JP6371863B2 - Citrus essential oil transparently soluble in hydrophilic solvent and method for producing the same - Google Patents

Citrus essential oil transparently soluble in hydrophilic solvent and method for producing the same Download PDF

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JP6371863B2
JP6371863B2 JP2016571679A JP2016571679A JP6371863B2 JP 6371863 B2 JP6371863 B2 JP 6371863B2 JP 2016571679 A JP2016571679 A JP 2016571679A JP 2016571679 A JP2016571679 A JP 2016571679A JP 6371863 B2 JP6371863 B2 JP 6371863B2
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康隆 大久保
康隆 大久保
尚子 田中
尚子 田中
哲朗 西沢
哲朗 西沢
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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
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    • C11B9/00—Essential oils; Perfumes
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B9/00—Essential oils; Perfumes
    • C11B9/02—Recovery or refining of essential oils from raw materials

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Description

本発明は、親水性溶媒に透明に溶解する柑橘精油精製物の製造方法、該製造方法によって製造された柑橘精油精製物、および該柑橘精油精製物を含有する香料組成物に関する。   The present invention relates to a method for producing a purified citrus essential oil that is transparently dissolved in a hydrophilic solvent, a purified citrus oil produced by the production method, and a fragrance composition containing the purified citrus essential oil.

柑橘は、フレッシュでフルーティーな香気を有し、多くの人から好まれるため、幅広く飲食品に使用されている。特に、柑橘果皮に重要な香気成分が存在することが知られており、この果皮から柑橘の香気を連想させる果皮油などの柑橘精油を採取することができる。   Citrus has a fresh and fruity aroma and is popular with many people, so it is widely used in food and drink. In particular, it is known that an important fragrance component exists in citrus peel, and citrus essential oil such as peel oil reminiscent of citrus fragrance can be collected from the peel.

柑橘精油は飲食品に柑橘様の香味付けや風味付けを行うために重要な素材であり、香味付けや風味付けに使用する際には、使用する飲食品に溶解しやすい溶媒で希釈し、使用されている。水分含有量の高い飲食品に対して使用する場合には、親水性溶媒、具体的には含水アルコール、プロピレングリコール、グリセリンなどが挙げられるが、これらの溶媒で希釈して使用されるのが一般的である。しかし、柑橘精油はこれらの親水性溶媒には溶解しにくい成分を多く含有し、透明に溶解しにくいことが知られている。そこで、溶解性を改善するために、親水性溶媒に溶解しにくい成分を除去するための柑橘精油の加工が広く行われている。親水性溶媒に溶解しにくい成分の多くはテルペン炭化水素であることから、これらの操作は一般的にテルペンレス化と称される。   Citrus essential oil is an important material for citrus-like flavoring and flavoring of foods and drinks. When used for flavoring and flavoring, it is diluted with a solvent that is easily dissolved in the foods and drinks used. Has been. When used for foods and drinks with a high water content, hydrophilic solvents, specifically hydrous alcohol, propylene glycol, glycerin, etc., can be mentioned, but it is generally diluted with these solvents and used. Is. However, it is known that citrus essential oil contains many components that are difficult to dissolve in these hydrophilic solvents and is difficult to dissolve transparently. Thus, in order to improve solubility, citrus essential oil is widely processed to remove components that are difficult to dissolve in hydrophilic solvents. Since many of the components that are difficult to dissolve in the hydrophilic solvent are terpene hydrocarbons, these operations are generally referred to as terpeneless.

テルペンレス化の方法として工業的に広く行われているのは、ウォッシングと呼ばれる、柑橘精油を含水アルコールで抽出する工程と、フォールディングと呼ばれる、減圧蒸留でモノテルペン炭化水素を除去する工程である。しかし、ウォッシングは溶媒が含水アルコールに限定されること、香気成分の多くは含水アルコール層よりもテルペン炭化水素層に分配されるため、抽出効率が悪く香気強度が限定されるという欠点がある。また、フォールディングは、テルペン炭化水素の除去率を高くしようとすると、加熱温度が高くなり、熱ダメージによる香気の劣化を引き起こす。そのため、テルペン炭化水素含有量を１０％まで低下させるのが限界とされており（非特許文献１）、このような方法で調製したテルペンレスオイルは親水性溶媒には懸濁液となって透明に溶解しない。そのため、他のテルペンレス化の手法と組み合わせなければならない。   Widely used industrially as a terpene-less method is a step called washing, which extracts a citrus essential oil with hydrous alcohol, and a step called folding, which removes monoterpene hydrocarbons by vacuum distillation. However, washing has the disadvantage that the solvent is limited to hydrous alcohol, and most of the fragrance component is distributed to the terpene hydrocarbon layer rather than the hydrous alcohol layer, so that extraction efficiency is poor and the fragrance intensity is limited. Further, in the folding, when the removal rate of the terpene hydrocarbon is increased, the heating temperature is increased, and the fragrance is deteriorated due to thermal damage. Therefore, the limit is to reduce the terpene hydrocarbon content to 10% (Non-Patent Document 1), and the terpeneless oil prepared by such a method is a transparent suspension in a hydrophilic solvent. Does not dissolve. Therefore, it must be combined with other terpene-less methods.

この他に、炭化水素系溶媒とアルコール系溶媒を用いた液／液向流多段抽出による方法が知られている。この方法はテルペン炭化水素の含有量をほぼゼロにすることが可能であるが、引火性の高い溶媒を大量に使用するため、安全性の問題により工業的規模での実施には困難を伴う。また、吸着剤を用いたクロマトグラフィーによる方法が知られているが、吸着剤や溶媒を大量に使用するため、工業的規模での実施はコストの問題がある。   In addition, a method by liquid / liquid countercurrent multistage extraction using a hydrocarbon solvent and an alcohol solvent is known. Although this method can reduce the content of terpene hydrocarbons to almost zero, since a large amount of highly flammable solvent is used, it is difficult to implement on an industrial scale due to safety issues. Further, a method by chromatography using an adsorbent is known, but since an adsorbent and a solvent are used in large quantities, implementation on an industrial scale has a problem of cost.

