎖両末端がトリメチルシロキシ基で封鎖されたメチルハイドロジェンポリシロキサン、分子鎖両末端がトリメチルシロキシ基で封鎖されたジメチルシロキサン・メチルハイドロジェンシロキサン共重合体、分子鎖両末端がトリメチルシロキシ基で封鎖されたメチルフェニルシロキサン・メチルハイドロジェンシロキサン共重合体、分子鎖両末端がジメチルハイドロジェンシロキシ基で封鎖されたジメチルポリシロキサン、分子鎖両末端がジメチルハイドロジェンシロキシ基で封鎖されたメチルハイドロジェンポリシロキサン、及び分子鎖両末端がジメチルハイドロジェンシロキシ基で封鎖されたジメチルシロキサン・メチルハイドロジェンシロキサン共重合体等が挙げられる。付加型液状シリコーンゴム組成物における(B)メチルハイドロジェンポリシロキサンの配合量は、(A)メチルビニルポリシロキサン中のケイ素原子結合ビニル基1モルに対して(B)メチルハイドロジェンポリシロキサン中のケイ素原子結合水素原子が0.5〜3モルの範囲内となる量であることが必要であり、5〜15質量%であることが好ましい。 (B) Methylhydrogenpolysiloxane acts as a cross-linking agent for (A) methylvinylpolysiloxane. That is, the silicon atom-bonded hydrogen atom in (B) methylhydrogenpolysiloxane undergoes a hydrosilylation reaction with the vinyl group in (A) methylvinylpolysiloxane, and the addition-type liquid silicone rubber composition is cured by cross-linking. Examples of such (B) methylhydrogenpolysiloxane include methylhydrogenpolysiloxane having both ends of the molecular chain sealed with a trimethylsiloxy group, and dimethylsiloxane / methyl having both ends of the molecular chain sealed with a trimethylsiloxy group. Hydrogen siloxane copolymer, methylphenylsiloxane / methylhydrogensiloxane copolymer with both ends of the molecular chain sealed with trimethylsiloxy groups, dimethylpolysiloxane with both ends of the molecular chain sealed with dimethylhydrogensiloxy groups, molecules Examples thereof include methylhydrogenpolysiloxane having both ends of the chain sealed with a dimethylhydrogensiloxy group, and a dimethylsiloxane / methylhydrogensiloxane copolymer having both ends of the molecular chain sealed with a dimethylhydrogensiloxy group. The blending amount of (B) methylhydrogenpolysiloxane in the additive liquid silicone rubber composition is (B) in methylhydrogenpolysiloxane with respect to 1 mol of silicon atom-bonded vinyl group in (A) methylvinylpolysiloxane. The amount of the hydrogen atom bonded to the silicon atom needs to be in the range of 0.5 to 3 mol, preferably 5 to 15% by mass.
(C)白金化合物は、ヒドロシリル化反応触媒として作用し、(B)メチルハイドロジェンポリシロキサン中のケイ素原子結合水素原子の(A)メチルビニルポリシロキサン中のビニル基へのヒドロシリル化反応を促進する。このような(C)白金化合物としては、例えば、白金黒、白金担持のアルミナ粉末、白金担持のシリカ粉末、白金担持のカーボン粉末、塩化白金酸、塩化白金酸とオレフィンとの錯体、塩化白金酸とジケトンとの錯体、及び塩化白金酸と1,3−ジビニルテトラメチルジシロキサンとの錯体等のヒドロシリル化反応触媒として周知の化合物が挙げられる。付加型液状シリコーンゴム組成物における(C)白金化合物の配合量は、触媒量で十分であり、飛翔害虫忌避製品の価格の上昇を抑制するために0.01〜1.0質量%であることが好ましい。 The platinum compound (C) acts as a hydrosilylation reaction catalyst and promotes the hydrosilylation reaction of the silicon atom-bonded hydrogen atom in (B) methylhydrogenpolysiloxane to the vinyl group in (A) methylvinylpolysiloxane. .. Examples of such a platinum compound (C) include platinum black, platinum-supported alumina powder, platinum-supported silica powder, platinum-supported carbon powder, platinum chloride acid, a complex of platinum chloride acid and an olefin, and platinum chloride acid. Examples of compounds known as hydrosilylation reaction catalysts such as a complex of diketone and diketone and a complex of platinum chloride and 1,3-divinyltetramethyldisiloxane can be mentioned. The amount of the platinum compound (C) to be blended in the addition type liquid silicone rubber composition is sufficient in the amount of the catalyst, and is 0.01 to 1.0% by mass in order to suppress an increase in the price of the flying pest repellent product. Is preferable.
(D)補強性充填剤は、付加型液状シリコーンゴム組成物を粘調にして成形作業性を向上させ、シリコーンゴム成形体の機械特性を向上させ、ひいては金型からの離型性を向上させる。このような(D)補強性充填剤としては、例えば、ヒュームドシリカ(乾式法シリカ)、沈殿シリカ(湿式法シリカ)、軽質炭酸カルシウム、ヒュームド酸化チタン、カーボンブラック等が挙げられ、特に、乾式法シリカ、又は湿式法シリカの表面に、ヘキサメチルジシラザン(HMDS)、ポリジメチルシロキサン(PDMS)、ジメチルジクロロシラン(DDS)等の表面処理剤を用いて疎水性を付与したシロキサン改質シリカが好ましい。付加型液状シリコーンゴム組成物における(D)補強性充填剤の配合量は、付加型液状シリコーンゴム組成物の粘度とシリコーンゴム成形体の機械特性等を考慮して適宜設定することが可能であり、10〜50質量%であることが好ましい。 (D) The reinforcing filler makes the additive liquid silicone rubber composition viscous to improve molding workability, improves the mechanical properties of the silicone rubber molded product, and thus improves the mold releasability from the mold. .. Examples of such (D) reinforcing filler include fumed silica (dry silica), precipitated silica (wet silica), light calcium carbonate, fumed titanium oxide, carbon black, and the like, and in particular, dry silica. A siloxane-modified silica obtained by imparting hydrophobicity to the surface of legal silica or wet method silica using a surface treatment agent such as hexamethyldisilazane (HMDS), polydimethylsiloxane (PDMS), or dimethyldichlorosilane (DDS). preferable. The blending amount of the (D) reinforcing filler in the additive-type liquid silicone rubber composition can be appropriately set in consideration of the viscosity of the additive-type liquid silicone rubber composition, the mechanical properties of the silicone rubber molded product, and the like. , 10 to 50% by mass is preferable.
(E)反応抑制剤は、付加型液状シリコーンゴム組成物の常温での硬化を防止し、加熱時に硬化可能とする。このような(E)反応抑制剤としては、例えば、3−メチル−1−ブチン−3−オール、3,5−ジメチル−1−ヘキシン−3−オール、1−エチニルシクロヘキサノール、プロパルギルアルコール等が挙げられる。付加型液状シリコーンゴム組成物における(E)反応抑制剤の配合量は、0.001〜0.1質量%であることが好ましい。 The reaction inhibitor (E) prevents the addition-type liquid silicone rubber composition from curing at room temperature, and makes it possible to cure when heated. Examples of such (E) reaction inhibitor include 3-methyl-1-butyne-3-ol, 3,5-dimethyl-1-hexin-3-ol, 1-ethynylcyclohexanol, propargyl alcohol and the like. Can be mentioned. The blending amount of the reaction inhibitor (E) in the addition type liquid silicone rubber composition is preferably 0.001 to 0.1% by mass.
本発明で用いる付加型液状シリコーンゴム組成物は、上記の(A)成分〜(E)成分に加えて、増量充填剤として、例えば、焼成シリカ微粉末、微珪粉、粉砕石英、クリストバライト粉末、酸化チタン粉末、酸化マグネシウム粉末等を配合したり、更には、顔料、耐熱剤、難燃剤、非架橋性シリコーンオイル、抗菌剤、防カビ剤等の周知の添加剤を適宜配合してもよい。 In addition to the above-mentioned components (A) to (E), the additive-type liquid silicone rubber composition used in the present invention can be used as an additional filler, for example, calcined silica fine powder, fine silica powder, crushed quartz, or Christovalite powder. Titanium oxide powder, magnesium oxide powder and the like may be blended, and well-known additives such as pigments, heat-resistant agents, flame-retardant agents, non-crosslinkable silicone oils, antibacterial agents and antifungal agents may be blended as appropriate.
付加型液状シリコーンゴム組成物は、周知の成形装置及び成形法により硬化させ成形することができる。硬化成形装置としては、通常の液状シリコーンゴム組成物成形法で用いられる圧縮成形機、トランスファー成形機、及び射出成型機等を用いることができる。この際、液状シリコーンゴム組成物の硬化温度が低すぎると、硬化速度が遅くなって生産性が低下し、一方、硬化温度が高すぎるとシリコーンゴム成形体の機械的強度が低下するため、硬化温度としては、50〜240℃であることが好ましく、120〜210℃であることがより好ましい。 The addition type liquid silicone rubber composition can be cured and molded by a well-known molding apparatus and molding method. As the curing molding apparatus, a compression molding machine, a transfer molding machine, an injection molding machine, or the like used in a normal liquid silicone rubber composition molding method can be used. At this time, if the curing temperature of the liquid silicone rubber composition is too low, the curing rate becomes slow and the productivity decreases, while if the curing temperature is too high, the mechanical strength of the silicone rubber molded body decreases, so that it is cured. The temperature is preferably 50 to 240 ° C, more preferably 120 to 210 ° C.
なお、付加型液状シリコーンゴム組成物の硬化物の架橋密度を調整したり、付加型液状シリコーンゴム組成物の添加剤として用いる補強性充填剤や増量充填剤、あるいは非架橋性シリコーンオイルの添加量を調整することで、後で添加する飛翔害虫忌避香料組成物の揮散量をコントロールすることもできる。 The amount of the reinforcing filler, the bulking filler, or the non-crosslinkable silicone oil added to adjust the cross-linking density of the cured product of the additive-type liquid silicone rubber composition or as an additive of the additive-type liquid silicone rubber composition. It is also possible to control the amount of volatilization of the flying pest repellent fragrance composition to be added later by adjusting.
付加型液状シリコーンゴム組成物を硬化、成形したシリコーンゴム成形体は物性的に安定なものであるが、ゴム成形体中に低分子シロキサン成分等が残存する場合、これらが物性上悪影響を及ぼしたり、ゴム成形体自体に黄変を生じる虞があることが知られている。また、本発明者らによる飛翔害虫忌避香料成分についての検討過程において、シトラールのようにゴム成形体中の残存成分の影響を受けやすい香料が存在することが明らかとなった。そのため、本発明で用いるシリコーンゴム成形体は、硬化後にオーブン等を用いて160〜240℃の温度で1〜15時間程度、好ましくは、190〜220℃の温度で2〜7時間程度のポストキュア処理(二次加硫処理)を施すことで、低分子シロキサンを低減した二次加硫物であることが好ましい。ポストキュア処理を施すことによって、ゴム成形体が物性的により安定してゴム成形体自体の黄変若しくは褐変を抑制できるだけでなく、香料との相互作用により生じ得る黄変若しくは褐変を抑制できることが認められた。 The silicone rubber molded product obtained by curing and molding the additive liquid silicone rubber composition is physically stable, but if low molecular weight siloxane components or the like remain in the rubber molded product, these may adversely affect the physical properties. , It is known that the rubber molded body itself may cause yellowing. In addition, in the process of studying the flying pest repellent fragrance component by the present inventors, it was clarified that there is a fragrance that is easily affected by the residual component in the rubber molded body such as citral. Therefore, the silicone rubber molded product used in the present invention is post-cured at a temperature of 160 to 240 ° C. for about 1 to 15 hours, preferably at a temperature of 190 to 220 ° C. for about 2 to 7 hours after curing. It is preferable that the secondary vulcanized product has a reduced amount of low molecular weight siloxane by subjecting it to a treatment (secondary vulcanization treatment). It is recognized that the post-cure treatment not only makes the rubber molded body more stable in physical properties and suppresses yellowing or browning of the rubber molded body itself, but also suppresses yellowing or browning that may occur due to interaction with the fragrance. Was done.