また、柑橘精油のテルペンレス化の他の方法としては、テルペン系炭化水素含有天然精油（特に柑橘精油）を含水アルコールで処理し、含水アルコール層を該含水アルコール層と難混和性乃至非混和性の低沸点炭化水素溶媒でさらに抽出処理をして該低沸点炭化水素溶媒層を採取し、得られた該溶媒層から溶媒を除去することにより脱テルペン化精油を得る方法、（特許文献１）天然精油のサイクロデキストリン包接化合物を溶媒抽出することによりテルペンレス精油を得る方法、（特許文献２）シトラスオイルをプロピレングリコールと炭化水素数１〜４のアルカノールとの混合物で処理する方法（特許文献３）などが挙げられる。しかしながらこれらの方法は工業的に煩雑であるなどの欠点があった。   Further, as another method for making citrus essential oil terpeneless, terpene hydrocarbon-containing natural essential oil (especially citrus essential oil) is treated with hydrous alcohol, and the hydrous alcohol layer is hardly miscible or immiscible with the hydrous alcohol layer. A method for obtaining a deterpened essential oil by further extracting with a low-boiling point hydrocarbon solvent, collecting the low-boiling point hydrocarbon solvent layer, and removing the solvent from the obtained solvent layer (Patent Document 1) Method of obtaining terpeneless essential oil by solvent extraction of cyclodextrin inclusion compound of natural essential oil, (Patent Document 2) Method of treating citrus oil with a mixture of propylene glycol and alkanol having 1 to 4 hydrocarbons (Patent Document) 3). However, these methods have drawbacks such as industrial complexity.

また、レモン果皮油から蒸留により低沸点香気成分の一部を除去した後の蒸留残渣を薄膜蒸留する方法が開示されている（特許文献４）。しかしながら、この方法では沸点の低い含酸素揮発性成分が除去されているために、レモンのフレッシュな香気を損なわれるという欠点がある。   Moreover, the method of carrying out thin film distillation of the distillation residue after removing a part of low boiling point aromatic component from lemon peel oil by distillation is disclosed (patent document 4). However, this method has the disadvantage that the fresh aroma of lemon is impaired because the oxygen-containing volatile components having a low boiling point are removed.

さらに、柑橘精油に薄膜蒸留もしくはこれに類似する技術である短工程蒸留や分子蒸留を適用する製造方法については、農薬等の汚染物質を除去する方法として開示されている（特許文献５）。しかし、このような蒸留方法を精密蒸留と組み合わせることにより、柑橘精油の親水性溶媒への溶解性を向上させる手段となることについてはこれまで知られていなかった。   Furthermore, a manufacturing method in which thin film distillation or molecular distillation, which is a technique similar to this, is applied to citrus essential oil is disclosed as a method for removing contaminants such as agricultural chemicals (Patent Document 5). However, it has not been known so far that combining such a distillation method with precision distillation provides a means for improving the solubility of citrus essential oil in a hydrophilic solvent.

特開昭５９−２４７９５号公報JP 59-24795 A 特開昭６３−１１８３９９号公報JP 63-118399 A 特表２００３−５３５２０７号公報Special table 2003-535207 gazette 特開２０１１−５７９２３号公報JP 2011-57923 A 米国特許第５５５８８９３号明細書US Pat. No. 5,558,893

Ｄａｖｉｄ Ｍｏｙｌｅｒ、”Ｔｅｒｐｅｎｅｌｅｓｓ ａｎｄ Ｓｅｓｑｕｉｔｅｒｐｅｎｅｌｅｓｓ ｏｉｌｓ”、Ｇ．Ｄｕｇｏ、Ａ．Ｄｉ Ｇｉａｃｏｍｏ編、”Ｃｉｔｒｕｓ： Ｔｈｅ Ｇｅｎｕｓ Ｃｉｔｒｕｓ”、ＣＲＣ Ｐｒｅｓｓ、２００２年、ｐｐ．３９１−４０１David Moyler, “Terpenless and Sequiterpenels oils”, G.M. Dugo, A.D. Di Giacomo, “Citrus: The Genus Citrus”, CRC Press, 2002, pp. 391-401

本発明の目的は、工業的規模で実施容易な方法により、柑橘精油を親水性溶媒に透明に溶解するための精製方法を提供することにある。   An object of the present invention is to provide a purification method for transparently dissolving citrus essential oil in a hydrophilic solvent by a method that can be easily carried out on an industrial scale.

本発明者らは、上記の課題を解決するために鋭意研究を行ってきた結果、柑橘精油中の親水性溶媒に溶解しにくい不揮発性成分を、一定の圧力で薄膜蒸留することにより香気成分の損失を最小限にして不揮発性成分を除去できること、また、薄膜蒸留により得られた留出物を精密蒸留によりテルペンレス化すると、驚くべきことに、従来の知見とは異なり、蒸留の際の加熱温度が低くても、モノテルペン炭化水素含有量が５質量％以下である柑橘精油精製物を得ることが可能であることを見出した。   As a result of intensive studies to solve the above problems, the present inventors have conducted a thin film distillation of a non-volatile component that is difficult to dissolve in a hydrophilic solvent in citrus essential oil at a constant pressure, thereby reducing the aroma component. Surprisingly, if the distillate obtained by thin-film distillation is made terpene-less by precision distillation, the loss during heating can be surprisingly different from conventional knowledge. It has been found that even if the temperature is low, it is possible to obtain a purified product of citrus essential oil having a monoterpene hydrocarbon content of 5% by mass or less.

さらに、本発明の製造方法により得られた柑橘精油精製物は、親水性溶媒、具体的にはエタノール水溶液、イソプロパノール水溶液、プロピレングリコールに対して良好な溶解性を示すことを見出し、本発明を完成するに至った。   Furthermore, the citrus essential oil refined product obtained by the production method of the present invention has been found to exhibit good solubility in hydrophilic solvents, specifically ethanol aqueous solution, isopropanol aqueous solution, propylene glycol, and completed the present invention. It came to do.

本発明は、以下の柑橘精油精製物および柑橘精油精製物の製造方法を提供することができる。
［１］不揮発性成分を含有せず、かつモノテルペン炭化水素が５％以下である柑橘精油精製物。
［２］エタノール濃度５０質量％水溶液に１質量％溶解させた場合の６８０ｎｍの吸光度が０．５以下である［１］に記載の柑橘精油精製物。
［３］プロピレングリコールに１質量％溶解させた場合の６８０ｎｍの吸光度が０．１以下である［１］または［２］に記載の柑橘精油精製物。
［４］［１］〜［３］のいずれか一つに記載の柑橘精油精製物を配合した香料組成物。
［５］［１］〜［３］のいずれか一つに記載の柑橘精油精製物、ならびにエタノール水溶液、イソプロパノール水溶液およびプロピレングリコールからなる群から選ばれる１種以上を含有する香料組成物。
［６］以下の（１）および（２）の工程を含む、柑橘精油精製物の製造方法。
（１）柑橘精油または柑橘精油を減圧蒸留してモノテルペン炭化水素の含量を減らした精油を、圧力を１００〜１０００Ｐａ、温度を１０〜１００℃の条件で薄膜蒸留した留出物を得る工程、
（２）前記留出物を、圧力を２００〜２０００Ｐａ、加熱温度を２０〜１２５℃、留出温度を２０〜９０℃の条件で少なくとも１回以上の精密蒸留をして蒸留残渣を得る工程。
［７］［６］に記載の製造方法であって、不揮発性成分を含有せず、かつモノテルペン炭化水素が５％以下である柑橘精油精製物の製造方法。The present invention can provide the following purified citrus essential oil and a method for producing the purified citrus essential oil.
[1] A refined citrus essential oil containing no non-volatile components and containing 5% or less monoterpene hydrocarbon.
[2] The refined citrus essential oil according to [1], wherein the absorbance at 680 nm when dissolved in an aqueous solution containing 50% by mass of ethanol is 1% by mass.
[3] The purified citrus essential oil according to [1] or [2], wherein the absorbance at 680 nm when dissolved in 1% by mass in propylene glycol is 0.1 or less.
[4] A fragrance composition containing the purified citrus oil according to any one of [1] to [3].
[5] A fragrance composition containing the citrus essential oil purified product according to any one of [1] to [3], and one or more selected from the group consisting of an ethanol aqueous solution, an isopropanol aqueous solution, and propylene glycol.
[6] A method for producing a purified product of citrus essential oil, comprising the following steps (1) and (2):
(1) A step of obtaining a distillate obtained by thin-film distillation of a citrus essential oil or an essential oil having a reduced content of monoterpene hydrocarbons under reduced pressure by distillation under reduced pressure at a pressure of 100 to 1000 Pa and a temperature of 10 to 100 ° C.,
(2) A step of obtaining a distillation residue by subjecting the distillate to precision distillation at least once under the conditions of a pressure of 200 to 2000 Pa, a heating temperature of 20 to 125 ° C., and a distillation temperature of 20 to 90 ° C.
[7] The method for producing a refined citrus essential oil according to [6], which does not contain a non-volatile component and has a monoterpene hydrocarbon content of 5% or less.

本発明により製造された柑橘精油精製物は、不揮発性成分を含まず、モノテルペン炭化水素含有量が５質量％以下であるため、エタノール水溶液、イソプロパノール水溶液、プロピレングリコールに対して良好な溶解性を示し、透明に溶解することができる。   The refined citrus essential oil produced according to the present invention does not contain a non-volatile component and has a monoterpene hydrocarbon content of 5% by mass or less, and therefore has good solubility in an ethanol aqueous solution, an isopropanol aqueous solution, and propylene glycol. Can be dissolved transparently.

以下、本発明について更に詳細に説明する。   Hereinafter, the present invention will be described in more detail.

本発明で使用される柑橘精油は、柑橘果皮から圧搾法と呼ばれるローラーや遠心法などで低温のまま果皮を圧搾し、精油を採取する方法が主に用いられている。圧搾法により採取された精油はコールドプレスオイルとも呼ばれている。本発明で使用される柑橘精油の種類は、柑橘であれば特に限定されないが、例えばレモン精油、ライム精油、マンダリン精油、グレープフルーツ精油、オレンジ精油などを挙げることができる。さらに、柑橘精油は市販されているものを用いてもよい。   The citrus essential oil used in the present invention mainly uses a method of extracting essential oil from a citrus peel by pressing the peel with a roller called a pressing method or a centrifugal method at a low temperature. The essential oil collected by the pressing method is also called cold press oil. Although the kind of citrus essential oil used by this invention will not be specifically limited if it is citrus, For example, lemon essential oil, lime essential oil, mandarin essential oil, grapefruit essential oil, orange essential oil etc. can be mentioned. Further, commercially available citrus essential oils may be used.

本発明で使用される柑橘精油はあらかじめテルペンレス化したものを用いてもよい。テルペンレス化の方法は、前記のウォッシングやフォールディングといった方法やこれらの組み合わせによる方法などが挙げられる。   The citrus essential oil used in the present invention may be terpeneless. Examples of the terpeneless method include the above-described methods such as washing and folding, and methods using a combination thereof.