シリコーンゴム成形体は気体透過性に優れ、香料の吸着・発散に優れるという特性を有する。これは、香料の分子構造は主鎖が炭素で構成されており、香料分子が3次元的に架橋しているゴムの分子構造の隙間に入り込み易いためと考えられている。特にゴム成形体の硬度が50度以下の場合、シリコーンゴムの分子構造が密になり過ぎないため、香料分子がゴムの分子構造の隙間に入り込み易くなる。ゴム成形体の硬度が50度を超えるとゴム成形体の分子構造が密になり過ぎ、香料分子がゴムの分子構造の隙間に入り込み難くなり、本発明の趣旨に適合しない。なお、ゴム成形体の硬度は、日本工業規格(JIS K6253)に準拠した方法又は装置によって測定される。本発明では、上記規格に適合したデュロメータを用いてゴム成形体の硬度が測定される。 The silicone rubber molded product has excellent gas permeability and excellent adsorption and divergence of fragrance. It is considered that this is because the main chain of the molecular structure of the fragrance is composed of carbon, and the fragrance molecule easily enters the gap of the molecular structure of the rubber in which the fragrance molecule is three-dimensionally crosslinked. In particular, when the hardness of the rubber molded product is 50 degrees or less, the molecular structure of the silicone rubber does not become too dense, so that the fragrance molecules easily enter the gaps in the molecular structure of the rubber. If the hardness of the rubber molded body exceeds 50 degrees, the molecular structure of the rubber molded body becomes too dense, and it becomes difficult for the fragrance molecules to enter the gaps in the molecular structure of the rubber, which does not conform to the gist of the present invention. The hardness of the rubber molded product is measured by a method or apparatus conforming to the Japanese Industrial Standards (JIS K6253). In the present invention, the hardness of the rubber molded product is measured using a durometer conforming to the above standards.
本発明の特徴は、こうして得られた付加型液状シリコーンゴム組成物の硬化物であって硬度が50度以下のゴム成形体を用いることで、成形作業性や機械特性等を改良するとともに、当該ゴム成形体に最適な飛翔害虫忌避香料組成物を見出すことで、その飛翔害虫に対する忌避効果が従来品に較べてより一層優れる飛翔害虫忌避製品を実現したことにある。本発明者らは、特許第5832649号(特許文献6)において、(I)ミラブル型シリコーンゴム組成物の硬化物、及び(II)液状シリコーンゴム組成物の硬化物である両者のゴム成形体を用いた場合、これらと適合性を有する飛翔害虫忌避香料組成物として、(m)特定の酢酸エステル化合物と(n)モノテルペン系アルコール及び/又は炭素数10の芳香族アルコールを含有する混合物が良好であった旨を開示した。 The feature of the present invention is to improve molding workability, mechanical properties, etc. by using a cured product of the additive liquid silicone rubber composition thus obtained and having a hardness of 50 degrees or less. By finding the optimum flying pest repellent fragrance composition for a rubber molded product, we have realized a flying pest repellent product whose repellent effect against flying pests is even better than that of conventional products. In Patent No. 5823649 (Patent Document 6), the present inventors have described both rubber molded bodies, which are (I) a cured product of a mirable type silicone rubber composition and (II) a cured product of a liquid silicone rubber composition. When used, as a flying pest repellent fragrance composition compatible with these, a mixture containing (m) a specific acetate compound and (n) a monoterpene-based alcohol and / or an aromatic alcohol having 10 carbon atoms is preferable. It was disclosed that it was.
その後、本発明者らが、(II)液状シリコーンゴム組成物のうち付加型の硬化物であるゴム成形体を対象として更に検討を継続した結果、特許文献6の場合とは異なり、特定の飛翔害虫忌避香料成分が、付加型液状シリコーンゴム組成物の硬化物であるゴム成形体との適合性において最適であることを知見し、本発明の飛翔害虫忌避製品を達成するに至った。 After that, as a result of further studies by the present inventors on a rubber molded product which is an addition-type cured product among (II) liquid silicone rubber compositions, a specific flight is different from the case of Patent Document 6. It has been found that the pest repellent fragrance component is optimal in compatibility with a rubber molded product which is a cured product of the additive liquid silicone rubber composition, and the flying pest repellent product of the present invention has been achieved.
本発明の飛翔害虫忌避製品に用いる飛翔害虫忌避香料組成物は、実質的に殺虫成分を用いず、香料成分を飛翔害虫忌避成分として使用する。このような香料成分を「飛翔害虫忌避香料成分」と称する。飛翔害虫忌避香料組成物は、飛翔害虫忌避香料成分として、下記の(a)成分、(b)成分、及び(c)成分を含有する。 The flying pest repellent fragrance composition used in the flying pest repellent product of the present invention does not substantially use an insecticidal component, and uses the fragrance component as a flying pest repellent component. Such a fragrance component is referred to as a "flying pest repellent fragrance component". The flying pest repellent fragrance composition contains the following components (a), (b), and (c) as the flying pest repellent fragrance component.
(a)成分としては、リモネン、ピネン、カンフェン、及びテルピネン等のテルペン系炭化水素化合物、及び/又はカルボン、プレゴン、メントン、カンファー、及びピペリトン等のテルペン系ケトン化合物が挙げられる。これらのテルペン系炭化水素化合物及び/又はテルペン系ケトン化合物は、単独で使用してもよいし、任意に組み合わせて使用してもよい。 Examples of the component (a) include terpene hydrocarbon compounds such as limonene, pinene, camphene, and terpinene, and / or terpene ketone compounds such as carboxylic, pregon, menthone, camphor, and piperitone. These terpene-based hydrocarbon compounds and / or terpene-based ketone compounds may be used alone or in any combination.
(b)成分としては、ベンジルアセテート、p−t−ブチルシクロヘキシルアセテート、メンチルアセテート、リナリルアセテート、ベンジルベンゾエート、アリルヘキサノエート、アリルヘプタノエート、及びアリルオクタノエート等のエステル化合物が挙げられる。これらのエステル化合物は、単独で使用してもよいし、任意に組み合わせて使用してもよい。 Examples of the component (b) include ester compounds such as benzyl acetate, pt-butylcyclohexyl acetate, menthyl acetate, linalyl acetate, benzyl benzoate, allyl hexanoate, allyl heptanoate, and allyl octanoate. These ester compounds may be used alone or in any combination.
(c)成分としては、リナロール、テルピネオール、メントール、ジヒドロミルセノール、シトロネロール、及びゲラニオール等のテルペン系アルコール化合物が挙げられる。これらのテルペン系アルコール化合物は、単独で使用してもよいし、任意に組み合わせて使用してもよい。 Examples of the component (c) include terpene-based alcohol compounds such as linalool, terpineol, menthol, dihydromilsenol, citronellol, and geraniol. These terpene-based alcohol compounds may be used alone or in any combination.
本発明の飛翔害虫忌避製品においては、(a)成分の配合量Xと(b)成分の配合量Yとの合計と、(c)成分の配合量Zとの配合比率{(X+Y)/Z}を、0.2〜4.0に、好ましくは0.78〜1.8に設定すると、付加型液状シリコーンゴム組成物の硬化物であるゴム成形体と適合し、優れた揮散性能及び飛翔害虫忌避結果が得られることが本発明者らによる鋭意研究の結果より認められた。 In the flying pest repellent product of the present invention, the total of the blending amount X of the component (a) and the blending amount Y of the component (b) and the blending ratio of the blending amount Z of the component (c) {(X + Y) / Z } Is set to 0.2 to 4.0, preferably 0.78 to 1.8, and is compatible with a rubber molded body which is a cured product of an add-on liquid silicone rubber composition, and has excellent volatilization performance and flight. It was confirmed from the results of diligent research by the present inventors that pest repellent results were obtained.
飛翔害虫忌避香料組成物は、飛翔害虫忌避香料成分として、下記の(d)成分をさらに含有してもよい。 The flying pest repellent fragrance composition may further contain the following component (d) as a flying pest repellent fragrance component.
(d)成分としては、スチラリルアセテート、o−t−ブチルシクロヘキシルアセテート、シトロネリルアセテート、フェネチルアセテート、ゲラニルアセテート、シンナミルアセテート、トリシクロデセニルアセテート、アニシルアセテート、アリルシクロヘキシルアセテート、アリルシクロヘキシルプロピオネート、アリルイソブチルオキシアセテート、アリルn−アミルオキシアセテート、アリルシクロヘキシルオキシアセテート、アリルフェノキシアセテート、フェネチルアルコール、ボルネオール、オイゲノール、ネロール、エチルリナロール、チモール、p−メンタン−3,8−ジオール、1,8−シネオール、ジフェニルオキサイド、シトロネラール、ダマスコン、シス−ジャスモン、及びジヒドロジャスモン等の香料が挙げられる。これらの香料は、単独で使用してもよいし、任意に組み合わせて使用してもよい。なお、シトラールは、ゴム成形体中の残存成分の影響を受けて着色の問題を生じる虞を有するため、本発明の飛翔害虫忌避製品では、飛翔害虫忌避香料組成物にシトラールを実質的に含有しないことが好ましい。 As the component (d), styralyl acetate, ot-butylcyclohexyl acetate, citronellyl acetate, phenethyl acetate, geranyl acetate, cinnamyl acetate, tricyclodecenyl acetate, anisyl acetate, allylcyclohexyl acetate, allylcyclohexyl Propionate, allylisobutyloxyacetate, allyl n-amyloxyacetate, allylcyclohexyloxyacetate, allylphenoxyacetate, phenethyl alcohol, borneol, eugenol, nerol, ethyllinalol, timol, p-menthan-3,8-diol, 1 , 8-Cineol, diphenyloxide, citronellal, damascon, cis-jasmon, dihydrojasmon and the like. These fragrances may be used alone or in any combination. Since citral may cause a coloring problem due to the influence of residual components in the rubber molded body, the flying pest repellent product of the present invention does not substantially contain citral in the flying pest repellent fragrance composition. Is preferable.
飛翔害虫忌避香料組成物には、上記香料成分を含む種々の精油類、例えば、ジャスミン油、ネロリ油、ペパーミント油、ラベンダー油、ベルガモット油、オレンジ油、ゼラニウム油、プチグレン油、レモン油、シトロネラ油、シナモン油、ユーカリ油、レモンユーカリ油、タイム油等を適宜添加してもよい。このような精油類には上記の(a)成分、(b)成分、及び(c)成分が含有されているため、精油類の添加量を調整することで、飛翔害虫忌避香料組成物に(a)成分、(b)成分、及び(c)成分を補充し、より強い飛翔害虫忌避効果を発揮させることも可能である。 The flying pest repellent fragrance composition includes various essential oils containing the above fragrance components, for example, jasmine oil, neroli oil, peppermint oil, lavender oil, bergamot oil, orange oil, geranium oil, petitgrain oil, lemon oil, citronella oil. , Cinnamon oil, eucalyptus oil, lemon eucalyptus oil, thyme oil and the like may be added as appropriate. Since such essential oils contain the above-mentioned components (a), (b), and (c), the amount of the essential oils added can be adjusted to make a flying pest repellent fragrance composition ( It is also possible to supplement the a) component, the (b) component, and the (c) component to exert a stronger effect of repelling flying pests.