本発明では、まず前記柑橘精油を用いて薄膜蒸留を行い、不揮発性成分を取り除き、留出物を得る。薄膜蒸留の条件は、蒸留装置の圧力を１００〜１０００Ｐａ、好ましくは２００〜９００Ｐａに設定し、蒸留装置の温度は、１０〜１００℃、好ましくは蒸留装置の圧力における、モノテルペン炭化水素化合物であるリモネンの沸点〜９０℃に設定することが望ましい。なお、１００Ｐａにおけるリモネンの沸点は１１℃、１０００Ｐａにおいては４７℃である。   In the present invention, first, thin film distillation is performed using the citrus essential oil to remove non-volatile components, and a distillate is obtained. The conditions for the thin film distillation are monoterpene hydrocarbon compounds in which the pressure of the distillation apparatus is set to 100 to 1000 Pa, preferably 200 to 900 Pa, and the temperature of the distillation apparatus is 10 to 100 ° C., preferably at the pressure of the distillation apparatus. It is desirable to set the boiling point of limonene to 90 ° C. In addition, the boiling point of limonene at 100 Pa is 11 ° C., and it is 47 ° C. at 1000 Pa.

本発明において薄膜蒸留とは、ある一定の温度に加熱された面上に被蒸留物を連続的に供給して均一な薄膜を形成させ、該被蒸留物をその面上にある間だけ加熱し、揮発性成分を蒸発させることにより揮発性成分と不揮発性成分を分離する蒸留方法である。本発明で使用される薄膜蒸留装置は、前記の均一な薄膜が形成されるのであれば、特に限定されないが、回転薄膜蒸留装置、流下式薄膜蒸留装置、遠心式薄膜蒸留装置、分子蒸留装置などを挙げることができる。   In the present invention, thin film distillation refers to continuously supplying a product to be distilled on a surface heated to a certain temperature to form a uniform thin film, and heating the product to be distilled only on the surface. The distillation method separates a volatile component and a non-volatile component by evaporating the volatile component. The thin film distillation apparatus used in the present invention is not particularly limited as long as the uniform thin film is formed, but a rotating thin film distillation apparatus, a falling film distillation apparatus, a centrifugal thin film distillation apparatus, a molecular distillation apparatus, etc. Can be mentioned.

薄膜蒸留は１回の操作で不揮発性成分を取り除くことができるが、蒸留残渣について繰り返し薄膜蒸留を実施することにより、揮発性成分の回収率を上げることができる。   Thin film distillation can remove non-volatile components by a single operation, but by repeatedly performing thin film distillation on the distillation residue, the recovery rate of volatile components can be increased.

本発明では、次に薄膜蒸留により得られた留出物について精密蒸留を行い、柑橘精油に含有するテルペン炭化水素を留去し、テルペンレス化を行う。精密蒸留の条件は、蒸留装置の圧力を２００〜２０００Ｐａ、好ましくは４００〜１８００Ｐａに設定し、蒸留装置の加熱温度を２０〜１２５℃、好ましくは蒸留装置の圧力におけるリモネンの沸点〜１１０℃に設定する。留出温度は２０〜９０℃、好ましくは２０〜蒸留装置の圧力におけるリモネンの沸点＋２０℃の画分を留去することにより、効率よくテルペン炭化水素を、特にモノテルペン炭化水素を留去することができる。なお、２００Ｐａにおけるリモネンの沸点は２０℃、２０００Ｐａにおいては６２℃である。   In the present invention, the distillate obtained by thin film distillation is then subjected to precision distillation to distill off the terpene hydrocarbons contained in the citrus essential oil, thereby performing terpeneless. The conditions for precision distillation are that the pressure of the distillation apparatus is set to 200 to 2000 Pa, preferably 400 to 1800 Pa, and the heating temperature of the distillation apparatus is set to 20 to 125 ° C., preferably the boiling point of limonene at the pressure of the distillation apparatus to 110 ° C. To do. The distillation temperature is 20 to 90 ° C., preferably 20 to 20% by distilling off the fraction of the boiling point of limonene at the pressure of the distillation apparatus + 20 ° C. to efficiently distill off terpene hydrocarbons, particularly monoterpene hydrocarbons. Can do. The boiling point of limonene at 200 Pa is 20 ° C., and at 2000 Pa, it is 62 ° C.

前記の精密蒸留の圧力と温度の設定は、柑橘精油等を薄膜蒸留することにより得られた留出物から、モノテルペン炭化水素を留去でき、かつ、柑橘精油の重要香気成分となる含酸素化合物を残存させ、前記含酸素化合物を加熱より変化させない条件が好ましい。加熱温度を前記の温度以上に設定した場合は、含酸素化合物が変化してしまい、柑橘精油由来のフレッシュな香気が失われてしまう。   The precision distillation pressure and temperature are set so that monoterpene hydrocarbons can be distilled off from a distillate obtained by thin-film distillation of citrus essential oil, etc., and oxygen content that is an important aroma component of citrus essential oil The condition that the compound remains and the oxygen-containing compound is not changed by heating is preferable. When heating temperature is set more than the said temperature, an oxygen-containing compound will change and the fresh fragrance derived from citrus essential oil will be lost.

精密蒸留は１回の操作でテルペン炭化水素を留去することができるが、２回以上精密蒸留を実施することにより、確実にテルペン炭化水素を留去することができる。   In the precision distillation, the terpene hydrocarbon can be distilled off by one operation, but the terpene hydrocarbon can be surely distilled off by performing the precision distillation twice or more.