飛翔害虫忌避香料組成物には、飛翔害虫忌避香料成分の揮散時の忌避効果持続成分をさらに含有させることが好ましい。忌避効果持続成分とは、例えば、20℃における蒸気圧が0.2〜20Paのグリコール及び/又はグリコールエーテルである。 It is preferable that the flying pest repellent fragrance composition further contains a component that sustains the repellent effect at the time of volatilization of the flying pest repellent fragrance component. The repellent effect lasting component is, for example, glycol and / or glycol ether having a vapor pressure of 0.2 to 20 Pa at 20 ° C.
上記のグリコール及び/又はグリコールエーテルの具体例(20℃における蒸気圧を併記)としては、プロピレングリコール(10.7Pa)、ジプロピレングリコール(1.3Pa)、トリプロピレングリコール(0.67Pa)、ジエチレングリコール(3Pa)、トリエチレングリコール(1Pa)、1,3−ブチレングリコール、ヘキシレングリコール(6.7Pa)、ベンジルグリコール(2.7Pa)、ジエチレングリコールモノブチルエーテル(3Pa)、ジプロピレングリコールモノブチルエーテル、及びトリプロピレングリコールモノメチルエーテルが挙げられ、その中でも、ジプロピレングリコールが本発明の目的に好適である。なお、上記のグリコール及び/又はグリコールエーテルは、単独で使用してもよいし、任意に組み合わせて使用してもよい。グリコール及び/又はグリコールエーテルの飛翔害虫忌避香料成分に対する配合比率は、0.2〜10倍程度が適当である。 Specific examples of the above glycol and / or glycol ether (with steam pressure at 20 ° C.) include propylene glycol (10.7 Pa), dipropylene glycol (1.3 Pa), tripropylene glycol (0.67 Pa), and diethylene glycol. (3Pa), triethylene glycol (1Pa), 1,3-butylene glycol, hexylene glycol (6.7Pa), benzyl glycol (2.7Pa), diethylene glycol monobutyl ether (3Pa), dipropylene glycol monobutyl ether, and tri. Propylene glycol monomethyl ether is mentioned, and among them, dipropylene glycol is suitable for the object of the present invention. The above-mentioned glycol and / or glycol ether may be used alone or in any combination. The appropriate blending ratio of glycol and / or glycol ether to the flying pest repellent fragrance component is about 0.2 to 10 times.
飛翔害虫忌避香料組成物には、本発明の効果に支障を来たさない限りにおいて、他の機能性成分を配合してもよい。他の機能性成分としては、例えば、殺虫成分、消臭成分、除菌・抗菌成分等が挙げられる。殺虫成分としては、常温揮散性ピレスロイド系のエムペントリン、プロフルトリン、トランスフルトリン、メトフルトリン等が挙げられる。殺虫成分を配合する場合は、本発明の趣旨に照らし、極力微量に留めるのが好ましい。消臭成分としては、イネ科、ツバキ科、イチョウ科、モクセイ科、クワ科、ミカン科、キントラノオ科、カキノキ科の中から選ばれる植物抽出物が代表的である。また、「緑の香り」と呼ばれる青葉アルコー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もできる。これらの機能性成分は、単独で使用してもよいし、任意に組み合わせて使用してもよい。 The flying pest repellent fragrance composition may contain other functional ingredients as long as the effects of the present invention are not impaired. Examples of other functional components include insecticidal components, deodorant components, sterilizing / antibacterial components, and the like. Examples of the insecticidal component include empentrin, profluthrin, transfluthrin, and metoflutrin, which are pyrethroids that volatilize at room temperature. When the insecticidal component is blended, it is preferable to keep the amount as small as possible in light of the gist of the present invention. As the deodorant component, a plant extract selected from Gramineae, Theaceae, Ginkgoaceae, Oleaceae, Moraceae, Rutaceae, Malpighiaceae, and Ebenaceae is typical. It is also possible to add a green leaf alcohol, a green leaf aldehyde, or the like called "green scent" to impart a relaxing effect. These functional ingredients may be used alone or in any combination.
飛翔害虫忌避香料組成物には、本発明の効果に支障を来たさない限りにおいて、必要に応じ、溶剤、界面活性剤、可溶化剤、分散剤、安定化剤、pH調整剤、着色剤等を適宜配合してもよい。また、飛翔害虫忌避香料組成物を、例えば、マイクロカプセル化したり、サイクロデキストリン化することにより、当該飛翔害虫忌避香料組成物の安定化を図ったり、飛翔害虫忌避香料成分の揮散性を調節することも可能である。 The flying pest repellent fragrance composition may contain a solvent, a surfactant, a solubilizer, a dispersant, a stabilizer, a pH adjuster, a colorant, as necessary, as long as the effects of the present invention are not impaired. Etc. may be appropriately blended. Further, by microencapsulating or cyclodextrinizing the flying pest repellent fragrance composition, for example, the flying pest repellent fragrance composition may be stabilized or the volatility of the flying pest repellent fragrance component may be adjusted. Is also possible.
飛翔害虫忌避製品の調製に用いる溶剤としては、例えば、水、エタノール、イソプロパノール等の低級アルコール、ケトン系溶剤、エステル系溶剤、ノルマルパラフィンやイソパラフィン等の炭化水素系溶剤等が挙げられる。これらの溶剤は、単独で使用してもよいし、任意に組み合わせて使用してもよい。界面活性剤としては、例えば、ポリオキシエチレン硬化ヒマシ油、ポリオキシエチレン高級アルキルエーテル類(ポリオキシエチレンラウリルエーテル、ポリオキシエチレンオレイルエーテル等)、ポリオキシエチレンアルキルフェニルエーテル類、ポリオキシエチレン高級脂肪酸エステル類、ポリオキシエチレンソルビタン脂肪酸エステル類、ポリオキシエチレングリセリン脂肪酸エステル類、ポリオキシエチレンポリオキシプロピレンアルキルエーテル等の非イオン系界面活性剤、ラウリルアミンオキサイド、ステアリルアミンオキサイド、ラウリン酸アミドプロピルジメチルアミンオキサイド等の高級アルキルアミンオキサイド系界面活性剤等が挙げられる。これらの界面活性剤は、単独で使用してもよいし、任意に組み合わせて使用してもよい。 Examples of the solvent used for preparing the flight pest repellent product include water, lower alcohols such as ethanol and isopropanol, ketone solvents, ester solvents, and hydrocarbon solvents such as normal paraffin and isoparaffin. These solvents may be used alone or in any combination. Examples of the surfactant include polyoxyethylene hydrogenated castor oil, polyoxyethylene higher alkyl ethers (polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, etc.), polyoxyethylene alkylphenyl ethers, and polyoxyethylene higher fatty acids. Nonionic surfactants such as esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene glycerin fatty acid esters, polyoxyethylene polyoxypropylene alkyl ethers, laurylamine oxide, stearylamine oxide, lauric acid amidopropyldimethylamine Higher alkylamine oxide-based surfactants such as oxides can be mentioned. These surfactants may be used alone or in any combination.
上記の飛翔害虫忌避香料組成物を、付加型液状シリコーンゴム組成物の硬化物であって硬度50度以下のシリコーンゴム成形体に添加し、所定の処理を行ってゴム成形体に飛翔害虫忌避香料組成物を保持させることで、本発明の飛翔害虫忌避製品が完成する。そして、本発明の飛翔害虫忌避製品を用い、シリコーンゴム成形体の表面から飛翔害虫忌避香料成分を揮散させることにより、本発明の飛翔害虫忌避方法を実施することができる。 The above-mentioned flying pest repellent fragrance composition is added to a silicone rubber molded product which is a cured product of an additive liquid silicone rubber composition and has a hardness of 50 degrees or less, and is subjected to a predetermined treatment to give the rubber molded body a flying pest repellent fragrance. By retaining the composition, the flying pest repellent product of the present invention is completed. Then, by using the flying pest repellent product of the present invention and volatilizing the flying pest repellent fragrance component from the surface of the silicone rubber molded product, the flying pest repellent method of the present invention can be carried out.
飛翔害虫忌避香料組成物をゴム成形体に添加する方法としては、従来公知の方法を適宜採用することができる。例えば、ゴム成形体の表面積が大きい場合は、飛翔害虫忌避香料組成物を薬液分注方式や塗布方式によって担持させる。ゴム成形体の表面積が小さい場合は、多数個のゴム成形体を密閉容器に入れ、これに飛翔害虫忌避香料組成物を必要に応じて溶剤と共に加えて噴霧又は滴下し、攪拌しながらゴム成形体に浸透させる。さらに、飛翔害虫忌避香料組成物の液中にゴム成形体を適当時間浸漬させたり、あるいは高濃度に飛翔害虫忌避香料組成物を含有させたゴム成形体と無処理のゴム成形体を密閉容器中に混在させ、適当時間放置してゴム成形体全体に亘って香料組成物濃度を平均化させる方法によって、飛翔害虫忌避製品を製造することも可能である。 As a method for adding the flying pest repellent fragrance composition to the rubber molded product, a conventionally known method can be appropriately adopted. For example, when the surface area of the rubber molded product is large, the flying pest repellent fragrance composition is supported by a chemical solution dispensing method or a coating method. When the surface area of the rubber molded product is small, a large number of rubber molded products are placed in a closed container, and a flying pest repellent fragrance composition is added thereto together with a solvent as necessary, sprayed or dropped, and the rubber molded product is stirred. Infiltrate into. Further, the rubber molded product is immersed in the liquid of the flying pest repellent fragrance composition for an appropriate time, or the rubber molded product containing the flying pest repellent fragrance composition in a high concentration and the untreated rubber molded product are placed in a closed container. It is also possible to produce a flying pest repellent product by a method of averaging the concentration of the fragrance composition over the entire rubber molded product by mixing the mixture and leaving it for an appropriate time.
本発明の飛翔害虫忌避製品における飛翔害虫忌避香料組成物の配合量(保持量)は、当該飛翔害虫忌避製品の使用用途、使用期間、及びゴム成形体の種類やその仕様等によって適宜決定すればよい。例えば、1回あたり5〜15時間使用する飛翔害虫忌避製品の場合では、ゴム成形体1個あたり20〜200mg程度の飛翔害虫忌避香料組成物を配合することが好ましい。15〜30日使用する飛翔害虫忌避製品の場合では、例えば、製品重量を2〜10g程度とし、ゴム成形体1個あたり100〜2000mg程度の飛翔害虫忌避香料組成物を配合することが好ましい。 The blending amount (retention amount) of the flying pest repellent fragrance composition in the flying pest repellent product of the present invention may be appropriately determined depending on the intended use, the period of use, the type of the rubber molded body, the specifications thereof, and the like. Good. For example, in the case of a flying pest repellent product that is used for 5 to 15 hours at a time, it is preferable to blend about 20 to 200 mg of a flying pest repellent fragrance composition per rubber molded product. In the case of a flying pest repellent product that is used for 15 to 30 days, for example, it is preferable that the product weight is about 2 to 10 g and a flying pest repellent fragrance composition of about 100 to 2000 mg is blended per rubber molded body.
以下、ゴム成形体の形状及び仕様について説明する。ゴム成形体の形状としては、環状、帯状、小片シート状等を適宜採用することができるが、ゴム成形体は、人体の一部若しくは物体が挿入又は装着される伸縮可能な環部を備えた環状ゴム成形体、或いは端部どうしを結合若しくは近接させて人体の一部若しくは物体が挿入又は装着される伸縮可能な環部を形成し得る帯状ゴム成形体として構成されることが好ましい。 Hereinafter, the shape and specifications of the rubber molded body will be described. As the shape of the rubber molded body, an annular shape, a strip shape, a small piece sheet shape or the like can be appropriately adopted, but the rubber molded body includes a stretchable ring portion into which a part or an object of the human body is inserted or attached. It is preferably configured as an annular rubber molded body or a strip-shaped rubber molded body capable of forming a stretchable ring portion into which a part or an object of a human body is inserted or attached by connecting or bringing the ends close to each other.
飛翔害虫忌避香料組成物を保持させた環状ゴム成形体、及び帯状ゴム成形体は、環部を手首や足首等の人体の一部、又はバギー、自転車等のハンドル等、バッグ、リュックサック、カバン等の持ち手等、帽子、靴等のひも等の物体に挿入又は装着すると、環状ゴム成形体、及び帯状ゴム成形体の表面から飛翔害虫忌避香料成分が徐々に揮散する。例えば、その揮散状態が5〜15時間に亘って持続する飛翔害虫忌避製品の場合、かかる揮散性能を維持するために、ゴム成形体の表面からの飛翔害虫忌避香料成分の平均揮散量(単位表面積あたりの平均揮散量)は、0.04〜0.9mg/cm2・hであることが好ましい。飛翔害虫忌避香料成分の平均揮散量がこの範囲であると、飛翔害虫忌避香料成分のゴム成形体内でのブリードが5〜15時間、好ましくは8〜12時間に亘って安定してスムーズに進行する。飛翔害虫忌避香料成分の平均揮散量が0.04mg/cm2・h未満であると、飛翔害虫忌避効果が不足する。飛翔害虫忌避香料成分の平均揮散量が1.0mg/cm2・hを超えると、忌避効果の持続時間が短くなったり、飛翔害虫忌避香料成分又は飛翔害虫忌避香料組成物のシリコーンゴム成形体内での保持量が過大になり過ぎて表面にベトツキを生じる可能性がある。なお、本発明において、平均揮散量とは0.02mg/cm2・h以上の揮散量を示す時間区について平均値を求めるものとする。The annular rubber molded body and the band-shaped rubber molded body that retain the flying pest repellent fragrance composition have a ring portion of a part of the human body such as a wrist or ankle, or a handle such as a buggy or a bicycle, a bag, a rucksack, or a bag. When inserted or attached to an object such as a handle, a hat, a shoe, or the like, the flying pest repellent fragrance component gradually volatilizes from the surface of the annular rubber molded body and the band-shaped rubber molded body. For example, in the case of a flying pest repellent product whose volatilization state lasts for 5 to 15 hours, the average volatilization amount (unit surface area) of the flying pest repellent fragrance component from the surface of the rubber molded body in order to maintain such volatilization performance. The average volatilization amount per unit) is preferably 0.04 to 0.9 mg / cm 2 · h. When the average volatilization amount of the flying pest repellent fragrance component is within this range, the bleeding of the flying pest repellent fragrance component in the rubber molded body proceeds stably and smoothly for 5 to 15 hours, preferably 8 to 12 hours. .. If the average volatilization amount of the flying pest repellent fragrance component is less than 0.04 mg / cm 2 · h, the flying pest repellent effect is insufficient. If the average volatilization amount of the flying pest repellent fragrance component exceeds 1.0 mg / cm 2 · h, the duration of the repellent effect will be shortened, or in the silicone rubber molded body of the flying pest repellent fragrance component or the flying pest repellent fragrance composition. There is a possibility that the holding amount of the material becomes excessive and the surface becomes sticky. In the present invention, the average volatilization amount is defined as an average value for a time group showing a volatilization amount of 0.02 mg / cm 2 · h or more.
環状ゴム成形体としては、手首や足首等の人体の一部や前記した物体に挿入又は装着し易いように、周囲が連結する1本の紐状体(線径:1〜3mm、長さ:約10〜20cm程度)であって、好ましくは図形又はキャラクターを形成したものが使用される。図1は、環状ゴム成形体1の模式図である。図1(a)は未装着時の環状ゴム成形体1を表し、図1(b)は環状ゴム成形体1を手首2に装着した状態を表している。環状ゴム成形体1は、人体の一部又は物体が挿入又は装着される伸縮可能な環部を備える。環部の輪郭は、図1(a)に示されるように、図形又はキャラクターのプロファイルを有している。図形又はキャラクターとしては、動物シリーズ、昆虫シリーズ、乗り物シリーズ、アルファベットシリーズ等様々挙げられるが、勿論これらに限定されるものではない。環状ゴム成形体1の原形は、その一部分を拡げて手首や足首等に装着させたときに、当該部分の少なくとも20%、好ましくは30%が手首や足首等の皮膚と離間した装着状態を形成するように伸縮するものであることが好ましい。これは、離間部分が忌避香料成分の揮散性向上に寄与するだけでなく、香料成分とはいえ、皮膚との接触はできるだけ避ける方が望ましいためである。図1(b)には、手首2からゴム成形体1の一部が離間することによって形成された離間部3が示されている。
The annular rubber molded body is a single string-like body (wire diameter: 1 to 3 mm, length: 1 to 3 mm, length: 1 to 3 mm) connected around the body so that it can be easily inserted or attached to a part of the human body such as a wrist or ankle or the above-mentioned object. It is about 10 to 20 cm), and preferably a figure or a character is used. FIG. 1 is a schematic view of the annular rubber molded body 1. FIG. 1A shows the annular rubber molded body 1 when not attached, and FIG. 1B shows the state in which the annular rubber molded body 1 is attached to the
環状ゴム成形体は、1本の紐状体から形成される図形又はキャラクターが主要部であるが、この紐状体の1箇所又は数箇所からゴム成形体を分枝させて分枝部を形成し、付属のアクセサリーを構成するようにしてもよい。こうすることによって、装飾性が付与されるとともに、ゴム成形体の重量を大きくし保持される飛翔害虫忌避香料成分量をアップできる結果、手首や足首等に装着する本発明の飛翔害虫忌避製品の個数を減らせるというメリットを有する。アクセサリーの形状や大きさは、この部分の香料成分揮散性が図形又はキャラクター主要部と比べて過大又は過小にならない程度であれば、特に限定されない。 The main part of the annular rubber molded body is a figure or character formed from one string-shaped body, and the rubber molded body is branched from one or several places of the string-shaped body to form a branched portion. However, the attached accessories may be configured. By doing so, the decorativeness is imparted, the weight of the rubber molded body is increased, and the amount of the flying pest repellent fragrance component held can be increased. As a result, the flying pest repellent product of the present invention to be attached to the wrist, ankle, etc. It has the advantage of reducing the number. The shape and size of the accessory are not particularly limited as long as the fragrance component volatilization property of this part is not excessive or too small as compared with the figure or the main part of the character.
帯状ゴム成形体としては、使用前の形状が帯状であれば特に限定されないが、その大きさは、幅が0.5〜2.0cm程度、長さが約10〜25cm程度、厚みが1〜3mm程度のものが使いやすく、例えば、少なくとも一つの中空と当該中空を囲む外郭部とを含むパーツが連なってなる帯状部と、帯状部の端部どうしを結合又は近接させて人体の一部又は物体が挿入又は装着される伸縮可能な環部を形成する結合部とを備えた形状、あるいは、一端側に少なくとも一つの突起部を有する帯状部と、突起部が嵌まることで人体の一部又は物体が挿入又は装着される伸縮可能な環部を形成する結合部とを備えた形状が好ましい。帯状部は、ゴム成形体の主材(本体)となるものである。帯状部は、単に紐状に成形したゴム成形体と比べて同等以上の伸縮性を保持することができ、強度的にも問題ないものとなる。結合部は、帯状である使用前のゴム成形体(飛翔害虫忌避製品)を、使用時に環状に変化させて仮固定するものである。結合部により、形成された環部の大きさを調整することができるため、人体の一部又は物体との接着状態を適度に調整することができる。例えば、ゴム成形体を人体の一部又は物体に挿入又は装着した際に、ゴム成形体が必要以上に移動するのを嫌う場合は、幾分締め付け度合が強くなるように結合部を調整すればよい。一方、香料成分とはいえ、皮膚との直接接触をできるだけ避けたい場合には、ゴム成形体が手首や足首等の皮膚とできるだけ離間した状態で装着されるように結合部を緩めに調整することも可能である。結合部の好ましい構成としては、帯状部の一端側(又は他端側)に複数の受け部を設け、他端側(又は一端側)に一つ又は複数の突起部を設ける仕様が挙げられる。具体的には、例えば、受け部として丸型の貫通孔を長さ方向に沿って3〜7個配設し、その何れかに、他端側に設けたT字型の突起部を嵌めて環部を形成させるように設計することができる。あるいは、受け部として丸型の貫通孔を長さ方向に沿って6〜10個配設し、当該貫通孔に、一端側に設けた2〜4個の突起部を嵌めて環部を形成させるように設計することができる。 The strip-shaped rubber molded body is not particularly limited as long as the shape before use is strip-shaped, but the size thereof is about 0.5 to 2.0 cm in width, about 10 to 25 cm in length, and 1 to 1 in thickness. A material of about 3 mm is easy to use. For example, a band-shaped portion in which at least one hollow and an outer shell portion surrounding the hollow are connected and the ends of the strip-shaped portion are joined or brought close to each other to form a part of the human body or a part of the human body. A shape having a joint portion forming an expandable ring portion into which an object is inserted or mounted, or a band-shaped portion having at least one protrusion on one end side and a part of the human body by fitting the protrusion. Alternatively, a shape including a joint portion forming a stretchable ring portion into which an object is inserted or mounted is preferable. The strip-shaped portion serves as the main material (main body) of the rubber molded body. The strip-shaped portion can maintain elasticity equal to or higher than that of a rubber molded body simply molded into a string shape, and there is no problem in terms of strength. The joint portion is a band-shaped rubber molded body (flying pest repellent product) before use, which is temporarily fixed by changing it into an annular shape at the time of use. Since the size of the formed ring portion can be adjusted by the connecting portion, the state of adhesion to a part of the human body or an object can be appropriately adjusted. For example, if you do not want the rubber molded body to move more than necessary when you insert or attach it to a part or object of the human body, you can adjust the joint so that the degree of tightening is somewhat stronger. Good. On the other hand, even if it is a fragrance component, if you want to avoid direct contact with the skin as much as possible, loosely adjust the joint so that the rubber molded body is attached as far as possible from the skin such as the wrist and ankle. Is also possible. A preferable configuration of the connecting portion includes a specification in which a plurality of receiving portions are provided on one end side (or the other end side) of the strip-shaped portion and one or a plurality of protrusions are provided on the other end side (or one end side). Specifically, for example, 3 to 7 round through holes are arranged along the length direction as a receiving portion, and a T-shaped protrusion provided on the other end side is fitted into any of them. It can be designed to form a ring. Alternatively, 6 to 10 round through holes are arranged as receiving portions along the length direction, and 2 to 4 protrusions provided on one end side are fitted into the through holes to form a ring portion. Can be designed as
帯状部に存在する中空は、拡散気流を生起し、揮散性の向上に寄与する。帯状部の中空の大きさや形状は、ゴム成形体からの飛翔害虫忌避香料成分の揮散性能の他、ゴム成形体の伸縮性や強度にも影響するため、これらのファクターを考慮して決定する必要がある。中空の大きさは、例えば、ゴム成形体が非伸縮状態にある場合において、平面視で、中空が占める総面積をS1とし、ゴム成形体の全面積(S1を含む)をS2としたとき、0.05 ≦ S1/S2 ≦ 0.6 を満たすように設定されることが好ましい。S1/S2の値が0.05未満(すなわち、ゴム成形体に対する中空の面積比率が5%未満)であると、ゴム成形体の単位重量当たりの揮散性能が紐状に成形したゴム成形体に及ばなくなる。一方、S1/S2の値が0.6超(すなわち、ゴム成形体に対する中空の面積比率が60%超)であると、ゴム成形体としての強度に問題を生じる虞がある。The hollow existing in the band-shaped portion creates a diffused air flow and contributes to the improvement of volatility. The size and shape of the hollow band-shaped part affect not only the volatilization performance of the flying pest repellent fragrance component from the rubber molded body, but also the elasticity and strength of the rubber molded body, so it is necessary to determine these factors in consideration. There is. Regarding the size of the hollow, for example, when the rubber molded body is in a non-stretchable state, the total area occupied by the hollow is S 1 and the total area (including S 1 ) of the rubber molded body is S 2 in a plan view. When this is done, it is preferable that 0.05 ≤ S 1 / S 2 ≤ 0.6 is set. When the value of S 1 / S 2 is less than 0.05 (that is, the hollow area ratio to the rubber molded body is less than 5%), the volatilization performance per unit weight of the rubber molded body is formed into a string shape. It will not reach the body. On the other hand, if the value of S 1 / S 2 is more than 0.6 (that is, the hollow area ratio to the rubber molded body is more than 60%), there is a possibility that the strength of the rubber molded body may be problematic.