このようにして得られた本発明の柑橘精油精製物は、不揮発性成分を含有せず、かつモノテルペン炭化水素類が５％以下、好ましくは４％以下、より好ましくは３．５％以下であり、柑橘精油特有の成分である含酸素揮発性成分の損失が最小限に抑えられ、フレッシュな香気が保持されている。本発明の柑橘精油精製物が本発明の方法で得られたオレンジ精油精製物である場合、本発明の柑橘精油精製物における柑橘精油特有の成分である含酸素揮発性成分の割合が５０％以上であることが好ましく、６０％以上であることがより好ましく、７０％以上であることが特に好ましく、８０％以上であることがより特に好ましい。本発明の柑橘精油精製物が本発明の方法で得られたレモン精油精製物である場合、本発明の柑橘精油精製物における柑橘精油特有の成分である含酸素揮発性成分の割合が５０％以上であることが好ましく、６０％以上であることがより好ましく、６５％以上であることが特に好ましい。   The purified citrus essential oil of the present invention thus obtained contains no non-volatile components, and monoterpene hydrocarbons are 5% or less, preferably 4% or less, more preferably 3.5% or less. In addition, the loss of oxygen-containing volatile components, which are characteristic components of citrus essential oil, is minimized, and a fresh aroma is maintained. When the citrus essential oil refined product of the present invention is an orange essential oil refined product obtained by the method of the present invention, the proportion of the oxygen-containing volatile component that is a component unique to the citrus essential oil in the purified citrus essential oil of the present invention is 50% or more. It is preferably 60% or more, more preferably 70% or more, and particularly preferably 80% or more. When the purified citrus essential oil of the present invention is a purified lemon essential oil obtained by the method of the present invention, the proportion of the oxygen-containing volatile component, which is a component unique to the citrus essential oil in the purified citrus essential oil of the present invention, is 50% or more. Preferably, it is 60% or more, more preferably 65% or more.

また、本発明で得られた柑橘精油精製物は、エタノール水溶液やイソプロパノール水溶液および／またはプロピレングリコールに容易に溶解する。例えば、オレンジ果皮を圧搾して得られた一般的なオレンジ精油については、エタノール８０〜１００質量％の水溶液に１質量％溶解させたところ、完全に透明に溶解することができるが、エタノール６０質量％水溶液に、前記オレンジ精油を１質量％溶解させたところ白濁化してしまった。一方、本発明の方法で得られたオレンジ精油精製物については、エタノール６０〜１００質量％の水溶液に１質量％溶解させたところ、実質的に完全に透明に溶解することができた。本発明の柑橘精油精製物は、プロピレングリコールに１質量％溶解させた場合の６８０ｎｍの吸光度が（イオン交換水をブランクとして）０．１以下であることが好ましく、０．０５以下であることがより好ましく、０．０１以下であることが特に好ましい。本発明の柑橘精油精製物は、エタノール濃度５０質量％水溶液に１質量％溶解させた場合の６８０ｎｍの吸光度が（イオン交換水をブランクとして）０．５以下であることが好ましい。特に本発明の柑橘精油精製物が本発明の方法で得られたオレンジ精油精製物である場合、本発明の柑橘精油精製物は、エタノール濃度５０質量％水溶液に１質量％溶解させた場合の６８０ｎｍの吸光度が（イオン交換水をブランクとして）０．５以下であることが好ましく、０．３以下であることがより好ましく、０．１５以下であることが特に好ましく、０．０５以下であることがより特に好ましく、０．０１以下であることがさらにより特に好ましい。本発明の柑橘精油精製物が本発明の方法で得られたレモン精油精製物である場合、本発明の柑橘精油精製物は、エタノール濃度５０質量％水溶液に１質量％溶解させた場合の６８０ｎｍの吸光度が（イオン交換水をブランクとして）０．５以下であることが好ましく、０．４以下であることがより好ましく、０．３５以下であることが特に好ましく、０．０５以下であることがより特に好ましく、０．０１以下であることがさらにより特に好ましい。本発明の柑橘精油精製物が本発明の方法で得られたグレープフルーツの精油精製物である場合、本発明の柑橘精油精製物は、エタノール濃度５０質量％水溶液に１質量％溶解させた場合の６８０ｎｍの吸光度が（イオン交換水をブランクとして）０．５以下であることが好ましく、０．４５以下であることがより好ましく、０．４以下であることが特に好ましい。本発明の柑橘精油精製物が本発明の方法で得られたライムの精油精製物である場合、本発明の柑橘精油精製物は、エタノール濃度５０質量％水溶液に１質量％溶解させた場合の６８０ｎｍの吸光度が（イオン交換水をブランクとして）０．５以下であることが好ましく、０．４以下であることがより好ましく、０．３５以下であることが特に好ましい。   Moreover, the refined citrus essential oil obtained in the present invention is easily dissolved in an aqueous ethanol solution, an aqueous isopropanol solution and / or propylene glycol. For example, a general orange essential oil obtained by squeezing orange peel can be dissolved completely in an aqueous solution of 80 to 100% by mass of ethanol, and can be completely transparently dissolved, but 60% by mass of ethanol. When 1% by mass of the orange essential oil was dissolved in a 1% aqueous solution, it became cloudy. On the other hand, when the purified orange essential oil obtained by the method of the present invention was dissolved in an aqueous solution of 60 to 100% by mass of ethanol in an amount of 1% by mass, it could be dissolved substantially completely transparently. In the citrus essential oil refined product of the present invention, the absorbance at 680 nm when dissolved in 1% by mass in propylene glycol (with ion-exchanged water as a blank) is preferably 0.1 or less, and preferably 0.05 or less. More preferred is 0.01 or less. The purified citrus essential oil of the present invention preferably has an absorbance at 680 nm of 0.5% or less (using ion-exchanged water as a blank) when 1% by mass is dissolved in a 50% by mass aqueous solution of ethanol. In particular, when the purified citrus essential oil of the present invention is a purified orange essential oil obtained by the method of the present invention, the purified citrus essential oil of the present invention is 680 nm when dissolved in an aqueous solution of 50% by mass of ethanol at 1% by mass. Is preferably 0.5 or less (with ion-exchanged water as a blank), more preferably 0.3 or less, particularly preferably 0.15 or less, and 0.05 or less. Is more particularly preferable, and it is even more particularly preferable that it is 0.01 or less. When the refined citrus essential oil of the present invention is a refined lemon essential oil obtained by the method of the present invention, the refined citrus essential oil of the present invention has a 680 nm of 1% by mass dissolved in a 50% by mass aqueous solution of ethanol. The absorbance is preferably 0.5 or less (using ion-exchanged water as a blank), more preferably 0.4 or less, particularly preferably 0.35 or less, and 0.05 or less. More particularly preferred is 0.01 or less, even more particularly preferred. When the refined citrus essential oil of the present invention is a refined refined grapefruit oil obtained by the method of the present invention, the refined citrus essential oil of the present invention is 680 nm when dissolved in an ethanol concentration of 50% by mass in an aqueous solution of 1% by mass. Is preferably 0.5 or less (using ion-exchanged water as a blank), more preferably 0.45 or less, and particularly preferably 0.4 or less. When the refined citrus essential oil of the present invention is a refined lime essential oil obtained by the method of the present invention, the refined citrus essential oil of the present invention is 680 nm when dissolved in an aqueous solution of 50% by mass of ethanol at 1% by mass. Is preferably 0.5 or less (using ion-exchanged water as a blank), more preferably 0.4 or less, and particularly preferably 0.35 or less.