中空の形状としては、その輪郭が、図形又はキャラクター形状となるように構成されたものが挙げられる。図形又はキャラクター形状としては、動物シリーズ、昆虫シリーズ、乗り物シリーズ、アルファベットシリーズ等様々挙げられるが、勿論これらに限定されるものではない。更に、中空のいくつかについて、これを埋めて凹窪み状に改変することもできる。このようにすることによって、中空のデザイン性を保持しつつ、ゴム成形体の重量を増加させ、飛翔害虫忌避香料成分の充填量を増やすことも可能となる。なお、中空を囲む外郭部から外方に延びる分枝部を形成し、キャラクター性やデザイン性を付与するようにしても勿論構わない。 Examples of the hollow shape include those whose contour is configured to have a figure or character shape. Examples of the figure or character shape include, but are not limited to, animal series, insect series, vehicle series, alphabet series, and the like. Further, some of the hollows can be filled in and modified into a concave shape. By doing so, it is possible to increase the weight of the rubber molded product and increase the filling amount of the flying pest repellent fragrance component while maintaining the hollow design. Of course, it is also possible to form a branch portion extending outward from the outer shell portion surrounding the hollow to give character and design.
帯状ゴム成形体においては、人体の一部又は物体が挿入又は装着される伸縮可能な環部を形成した時に、環部の少なくとも20%、好ましくは30%が手首や足首等の皮膚と離間した装着状態を形成するように伸縮するものであることが好ましい。 In a band-shaped rubber molded body, when a part or an object of a human body is inserted or attached to form a stretchable ring portion, at least 20%, preferably 30% of the ring portion is separated from the skin such as a wrist or ankle. It is preferable that the material expands and contracts so as to form a mounted state.
本発明の飛翔害虫忌避製品として使用される帯状部10と結合部20とを備えた帯状ゴム成形体100の例を図2に示す。図2は、帯状ゴム成形体100の外観図である。図2(a)は未装着時の帯状ゴム成形体100であり、図2(b)は帯状ゴム成形体100の両端を結合して手首Hに装着した帯状ゴム成形体100である。帯状ゴム成形体100では、中空の輪郭としてスターを模したパーツ1Aが複数個連なっている。
FIG. 2 shows an example of a band-shaped rubber molded
飛翔害虫忌避製品の例として、上記の環状ゴム成形体、及び帯状ゴム成形体を用いたリストリング、リストバンド等が挙げられる。また、飛翔害虫忌避製品を時計バンド状に構成することもでき、この場合、その一部に小片状のゴム成形体を収納する収納部を形成し、ゴム成形体を取替え自在とすることも可能である。なお、この場合、ゴム成形体が腕の皮膚に直接触れないというメリットを有する。このようなゴム成形体と収納体との組合わせは、飛翔害虫忌避香料成分の揮散性能が確保される限り、人体用だけでなく、車内等の空間用に用いられる載置タイプ、吊下げタイプなど様々な形態の飛翔害虫忌避製品に適用可能である。 Examples of the flight pest repellent product include the above-mentioned annular rubber molded product, and a wrist ring, wrist band, etc. using the strip-shaped rubber molded product. In addition, the flying pest repellent product can be configured in the shape of a watch band. In this case, a storage portion for storing a small piece of rubber molded body can be formed in a part thereof so that the rubber molded body can be replaced freely. It is possible. In this case, there is an advantage that the rubber molded body does not come into direct contact with the skin of the arm. Such a combination of the rubber molded body and the stored body is a mounting type or a hanging type used not only for the human body but also for spaces such as in a car as long as the volatilization performance of the flying pest repellent fragrance component is secured. It can be applied to various forms of flying pest repellent products.
このようにして得られた本発明の飛翔害虫忌避製品は、玄関、台所、トイレ、リビングルーム、寝室等の室内、倉庫、車内等の空間や、庭先、屋外で、手首や足首等の各部位に必要に応じて1〜5個装着して使用することにより、アカイエカ、チカイエカ、ヒトスジシマカ等の蚊類、蚋、ユスリカ類、ハエ類、コバエ類(ショウジョウバエ類、ノミバエ類等)、チョウバエ類、イガ類等の飛翔害虫に対し、所定の期間にわたり優れた飛翔害虫忌避効果を発揮する。そして、芳香性の飛翔害虫忌避香料成分を用いた場合には初期の香調が変質することなく所定期間持続し、しかも、本製品は実質的に殺虫成分を含有していないため、殺虫剤の使用を好まない人であっても抵抗なく使用できるので、その実用性は極めて高い。 The flying pest repellent product of the present invention thus obtained can be used in spaces such as entrances, kitchens, toilets, living rooms, bedrooms, warehouses, cars, etc., and in gardens, outdoors, wrists, ankles, etc. Mosquitoes such as Culex pipiens, London Underground mosquito, and Black fly, flies, flies, flies (Psychodidae, flies, etc.), butterfly flies, and squid, by attaching 1 to 5 to the flight as needed. It exerts an excellent repellent effect on flying pests such as mosquitoes over a predetermined period of time. When an aromatic flying pest repellent fragrance component is used, the initial fragrance tone does not deteriorate and lasts for a predetermined period of time, and since this product does not substantially contain an insecticidal component, it is an insecticide. Even people who do not like to use it can use it without any resistance, so its practicality is extremely high.
以下、本発明の飛翔害虫忌避製品の実施例について説明する。 Hereinafter, examples of the flying pest repellent product of the present invention will be described.
〔実施例1〕
二液性の付加型液状シリコーンゴム組成物として、下記の処方でシリコーンゴム組成物1液、及び2液を調製し、調製したシリコーンゴム組成物1液、及び2液を室温で混合し、射出成形機を用い140℃で硬化させて、動物のキャラクターを模した紐リング状(線径:約2mm、重量:1.6g、硬度:32度)に成形した。成形後にオーブンに入れ、210℃で5時間ポストキュア処理を行い、シリコーンゴム成形体を得た。
・シリコーンゴム組成物1液
(A)成分:分子鎖両末端がジメチルビニルシロキサン基で封鎖されたメチルビニルポリシロキサン 63質量%
(C)成分:塩化白金酸と1,3−ジビニルテトラメチルジシロキサンとの錯体 0.05質量%
(D)成分:シロキサン改質シリカ(表面処理剤としてHMDSを使用) 20質量%
増量充填剤:微珪粉 16.95質量%
・シリコーンゴム組成物2液
(A)成分:分子鎖両末端がジメチルビニルシロキサン基で封鎖されたメチルビニルポリシロキサン 63質量%
(B)成分:分子鎖両末端がトリメチルシロキシ基で封鎖されたメチルハイドロジェンポリシロキサン 7.6質量%
(D)成分:シロキサン改質シリカ(表面処理剤としてHMDSを使用) 20質量%
(E)成分:1−エチニルシクロヘキサノール 0.05質量%
増量充填剤:微珪粉 9.35質量%[Example 1]
As a two-component additive liquid silicone rubber composition, one and two silicone rubber compositions are prepared according to the following formulation, and the prepared silicone rubber compositions and two are mixed at room temperature and injected. It was cured at 140 ° C. using a molding machine to form a string ring shape (wire diameter: about 2 mm, weight: 1.6 g, hardness: 32 degrees) imitating an animal character. After molding, it was placed in an oven and post-cured at 210 ° C. for 5 hours to obtain a silicone rubber molded product.
-Silicone rubber composition 1 liquid (A) component: Methylvinylpolysiloxane with both ends of the molecular chain sealed with dimethylvinylsiloxane groups 63% by mass
Component (C): Complex of chloroplatinic acid and 1,3-divinyltetramethyldisiloxane 0.05% by mass
Component (D): Siloxane-modified silica (HMDS is used as a surface treatment agent) 20% by mass
Increased filler: fine silica powder 16.95% by mass
-
Component (B): Methylhydrogenpolysiloxane with both ends of the molecular chain sealed with a trimethylsiloxy group 7.6% by mass
Component (D): Siloxane-modified silica (HMDS is used as a surface treatment agent) 20% by mass
(E) Ingredient: 1-ethynylcyclohexanol 0.05% by mass
Increased filler: fine silica powder 9.35% by mass
下記の処方で飛翔害虫忌避香料組成物を調製した。この飛翔害虫忌避香料組成物は、飛翔害虫忌避香料成分としてシトラールを含有せず、(a)成分の配合量Xと(b)成分の配合量Yとの合計と、(c)成分の配合量Zとの配合比率{(X+Y)/Z}が1.1であった。
・飛翔害虫忌避香料組成物(ゴム成形体1個あたり30mg)
(a)成分:l−カルボン 14.3質量%(4.3mg)
(b)成分:ベンジルアセテート 7.0質量%(2.1mg)
p−t−ブチルシクロヘキシルアセテート 4.0質量%(1.2mg)
ベンジルベンゾエート 6.7質量%(2.0mg)
アリルヘプタノエート 5.7質量%(1.7mg)
(c)成分:リナロール 10.3質量%(3.1mg)
テルピネオール 9.7質量%(2.9mg)
ジヒドロミルセノール 8.3質量%(2.5mg)
ゲラニオール 4.7質量%(1.4mg)
(d)成分:スチラリルアセテート、チモール、p−メンタン−3,8−ジオール 合計12.6質量%(3.8mg)
忌避効果持続成分:ジプロピレングリコール 16.7質量%(5.0mg)A flying pest repellent fragrance composition was prepared according to the following formulation. This flying pest repellent fragrance composition does not contain citral as a flying pest repellent fragrance component, and is the sum of the blending amount X of the component (a) and the blending amount Y of the component (b), and the blending amount of the component (c). The blending ratio with Z {(X + Y) / Z} was 1.1.