さらに、本発明で得られた柑橘精油精製物は、従来の精製方法と比較して、柑橘精油成分のシトラール等の特定のフレーバー成分が熱劣化や光劣化がきわめて起こりにくく、かつ、柑橘精油の香気に寄与するオフフレーバーが生成しづらいため、柑橘精油由来の香気が経時的に損なわれることがほとんどない。   Furthermore, the citrus essential oil refined product obtained in the present invention is less susceptible to thermal degradation and photodegradation of specific flavor components such as citral essential citrus components, compared to conventional purification methods, and Since it is difficult to produce an off-flavor that contributes to the fragrance, the fragrance derived from the citrus essential oil is hardly damaged over time.

本発明で得られた柑橘精油精製物は、そのまま飲食品や香粧品に添加することができるが、エタノール水溶液やイソプロパノール水溶液および／またはプロピレングリコールに容易に溶解するため、これらの溶媒に溶解させた組成物を飲食品や香粧品に添加することで、柑橘本来の香気を付与し、より天然に近い好ましい香気を付与することができる。好ましくは、オレンジ様、レモン様、ライム様、グレープフルーツ様、ユズ様などの柑橘香料組成物に本発明の柑橘精油精製物を微量配合して香料組成物を得、それを飲食品や香粧品に配合することで、さらに天然に近い柑橘本来のピール感、フレッシュ感、みずみずしさなどの香気を付与することができる。   The purified citrus essential oil obtained in the present invention can be added to foods and beverages and cosmetics as it is, but is easily dissolved in an ethanol aqueous solution, an isopropanol aqueous solution and / or propylene glycol. By adding the composition to foods and drinks and cosmetics, it is possible to impart the original aroma of citrus and to impart a more desirable natural aroma. Preferably, a fragrance composition is obtained by blending a small amount of the citrus essential oil refined product of the present invention into a citrus fragrance composition such as orange-like, lemon-like, lime-like, grapefruit-like, yuzu-like, etc. By blending, it is possible to impart fragrances such as natural citrus original peel, freshness, and freshness.

本発明で得られた柑橘精油精製物の配合量は、その目的あるいは柑橘香料組成物の種類によっても異なるが、例えば、柑橘香料組成物の全体重量に対して１ｐｐｍ〜５０％、好ましくは、１０ｐｐｍ〜１０％の範囲を例示することができる。これらの範囲内では、柑橘香料組成物に対し柑橘本来のピール感、フレッシュ感、みずみずしさなどを付与する優れた効果を有する。   The amount of the citrus essential oil refined product obtained in the present invention varies depending on the purpose or the type of the citrus fragrance composition, but for example, 1 ppm to 50%, preferably 10 ppm with respect to the total weight of the citrus fragrance composition. A range of -10% can be exemplified. Within these ranges, the citrus fragrance composition has an excellent effect of imparting a citrus original peel feeling, a fresh feeling, a freshness, and the like.

さらに、本発明で得られた柑橘精油精製物を有効成分とする柑橘香味増強剤を含有させた柑橘香料組成物を有効量添加したことを特徴とする飲食品または香粧品に関し、該製品に柑橘本来の香気を付与することができる。かかる飲食品または香粧品としては特に制限はなく、柑橘香味を有するものであればよく、広い分野の各種飲食品または香粧品に添加利用することができる。飲食品としては、例えば、コーラ飲料、果汁入炭酸飲料、乳類入炭酸飲料などの炭酸飲料類；果汁飲料、野菜飲料、スポーツドリンク、ハチミツ飲料、豆乳、ビタミン補給飲料、ミネラル補給飲料、栄養ドリンク、滋養ドリンク、乳酸菌飲料、乳飲料などの食系飲料類；緑茶、紅茶、ウーロン茶、ハーブティー、コーヒー飲料などの嗜好飲料類；チューハイ、カクテルドリンク、発泡酒、果実酒、薬味酒などのアルコール飲料類；アイスクリーム、ラクトアイス、氷菓、ヨーグルト、プリン、ゼリー、デイリーデザートなどのデザート類及びそれらを製造するためのミックス類；キャラメル、キャンディー、錠菓、クラッカー、ビスケット、クッキー、パイ、チョコレート、スナックなどの菓子類及びそれらを製造するためのケーキミックスなどのミックス類；パン、スープ、各種インスタント食品などの一般食品類；を挙げることができる。また、香粧品としては、例えば、香水；シャンプー、リンス、ヘアクリーム、ポマードなどのヘアケア製品；オシロイ、口紅などの化粧品類；フェイス用石鹸、ボデイ用石鹸、洗濯用石鹸、洗濯用洗剤、消毒用洗剤、防臭洗剤などの保健・衛生用洗剤類；歯みがき、ティッシュペーパー、トイレットペーパーなどの保健・衛生材料類；室内芳香剤、カーコロンなどの芳香製品；を挙げることができる。   Furthermore, the present invention relates to a food or drink or cosmetic comprising an effective amount of a citrus fragrance composition containing a citrus flavor enhancer containing the citrus essential oil refined product obtained in the present invention as an active ingredient. The original fragrance can be imparted. There is no restriction | limiting in particular as this food-drinks or cosmetics, What is necessary is just to have a citrus flavor, and it can be added and utilized for various food-drinks or cosmetics of a wide field | area. Examples of foods and drinks include carbonated beverages such as cola beverages, carbonated beverages containing fruit juice, carbonated beverages containing milk; fruit juice beverages, vegetable beverages, sports drinks, honey beverages, soy milk, vitamin supplemented beverages, mineral supplemented beverages, nutritional drinks , Nourishment drinks, lactic acid bacteria drinks, dairy drinks and other food drinks; green tea, black tea, oolong tea, herbal teas, coffee drinks and other favorite drinks; Desserts such as ice cream, lacto ice, ice confectionery, yogurt, pudding, jelly, daily desserts and mixes for producing them; caramel, candy, tablet confectionery, crackers, biscuits, cookies, pie, chocolate, snacks, etc. Confectionery and cake mix for making them What mix like; bread, soup, general foods such as various kinds of instant foods; can be mentioned. Cosmetics include, for example, perfumes; hair care products such as shampoos, rinses, hair creams, pomades; cosmetics such as oscillating and lipsticks; facial soaps, body soaps, laundry soaps, laundry detergents, disinfectants Health and hygiene detergents such as detergents and deodorants; Health and hygiene materials such as toothpaste, tissue paper, and toilet paper; Fragrance products such as indoor fragrances and carcolon;