・ Flying pest repellent fragrance composition (30 mg per rubber molded product)
(A) Ingredient: l-Carvone 14.3% by mass (4.3 mg)
(B) Ingredient: Benzyl acetate 7.0% by mass (2.1 mg)
pt-Butyl Cyclohexyl Acetate 4.0% by Mass (1.2 mg)
Benzyl benzoate 6.7% by mass (2.0 mg)
Allyl heptanoate 5.7% by mass (1.7 mg)
(C) Ingredient: Linalool 10.3% by mass (3.1 mg)
Terpineol 9.7% by mass (2.9 mg)
Dihydromilsenol 8.3% by mass (2.5 mg)
Geraniol 4.7% by mass (1.4 mg)
(D) Ingredients: styralyl acetate, thymol, p-menthane-3,8-diol Total 12.6% by mass (3.8 mg)
Repellent effect lasting ingredient: Dipropylene glycol 16.7% by mass (5.0 mg)
紐リング状のシリコーンゴム成形体100個を噴霧装置が付設された密閉容器に入れ、上記の噴霧装置を用いて、調製した飛翔害虫忌避香料組成物を、ゴム成形体1個当たりの吸着量が30mg(飛翔害虫忌避香料成分として25.0mg)になるように噴霧した。十分に攪拌した後、1日間放置してゴム成形体全体に飛翔害虫忌避香料組成物を均一に浸透させ、リストリング形態であって有効持続時間が約10時間の本発明の飛翔害虫忌避製品(実施例1)を得た。なお、別途、硬度が80度のシリコーンゴム成形体について同様に試してみたが、飛翔害虫忌避香料組成物は僅かしか吸着せず、本発明の飛翔害虫忌避製品は得られなかった。 100 string-ring-shaped silicone rubber molded bodies were placed in a closed container equipped with a spraying device, and the flying pest repellent fragrance composition prepared using the above spraying device was adsorbed by the amount of adsorption per rubber molded body. It was sprayed to 30 mg (25.0 mg as a flying pest repellent fragrance component). After sufficiently stirring, the product is left for 1 day to uniformly permeate the entire rubber molded body with the flying pest repellent composition, and is in a wristling form and has an effective duration of about 10 hours. Example 1) was obtained. Separately, a silicone rubber molded product having a hardness of 80 degrees was similarly tested, but the flying pest repellent fragrance composition adsorbed only a small amount, and the flying pest repellent product of the present invention could not be obtained.
実施例1の飛翔害虫忌避製品における飛翔害虫忌避香料成分の全表面積当たりの平均揮散量は、0.35mg/cm2・h(使用開始時から使用開始2時間後まで)であり、手首に装着した際に、リストリングの約44%が手首の皮膚から離間した状態であった。実施例1の飛翔害虫忌避製品を左右の手首に2個ずつ巻いて外出したところ、およそ10時間に亘り、蚊やコバエ等の飛翔害虫に煩わされることがなく、実用的な忌避効果が確認された。また、動物のキャラクターを身に付けることで遊び心を楽しめるとともに、身体の周囲空間には初期香調のままの芳香が漂い、快適な爽やかさをも満喫できた。The average volatilization amount of the flying pest repellent fragrance component in the flying pest repellent product of Example 1 per total surface area was 0.35 mg / cm 2 · h (from the start of use to 2 hours after the start of use) and was worn on the wrist. At that time, about 44% of the wrist ring was separated from the skin of the wrist. When two flying pest repellent products of Example 1 were wrapped around the left and right wrists and went out, a practical repellent effect was confirmed without being bothered by flying pests such as mosquitoes and flies for about 10 hours. It was. In addition, by wearing an animal character, you can enjoy the playfulness, and the space around your body has the fragrance of the initial scent, so you can enjoy the refreshing feeling.
〔実施例2〜10、比較例1〜5〕
付加型液状シリコーンゴム組成物の(A)成分と(D)成分とを表1に示す組成に変更し、その他は実施例1に準じて付加型液状シリコーンゴム組成物の硬化物である紐リング状のゴム成形体を成形し、これに表2に組成を示す飛翔害虫忌避香料組成物を吸着させて本発明の飛翔害虫忌避製品(実施例2〜10)を得た。なお、表1において、「A−1」は分子鎖両末端がジメチルビニルシロキサン基で封鎖されたジメチルポリシロキサンであり、「A−2」は分子鎖両末端がトリメチルシロキシ基で封鎖されたメチルビニルポリシロキサンであり、「A−3」は分子鎖両末端がジメチルビニルシロキサン基で封鎖されたメチルビニルポリシロキサンである。また、「シロキサン改質シリカP」はHMDSを用いて表面処理したシロキサン改質シリカであり、「シロキサン改質シリカQ」はPDMSを用いて表面処理したシロキサン改質シリカである。[Examples 2 to 10, Comparative Examples 1 to 5]
The components (A) and (D) of the additive-type liquid silicone rubber composition are changed to the compositions shown in Table 1, and the others are string rings which are cured products of the additive-type liquid silicone rubber composition according to Example 1. A rubber molded product in the shape of a shape was molded, and the flying pest repellent fragrance composition shown in Table 2 was adsorbed on the molded rubber molded product to obtain the flying pest repellent product of the present invention (Examples 2 to 10). In Table 1, "A-1" is a dimethylpolysiloxane having both ends of the molecular chain sealed with a dimethylvinylsiloxane group, and "A-2" is a methyl having both ends of the molecular chain sealed with a trimethylsiloxy group. It is a vinyl polysiloxane, and "A-3" is a methyl vinyl polysiloxane in which both ends of the molecular chain are sealed with a dimethylvinylsiloxane group. Further, "siloxane-modified silica P" is siloxane-modified silica surface-treated with HMDS, and "siloxane-modified silica Q" is siloxane-modified silica surface-treated with PDMS.
ミラブル型シリコーンゴム組成物の硬化物である紐リング状のゴム成形体を、実施例1と同形状に形成し、これに表3に組成を示す飛翔害虫忌避香料組成物を吸着させて本発明の範囲外となる飛翔害虫忌避製品(比較例1)を得た。また、付加型液状シリコーンゴム組成物の(A)成分と(D)成分とを表1に示す組成に変更し、その他は実施例1に準じて付加型液状シリコーンゴム組成物の硬化物である紐リング状のゴム成形体を成形し、これに表3に組成を示す飛翔害虫忌避香料組成物を吸着させて本発明の範囲外となる飛翔害虫忌避製品(比較例2〜5)を得た。 A string ring-shaped rubber molded product, which is a cured product of a mirable type silicone rubber composition, is formed in the same shape as in Example 1, and the flying pest repellent fragrance composition shown in Table 3 is adsorbed on the rubber molded product to repel flying pests. A flying pest repellent product (Comparative Example 1) outside the range of Further, the components (A) and (D) of the additive-type liquid silicone rubber composition are changed to the compositions shown in Table 1, and the others are cured products of the additive-type liquid silicone rubber composition according to Example 1. A string ring-shaped rubber molded body was molded, and the flying pest repellent fragrance composition shown in Table 3 was adsorbed on the rubber molded body to obtain a flying pest repellent product (Comparative Examples 2 to 5) outside the scope of the present invention. ..
得られた実施例2〜10の飛翔害虫忌避製品、及び比較例1〜5の飛翔害虫忌避製品について、〔1〕ゴム成形体の成形作業性の評価、〔2〕ゴム成形体の離型性の評価、〔3〕ゴム成形体表面における着色の評価、〔4〕飛翔害虫忌避効果試験、及び〔5〕飛翔害虫忌避香料成分の揮散量測定試験を実施した。 Regarding the obtained flying pest repellent products of Examples 2 to 10 and the flying pest repellent products of Comparative Examples 1 to 5, [1] evaluation of molding workability of the rubber molded body, and [2] releasability of the rubber molded body. , [3] Evaluation of coloring on the surface of the rubber molded body, [4] Test of repellent effect on flying pests, and [5] Test on measurement of volatilization amount of fragrance component repelling flying pests.
〔1〕ゴム成形体の成形作業性の評価
飛翔害虫忌避製品に用いたゴム成形体の成形作業性を、◎(非常に良い)、○(良い)、△(劣る)、及び×(非常に劣る)の四段階で評価した。[1] Evaluation of molding workability of rubber molded product The molding workability of the rubber molded product used for the flying pest repellent product was evaluated as ◎ (very good), ○ (good), △ (inferior), and × (very good). It was evaluated on a four-point scale (inferior).
〔2〕ゴム成形体の離型性の評価
飛翔害虫忌避製品に用いたゴム成形体の離型性を、◎(非常に良い)、○(良い)、△(劣る)、及び×(非常に劣る)の四段階で評価した。[2] Evaluation of mold releasability of rubber molded product The mold releasability of the rubber molded product used in the flying pest repellent product was evaluated as ◎ (very good), ○ (good), △ (inferior), and × (very good). It was evaluated on a four-point scale (inferior).
〔3〕ゴム成形体表面における着色の評価
飛翔害虫忌避製品のゴム成形体表面における着色の有無を、◎(着色なし)、〇(僅かに着色あり)、△(着色あり:黄変)、及び×(着色あり:褐色シミ)の四段階で評価した。[3] Evaluation of coloring on the surface of the rubber molded product The presence or absence of coloring on the surface of the rubber molded product of the flying pest repellent product was determined by ◎ (no coloring), 〇 (slightly colored), △ (colored: yellowing), and It was evaluated on a four-point scale of × (colored: brown stain).
〔4〕飛翔害虫忌避効果試験
試験室内(約6m3)に、蓋をしていないオープン状態のプラスチックカップ(約1L)を2個併設した。片方のプラスチックカップ内にアカイエカ成虫誘引源と供試飛翔害虫忌避製品を入れ(処理区)、他方のプラスチックカップ内にはアカイエカ成虫誘引源のみを入れた(無処理区)。使用開始2時間後、及び使用開始7時間後に、室内にアカイエカ成虫(雌)約50匹を放ち、両区プラスチックカップ内への侵入虫を計数し、次式に従って飛翔害虫忌避率を算出した。
飛翔害虫忌避率(%) = [(無処理区の侵入虫数−処理区の侵入虫数)/無処理区の侵入虫数] × 100[4] Flying pest repellent effect test Two open plastic cups (about 1 L) without lids were installed in the test room (about 6 m 3 ). One plastic cup contained an adult Culex pipiens attractant and a test flying pest repellent product (treated plot), and the other plastic cup contained only an adult Culex pipiens attractant (untreated plot). Approximately 50 adult Culex pipiens (female) were released indoors 2 hours after the start of use and 7 hours after the start of use, the invaders invading the plastic cups in both sections were counted, and the flight pest repellent rate was calculated according to the following formula.
Flying pest repellent rate (%) = [(Number of invaders in untreated plot-Number of invaders in treated plot) / Number of invaders in untreated plot] x 100
〔5〕飛翔害虫忌避香料成分の揮散量測定試験
飛翔害虫忌避製品の重量を、使用開始時、使用開始2時間後、及び使用開始7時間後に測定し、重量減少量に基づいて、使用開始時から使用開始2時間後までと、使用開始2時間後から使用開始7時間後までとの単位表面積・単位時間あたりの飛翔害虫忌避香料成分の平均揮散量を算出した。[5] Measurement test of volatilization amount of flying pest repellent fragrance component The weight of the flying pest repellent product is measured at the start of use, 2 hours after the start of use, and 7 hours after the start of use, and at the start of use based on the amount of weight loss. From 2 hours after the start of use and from 2 hours after the start of use to 7 hours after the start of use, the average volatilization amount of the flying pest repellent fragrance component per unit surface area and unit time was calculated.
評価及び試験の結果を表4に示す。 The evaluation and test results are shown in Table 4.