以下、本発明を実施例によりさらに具体的に説明する。なお、本発明はこれらに限定されるものではない。   Hereinafter, the present invention will be described more specifically with reference to examples. The present invention is not limited to these.

実施例１：オレンジ精油精製物の製造
市販のバレンシアオレンジ精油（比較品１）１０７２．０ｇを、分子蒸留装置を用いて、圧力５００Ｐａ、加熱温度８０℃、ワイパー回転速度３００ｒｐｍにて薄膜蒸留処理を行い、留出物１０３０．８ｇ、残渣３２．７ｇを得た。再度残渣を同じ条件で薄膜蒸留処理を行い、留出物５．１ｇ、残渣２７．９ｇを得た。前記薄膜蒸留処理で得られた留出物を合わせた１０３５．９ｇを、スルーザーパッキン充填蒸留塔を用い、１．５ｋＰａで、留出温度５５〜６５℃、加熱温度６５〜１００℃の条件により精密蒸留し、テルペン炭化水素を留出させることにより、オレンジ精油精製物９９．１ｇが得られた。さらに、テルペン炭化水素を留出させるために、スルーザーパッキン充填蒸留塔を用い、５００Ｐａ、留出温度４０〜５５℃、加熱温度７０〜１１０℃の条件により再度精密蒸留し、テルペン炭化水素を留出させることにより、オレンジ精油精製物１９．５ｇ（本発明品１）が得られた。Example 1: Production of purified orange essential oil 1072.0 g of a commercially available Valencia orange essential oil (Comparative product 1) was subjected to thin-film distillation using a molecular distillation apparatus at a pressure of 500 Pa, a heating temperature of 80 ° C., and a wiper rotation speed of 300 rpm. And 1030.8 g of distillate and 32.7 g of residue were obtained. The residue was again subjected to thin-film distillation under the same conditions to obtain 5.1 g of a distillate and 27.9 g of a residue. 1035.9 g of the distillate obtained by the thin-film distillation treatment was combined at 1.5 kPa with a distilling temperature of 55 to 65 ° C. and a heating temperature of 65 to 100 ° C. using a Sulzer packing packed distillation column. By carrying out precision distillation and distilling the terpene hydrocarbon, 99.1 g of purified orange essential oil was obtained. Furthermore, in order to distill terpene hydrocarbons, a distillation column packed with a sulzer packing was used and precision distillation was again performed under the conditions of 500 Pa, a distillation temperature of 40 to 55 ° C., and a heating temperature of 70 to 110 ° C. to distill the terpene hydrocarbons. As a result, 19.5 g of a purified orange essential oil (Product 1 of the present invention) was obtained.

参考例１：オレンジテルペンレス精油の製造
比較品１の４５０．８ｇを、マクマホンパッキン充填蒸留塔を用い、１．５ｋＰａで、留出温度５０〜６０℃、加熱温度５５〜６５℃の条件により減圧蒸留し、テルペン炭化水素を留出させることにより、オレンジテルペンレス精油１３１．４ｇ（比較品２）が得られた。Reference Example 1: Manufacture of orange terpeneless essential oil 450.8 g of Comparative Product 1 was depressurized under conditions of 1.5 kPa, distillation temperature 50-60 ° C, heating temperature 55-65 ° C using a McMahon packing packed distillation column. Distillation and distilling terpene hydrocarbons yielded 131.4 g of orange terpeneless essential oil (Comparative Product 2).

実施例２：オレンジ精油のＧＣ−ＭＳ測定
本発明品１、前記比較品１〜２、市販のオレンジオイル液々抽出品（比較品３）および市販のオレンジオイル液々抽出テルペンフリー品（比較品４）、以上計５品についてＧＣ−ＭＳを用いて揮発性成分の測定を行った。化合物の存在割合は、マススペクトル全体のトータルイオンクロマト面積値に対する、化合物のトータルイオンクロマト面積値の割合計算した。その存在割合の結果を、モノテルペン炭化水素、含酸素揮発性成分、セスキテルペン炭化水素、その他揮発性成分に分類した。Example 2: GC-MS Measurement of Orange Essential Oil Invention Product 1, Comparative Products 1 and 2, Commercial Orange Oil Liquid Extract (Comparative Product 3), and Commercial Orange Oil Liquid Extract Terpen Free Product (Comparative Product) 4) The volatile component was measured using GC-MS for a total of 5 products. The proportion of the compound was calculated by calculating the ratio of the total ion chromatogram area value of the compound to the total ion chromatogram area value of the entire mass spectrum. The results of the existence ratio were classified into monoterpene hydrocarbons, oxygen-containing volatile components, sesquiterpene hydrocarbons, and other volatile components.