試験の結果、実施例2〜10の飛翔害虫忌避製品(付加型液状シリコーンゴム組成物の硬化物であるシリコーンゴム成形体に、特定の飛翔害虫忌避香料成分を含む飛翔害虫忌避香料組成物を保持させたもの)は、使用開始時から使用開始2時間後までと使用開始2時間後から使用開始7時間後までとの平均揮散量、及び使用開始2時間後と使用開始7時間後との飛翔害虫忌避率を検証すると、飛翔害虫忌避香料成分の揮散性能に優れ、満足のいく飛翔害虫忌避効果を奏することが確認された。ここで、特定の飛翔害虫忌避香料成分とは(a)テルペン系炭化水素化合物及び/又はテルペン系ケトン化合物と、(b)エステル化合物と、(c)テルペン系アルコール化合物とを含有し、かつ、(a)テルペン系炭化水素化合物及び/又はテルペン系ケトン化合物の配合量Xと(b)エステル化合物の配合量Yとの合計量の(c)テルペン系アルコール化合物の配合量Zに対する配合比率{(X+Y)/Z}が、0.2〜4.0に調整されたものである。これに対し、特定の飛翔害虫忌避香料成分である(a)成分、(b)成分、及び(c)成分のいずれかを含有しない飛翔害虫忌避製品(比較例2〜4)、及びそれらの配合比率が本発明の規定の範囲を外れる飛翔害虫忌避製品(比較例5)は、飛翔害虫忌避香料成分の揮散性能、及び忌避効果が劣るものであった。また、シリコーンゴム成形体が付加型液状シリコーンゴム組成物の硬化物である実施例2〜10の飛翔害虫忌避製品は、シリコーンゴム成形体がミラブル型シリコーンゴム組成物の硬化物である比較例1の飛翔害虫忌避製品と比較して、成形作業性及び離型性に優れるものであった。 As a result of the test, the flying pest repellent product of Examples 2 to 10 (the flying pest repellent fragrance composition containing a specific flying pest repellent fragrance component is held in the silicone rubber molded product which is a cured product of the additive liquid silicone rubber composition. The average volatilization amount from the start of use to 2 hours after the start of use and from 2 hours after the start of use to 7 hours after the start of use, and the flight between 2 hours after the start of use and 7 hours after the start of use. When the pest repellent rate was verified, it was confirmed that the flying pest repellent fragrance component had excellent volatilization performance and had a satisfactory flying pest repellent effect. Here, the specific flying pest repellent fragrance component contains (a) a terpene-based hydrocarbon compound and / or a terpene-based ketone compound, (b) an ester compound, and (c) a terpene-based alcohol compound, and The total amount of (a) terpene-based hydrocarbon compound and / or terpene-based ketone compound compounding amount X and (b) ester compound compounding amount Y to (c) terpene-based alcohol compound compounding amount Z {( X + Y) / Z} is adjusted to 0.2 to 4.0. On the other hand, flying pest repellent products (Comparative Examples 2 to 4) that do not contain any of the components (a), (b), and (c), which are specific flying pest repellent fragrance components, and their formulations. The flying pest repellent product (Comparative Example 5) having a ratio outside the specified range of the present invention was inferior in the volatilization performance and the repellent effect of the flying pest repellent fragrance component. Further, in the flying insect repellent products of Examples 2 to 10 in which the silicone rubber molded product is a cured product of the additive liquid silicone rubber composition, Comparative Example 1 in which the silicone rubber molded product is a cured product of the miraculous silicone rubber composition. Compared with the flying pest repellent product, it was excellent in molding workability and mold releasability.
忌避効果持続成分を配合した実施例2〜4の飛翔害虫忌避製品では、使用開始7時間後も忌避効果を安定して持続させ得ることが確認された。また、付加型液状シリコーンゴム組成物の(A)成分として、(A−1)分子鎖両末端がジメチルビニルシロキサン基で封鎖されたジメチルポリシロキサンと(A−2)分子鎖両末端がトリメチルシロキシ基で封鎖されたメチルビニルポリシロキサンとを併用した実施例3では、離型性が向上することが確認された。また、実施例2、4〜6は、成形作業性が優れており、付加型液状シリコーンゴム組成物の(D)成分としてシロキサン改質シリカの使用は、成形作業性の改善に効果的であることが確認された。また、実施例8の飛翔害虫忌避製品と実施例9の飛翔害虫忌避製品とは、何れも飛翔害虫忌避香料成分としてシトラールを配合したが、シリコーンゴム成形体をポストキュア処理した実施例8では、実施例9よりも着色の程度が抑えられていた。このことから、シリコーンゴム成形体をポストキュア処理することにより、シリコーンゴム成形体を物性的に安定化させ、着色の問題を改善できることが確認された。 It was confirmed that the flying pest repellent products of Examples 2 to 4 containing the repellent effect lasting component can stably maintain the repellent effect even after 7 hours from the start of use. Further, as the component (A) of the additive liquid silicone rubber composition, dimethylpolysiloxane in which both ends of the (A-1) molecular chain are sealed with a dimethylvinylsiloxane group and trimethylsiloxy at both ends of the (A-2) molecular chain. In Example 3 in which the methylvinyl polysiloxane sealed with a group was used in combination, it was confirmed that the releasability was improved. Further, Examples 2, 4 to 6 have excellent molding workability, and the use of siloxane-modified silica as the component (D) of the additive liquid silicone rubber composition is effective in improving the molding workability. It was confirmed that. Further, the flying pest repellent product of Example 8 and the flying pest repellent product of Example 9 both contained citral as a flying pest repellent fragrance component, but in Example 8 in which the silicone rubber molded body was post-cured, The degree of coloring was suppressed as compared with Example 9. From this, it was confirmed that the problem of coloring can be improved by physically stabilizing the silicone rubber molded product by post-curing the silicone rubber molded product.
〔実施例11〜16〕
実施例5に準じて付加型液状シリコーンゴム組成物を硬化させ、紐リング状に成形した。成形後にオーブンに入れ、表5に示す種々の条件でポストキュア処理を行い、シリコーンゴム成形体を得た。得られたゴム成形体に、実施例5に準じて飛翔害虫忌避香料組成物を吸着させて本発明の飛翔害虫忌避製品(実施例11〜16)を得た。実施例11の飛翔害虫忌避製品は、実施例5の飛翔害虫忌避製品と同一のものである。得られた実施例11〜16の飛翔害虫忌避製品について、前述の〔4〕飛翔害虫忌避効果試験、及び〔5〕飛翔害虫忌避香料成分の揮散量測定試験を実施したところ、試験結果の詳細は省略するが、何れも実施例5の飛翔害虫忌避製品と同程度の優れた揮散性能、及び飛翔害虫忌避効果を奏することが確認された。さらに、実施例11〜16の飛翔害虫忌避製品について、前述の〔1〕ゴム成形体の成形作業性(ポストキュア処理作業性を含む)の評価、及び〔3〕ゴム成形体表面における着色の評価を行った。評価の結果を表5に示す。[Examples 11 to 16]
The addition type liquid silicone rubber composition was cured according to Example 5 and molded into a string ring shape. After molding, it was placed in an oven and post-cured under various conditions shown in Table 5 to obtain a silicone rubber molded product. The flying pest repellent fragrance composition of the present invention was adsorbed on the obtained rubber molded body according to Example 5 to obtain the flying pest repellent products (Examples 11 to 16). The flying pest repellent product of Example 11 is the same as the flying pest repellent product of Example 5. The above-mentioned [4] flying pest repellent effect test and [5] flying pest repellent fragrance component volatilization amount measurement test were carried out on the obtained flying pest repellent products of Examples 11 to 16, and the details of the test results are as follows. Although omitted, it was confirmed that all of them have excellent volatilization performance and a flying pest repellent effect comparable to those of the flying pest repellent product of Example 5. Further, with respect to the flying pest repellent products of Examples 11 to 16, the above-mentioned [1] evaluation of molding workability (including post-cure treatment workability) of the rubber molded product and [3] evaluation of coloring on the surface of the rubber molded product Was done. The evaluation results are shown in Table 5.
評価の結果、特に、実施例11〜14の飛翔害虫忌避製品は、何れもゴム成形体の成形作業性が非常に優れており、ゴム成形体表面における着色も一定以上抑制されたものであった。つまり、シリコーンゴム成形体が、ポストキュア処理によって低分子シロキサンを低減した二次加硫物となっていることが確認された。とりわけ、ポストキュア処理の処理温度が190〜210℃で、処理時間が4〜5時間である実施例11及び12の飛翔害虫忌避製品は、ゴム成形体の成形作業性が非常に優れたものでありながら、ゴム成形体表面に着色が全く見られなかった。 As a result of the evaluation, in particular, the flying pest repellent products of Examples 11 to 14 were all excellent in molding workability of the rubber molded body, and the coloring on the surface of the rubber molded body was suppressed to a certain extent or more. .. That is, it was confirmed that the silicone rubber molded product was a secondary vulcanized product in which low-molecular-weight siloxane was reduced by post-cure treatment. In particular, the flying pest repellent products of Examples 11 and 12 having a post-cure treatment temperature of 190 to 210 ° C. and a treatment time of 4 to 5 hours are extremely excellent in molding workability of the rubber molded product. However, no coloring was observed on the surface of the rubber molded product.
一方、ポストキュア処理の処理温度が160℃未満である実施例15の飛翔害虫忌避製品は、ゴム成形体表面に着色が見られたことから、ポストキュア処理による低分子シロキサンの低減が不十分であったと考えられる。ポストキュア処理の処理温度が240℃を越える実施例16の飛翔害虫忌避製品は、ゴム成形体自体に黄変が生じた。ただし、これら実施例15及び実施例16の飛翔害虫忌避製品においても、ゴム成形体の成形作業性は良好なものであり、実用上大きな問題はなかった。 On the other hand, in the flying pest repellent product of Example 15 in which the treatment temperature of the post-cure treatment was less than 160 ° C., the surface of the rubber molded body was colored, so that the reduction of low molecular weight siloxane by the post-cure treatment was insufficient. It is probable that there was. In the flying pest repellent product of Example 16 in which the treatment temperature of the post-cure treatment exceeded 240 ° C., the rubber molded body itself was yellowed. However, also in these flying pest repellent products of Examples 15 and 16, the molding workability of the rubber molded product was good, and there was no major problem in practical use.
以上より、本発明の飛翔害虫忌避製品についてポストキュア処理を行う場合、その処理条件は、上述の評価結果とともに現実的な処理条件を考慮すると、好ましい処理温度は160〜240℃であり、より好ましい温度は190〜220℃であると考えられる。また、好ましい処理時間は1〜15時間程度であり、より好ましい処理時間は2〜7時間程度であると考えられる。 From the above, when the post-cure treatment is performed on the flying pest repellent product of the present invention, the treatment conditions are more preferably 160 to 240 ° C. in consideration of the practical treatment conditions together with the above evaluation results. The temperature is considered to be 190-220 ° C. Further, it is considered that the preferable treatment time is about 1 to 15 hours, and the more preferable treatment time is about 2 to 7 hours.
〔実施例17〕
下記の処方で付加型液状シリコーンゴム組成物を調製し、このシリコーンゴム組成物を射出成形機を用い130℃で硬化させて、中空の輪郭としてスターを模したパーツを7個繋ぎ合わせて帯状部を構成するとともに当該帯状部の両端に結合部(一端側が6個の丸型の貫通孔(受け部)、他端側がT字型の突起部)を有する帯状ゴム成形体(長さ:20cm、重量:3.6g、硬度:34度、ゴム成形体の全面積(S2)に対して中空が占める総面積(S1)の比率(S1/S2):0.35)を成形した。成形後に、このゴム成形体をオーブンに入れ、220℃で7時間ポストキュア処理を行った。
・付加型液状シリコーンゴム組成物
(A)成分:分子鎖両末端がジメチルビニルシロキサン基で封鎖されたメチルビニルポリシロキサン 67質量%
(B)成分:分子鎖両末端がトリメチルシロキシ基で封鎖されたジメチルシロキサン・メチルハイドロジェンシロキサン共重合体 8.3質量%
(C)成分:塩化白金酸とオレフィンとの錯体 0.04質量%
(D)成分:シロキサン改質シリカ(表面処理剤としてDDSを使用) 15質量%
(E)成分:3−メチル−1−ブチン−3−オール 0.08質量%
増量充填剤:微珪粉 9.58質量%[Example 17]
An additive liquid silicone rubber composition is prepared according to the following formulation, and this silicone rubber composition is cured at 130 ° C. using an injection molding machine, and seven parts that imitate stars as hollow contours are joined together to form a strip-shaped portion. (Length: 20 cm, length: 20 cm,) having joints (six round through holes (receiving parts) on one end side and T-shaped protrusions on the other end side) at both ends of the strip-shaped portion. Weight: 3.6 g, hardness: 34 degrees, ratio (S1 / S2): 0.35) of the total area (S1) occupied by the hollow to the total area (S2) of the rubber molded body was molded. After molding, the rubber molded product was placed in an oven and post-cured at 220 ° C. for 7 hours.
-Additional liquid silicone rubber composition (A) component: Methylvinylpolysiloxane 67% by mass in which both ends of the molecular chain are sealed with a dimethylvinylsiloxane group.
Component (B): 8.3% by mass of dimethylsiloxane / methylhydrogensiloxane copolymer having both ends of the molecular chain sealed with a trimethylsiloxy group
Component (C): Complex of chloroplatinic acid and olefin 0.04% by mass
Component (D): Siloxane-modified silica (DDS is used as a surface treatment agent) 15% by mass
(E) Component: 3-Methyl-1-butyne-3-ol 0.08% by mass
Increased filler: fine silica powder 9.58% by mass
下記の処方で飛翔害虫忌避香料組成物を調製した。この飛翔害虫忌避香料組成物は、飛翔害虫忌避香料成分としてシトラールを含有せず、(a)成分の配合量Xと(b)成分の配合量Yとの合計量の(c)成分の配合量Zに対する配合比率{(X+Y)/Z}が1.2であった。
・飛翔害虫忌避香料組成物(ゴム成形体1個あたり90mg)
(a)成分:メントン 6.4質量%(5.8mg)
β−ダマスコン 4.1質量%(3.7mg)
(b)成分:メンチルアセテート 9.2質量%(8.3mg)
ベンジルベンゾエート 7.8質量%(7.0mg)
アリルオクタノエート 8.5質量%(7.7mg)
(c)成分:リナロール 9.0質量%(8.1mg)
l−メントール 11.4質量%(10.3mg)
シトロネロール 3.7質量%(3.3mg)
ゲラニオール 5.4質量%(4.9mg)
(d)成分:アリルシクロヘキシルオキシアセテート、エチルリナロール、1,8−シネオール 合計14.5質量%(13.1mg)
忌避効果持続成分:トリプロピレングリコールモノメチルエーテル 20.0質量%(18.0mg)A flying pest repellent fragrance composition was prepared according to the following formulation. This flying pest repellent fragrance composition does not contain citral as a flying pest repellent fragrance component, and the blending amount of the component (c), which is the total amount of the blending amount X of the component (a) and the blending amount Y of the component (b). The blending ratio {(X + Y) / Z} with respect to Z was 1.2.
-Flying pest repellent fragrance composition (90 mg per rubber molded product)
(A) Ingredient: Menthone 6.4% by mass (5.8 mg)
β-Damascone 4.1% by mass (3.7 mg)
(B) Ingredient: Mentyl acetate 9.2% by mass (8.3 mg)
Benzyl benzoate 7.8% by mass (7.0 mg)
Allyl octanoate 8.5% by mass (7.7 mg)
(C) Ingredient: Linalool 9.0% by mass (8.1 mg)
l-Menthol 11.4% by mass (10.3 mg)
Citronellol 3.7% by mass (3.3 mg)
Geraniol 5.4% by mass (4.9 mg)
(D) Ingredients: allylcyclohexyloxyacetate, ethyllinalool, 1,8-cineole total 14.5% by mass (13.1 mg)
Repellent effect lasting ingredient: Tripropylene glycol monomethyl ether 20.0% by mass (18.0 mg)
帯状ゴム成形体の外表面の一箇所に、上記の飛翔害虫忌避香料組成物90mg(飛翔害虫忌避香料成分として72mg)を注加した。密閉下に2日間放置して飛翔害虫忌避香料組成物をゴム成形体全体に均一に浸透させ、有効持続時間が約12時間の本発明の飛翔害虫忌避製品(実施例17)を得た。 90 mg of the above-mentioned flying pest repellent fragrance composition (72 mg as a flying pest repellent fragrance component) was added to one place on the outer surface of the strip-shaped rubber molded body. The flying pest repellent fragrance composition was allowed to stand in a hermetically sealed state for 2 days to uniformly permeate the entire rubber molded body to obtain a flying pest repellent product (Example 17) of the present invention having an effective duration of about 12 hours.
実施例17の飛翔害虫忌避製品を手首に巻き付け、帯状部の一端側に設けた丸型の貫通孔の一つに他端側に設けたT字型の突起部を嵌め込んで環部を形成した。この際、実施例17の飛翔害虫忌避製品は伸縮性に優れるため操作しやすく、また、環部の大きさを調整して帯状ゴム成形体が手首上であまり移動しない接着状態にすることができた。実施例17の飛翔害虫忌避製品の揮散性能は、紐状タイプの製品の3本分に相当するため、本製品1本を手首に装着して使用すれば十分である。このように、本製品は非常に実用的なものであり、しかも約12時間にわたる使用期間中において、蚊やコバエ等の飛翔害虫に煩わされることがなかった。 The flying pest repellent product of Example 17 is wrapped around the wrist, and a T-shaped protrusion provided on the other end is fitted into one of the round through holes provided on one end side of the band-shaped portion to form a ring portion. did. At this time, the flying pest repellent product of Example 17 has excellent elasticity and is easy to operate, and the size of the ring portion can be adjusted so that the strip-shaped rubber molded body does not move much on the wrist. It was. Since the volatilization performance of the flying pest repellent product of Example 17 is equivalent to that of three string-type products, it is sufficient to wear one of the products on the wrist. As described above, this product is very practical, and during the period of use for about 12 hours, it was not bothered by flying pests such as mosquitoes and flies.
〔実施例18〕
実施例17で用いた一液性の付加型液状シリコーンゴム組成物を硬化させて、小片シート状のゴム成形体(直径:3cm、厚さ:1.2mm、片面の表面積:7.1cm2)を成形した。得られたゴム成形体の表面の一箇所に、実施例17で用いた飛翔害虫忌避香料組成物50mg(飛翔害虫忌避香料成分として40mg)を注加し、密閉下に2日間放置して飛翔害虫忌避香料組成物をゴム成形体全体に均一に浸透させた。これを、環状(直径:3.5cm)で、中央に円形穴(直径:2.7cm)をそれぞれ備える前面部と後面部をヒンジ部を介して一体成形したプラスチック製収納体に収納し、有効持続時間が約10時間の車内用の本発明の飛翔害虫忌避製品(実施例18)を得た。[Example 18]
The one-component additive liquid silicone rubber composition used in Example 17 was cured to form a small sheet-shaped rubber molded body (diameter: 3 cm, thickness: 1.2 mm, surface area on one side: 7.1 cm 2 ). Was molded. 50 mg of the flying pest repellent fragrance composition used in Example 17 (40 mg as a flying pest repellent fragrance component) was poured into one place on the surface of the obtained rubber molded body, and left to stand in a sealed state for 2 days for flying pests. The repellent fragrance composition was uniformly permeated throughout the rubber molded body. This is effectively stored in a plastic storage body that is annular (diameter: 3.5 cm) and has a circular hole (diameter: 2.7 cm) in the center, and the front and rear surfaces are integrally molded via a hinge. A flying pest repellent product of the present invention (Example 18) for in-vehicle use having a duration of about 10 hours was obtained.
実施例18の飛翔害虫忌避製品を車内に吊るして使用したところ、使用開始時から使用開始5時間後までにおける飛翔害虫忌避香料成分の平均揮散量は0.32mg/cm2・hであり、さらに、およそ10時間にわたり蚊やコバエ等の飛翔害虫が車内に侵入するのを防止できた。When the flying pest repellent product of Example 18 was hung in a vehicle and used, the average volatilization amount of the flying pest repellent fragrance component from the start of use to 5 hours after the start of use was 0.32 mg / cm 2 · h, and further. It was possible to prevent flying pests such as mosquitoes and flies from invading the vehicle for about 10 hours.
本発明の飛翔害虫忌避製品は、飛翔害虫用だけでなく広範な害虫駆除を目的として利用することが可能である。 The flying pest repellent product of the present invention can be used not only for flying pests but also for a wide range of pest control purposes.
1 環状ゴム成形体
100 帯状ゴム成形体1 Circular rubber molded
Claims (10)
前記シリコーンゴム成形体は、(A)メチルビニルポリシロキサン、(B)架橋シリコーンポリマーとしてのメチルハイドロジェンポリシロキサン、(C)反応触媒としての白金化合物、(D)補強性充填剤、及び(E)反応抑制剤を含む付加型液状シリコーンゴム組成物の硬化物であり、
前記飛翔害虫忌避香料組成物は、前記飛翔害虫忌避香料成分として、以下の(a)、(b)、及び(c):
(a)リモネン、ピネン、カンフェン、及びテルピネンからなる群より選ばれる少なくとも一種のテルペン系炭化水素化合物、及び/又はカルボン、プレゴン、メントン、カンファー、及びピペリトンからなる群より選ばれる少なくとも一種のテルペン系ケトン化合物、
(b)ベンジルアセテート、p−t−ブチルシクロヘキシルアセテート、メンチルアセテート、リナリルアセテート、ベンジルベンゾエート、アリルヘキサノエート、アリルヘプタノエート、及びアリルオクタノエートからなる群より選ばれる少なくとも一種のエステル化合物、
(c)リナロール、テルピネオール、メントール、ジヒドロミルセノール、シトロネロール、及びゲラニオールからなる群より選ばれる少なくとも一種のテルペン系アルコール化合物
を含有し、
前記飛翔害虫忌避香料組成物における(a)テルペン系炭化水素化合物及び/又はテルペン系ケトン化合物の配合量Xと(b)エステル化合物の配合量Yとの合計と、(c)テルペン系アルコール化合物の配合量Zとの配合比率{(X+Y)/Z}が、0.2〜4.0に設定されている飛翔害虫忌避製品。In a silicone rubber molded body having a hardness of 50 degrees or less, a flying pest repellent fragrance composition containing a flying pest repellent fragrance component is held in a state of being inserted into a gap in the molecular structure of the rubber constituting the silicone rubber molded body. It is a flying pest repellent product,
The silicone rubber molded product includes (A) methylvinylpolysiloxane, (B) methylhydrogenpolysiloxane as a crosslinked silicone polymer, (C) a platinum compound as a reaction catalyst, (D) a reinforcing filler, and (E). ) A cured product of an additive-type liquid silicone rubber composition containing a reaction inhibitor.
The flying pest repellent fragrance composition contains the following (a), (b), and (c) as the flying pest repellent fragrance component.
(A) At least one terpene hydrocarbon compound selected from the group consisting of limonene, pinene, camphene, and terpinene, and / or at least one terpene compound selected from the group consisting of carboxylic, pregon, menthone, camphor, and piperiten. Ketone compound,
(B) At least one ester compound selected from the group consisting of benzyl acetate, pt-butylcyclohexyl acetate, menthyl acetate, linalyl acetate, benzyl benzoate, allyl hexanoate, allyl heptanoate, and allyl octanoate.
(C) Containing at least one terpene alcohol compound selected from the group consisting of linalool, terpineol, menthol, dihydromilsenol, citronellol, and geraniol.
The total of (a) the total amount X of the terpene hydrocarbon compound and / or the terpene ketone compound and (b) the amount Y of the ester compound in the flying pest repellent fragrance composition, and (c) the terpene alcohol compound. A flying pest repellent product in which the compounding ratio {(X + Y) / Z} with the compounding amount Z is set to 0.2 to 4.0.
前記ゴム成形体の表面から前記飛翔害虫忌避香料成分を揮散させる飛翔害虫忌避方法。A method for repelling flying pests using the flying pest repellent product according to any one of claims 1 to 9.
A method for repelling flying pests by volatilizing the flying pest repellent fragrance component from the surface of the rubber molded body.
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