ＧＣ−ＭＳ測定条件
ＧＣ条件、カラム：ＩｎｅｒｔＣａｐＷＡＸ（６０ｍ×０．２５ｍｍ、膜厚０．２５μｍ）、昇温条件：４０℃〜２３０℃、５．０℃／ｍｉｎ昇温、２３０℃で３０分保持、キャリアガス：ヘリウム、線速度：２５ｃｍ／ｓｅｃ
ＭＳ条件、測定モード：ＥＩ／ＳＣＡＮ、７０ｅＶ、ＭＳ温度：２３０℃（イオン源）、１５０℃（四重極）、スキャンレンジ：３５−３５０ａｍｕ
それぞれの分類における存在割合の結果を表１に示す。 GC-MS measurement conditions GC conditions, column: InertCapWAX (60 m × 0.25 mm, film thickness 0.25 μm), temperature rising conditions: 40 ° C. to 230 ° C., 5.0 ° C./min temperature rising, maintained at 230 ° C. for 30 minutes , Carrier gas: helium, linear velocity: 25 cm / sec
MS conditions, measurement mode: EI / SCAN, 70 eV, MS temperature: 230 ° C. (ion source), 150 ° C. (quadrupole), scan range: 35-350 amu
Table 1 shows the result of the existence ratio in each classification.

Figure 0006371863
Figure 0006371863

表１の結果より、本発明品１はモノテルペン炭化水素の割合が０．４２％であり、実施例１の操作を行うことにより、モノテルペン炭化水素を除去することができた。また、比較品４は、液々抽出により炭化水素を除去した一般的にテルペンフリー品と呼ばれる製品であり、炭化水素を除去したため、モノテルペン炭化水素およびセスキテルペン炭化水素の存在割合が低い。   From the results shown in Table 1, the product 1 of the present invention had a monoterpene hydrocarbon ratio of 0.42%, and the monoterpene hydrocarbon could be removed by the operation of Example 1. Comparative product 4 is a product generally called a terpene-free product from which hydrocarbons have been removed by liquid-liquid extraction. Since hydrocarbons have been removed, the proportion of monoterpene hydrocarbons and sesquiterpene hydrocarbons is low.

実施例３：オレンジ精油の不揮発性成分の割合
本発明品１、比較品１、４の計３品についてのオレンジ精油を、実施例１に示す条件で薄膜蒸留処理した際の残渣と薄膜蒸留処理に供したオレンジ精油との割合を計算し、これを不揮発性成分の割合とした。本発明品１、比較品１、４の不揮発性成分の割合を表２に示す。Example 3: Ratio of non-volatile components of orange essential oil Residue and thin film distillation treatment of orange essential oil of a total of three products of the present invention product 1 and comparative products 1 and 4 under the conditions shown in Example 1 The ratio with the orange essential oil subjected to was calculated, and this was defined as the ratio of the nonvolatile component. Table 2 shows the ratio of nonvolatile components of the present invention product 1 and comparative products 1 and 4.

Figure 0006371863
Figure 0006371863

表２の結果より、本発明品１はすでに薄膜蒸留処理を行っているため、不揮発性成分は存在しない。一方で、液々抽出テルペンフリー品である比較品４は、不揮発性成分が含まれていることが示された。   From the result of Table 2, since the product 1 of the present invention has already been subjected to the thin film distillation treatment, there is no non-volatile component. On the other hand, it was shown that the comparative product 4 which is a liquid-extracted terpene-free product contains a non-volatile component.

実施例４：オレンジ精油の溶解性試験
本発明品１および比較品１の有機溶媒に対する溶解性試験を行った。溶媒は、プロピレングリコールおよびエタノール５０〜１００質量％の水溶液を用い、溶媒に対してオレンジ精油を１質量％溶解させ、オレンジ精油溶液の吸光度を以下の濁度測定法にしたがって評価した。
濁度測定法：イオン交換水をブランクとして、表３に記載の各溶媒に本発明品１および比較品１の試料を１％溶解させた場合の６８０ｎｍの吸光度を、日本分光（ＪＡＳＣＯ）Ｖ−５６０紫外可視分光光度計を用いて、２５℃で測定する。なお、エタノール濃度５０〜１００質量％水溶液は、水１００質量％に対してエタノール５０〜１００質量％をそれぞれ混合した水溶液である。結果を表３に示す。Example 4: Orange essential oil solubility test The solubility test of the product 1 of the present invention and the comparative product 1 in an organic solvent was conducted. The solvent used was an aqueous solution of 50 to 100% by mass of propylene glycol and ethanol, 1% by mass of orange essential oil was dissolved in the solvent, and the absorbance of the orange essential oil solution was evaluated according to the following turbidity measurement method.
Turbidity measurement method: Absorbance at 680 nm when 1% of the sample of the product 1 of the present invention and the comparative product 1 was dissolved in each solvent described in Table 3 using ion-exchanged water as a blank was measured by JASCO V- Measurements are made at 25 ° C. using a 560 UV-Vis spectrophotometer. In addition, 50-100 mass% ethanol density | concentration aqueous solution is an aqueous solution which mixed 50-100 mass% of ethanol with respect to 100 mass% of water, respectively. The results are shown in Table 3.

Figure 0006371863
Figure 0006371863

表３の結果より、本発明品１はエタノール濃度６０〜９０質量％の水溶液には透明に溶解するが、エタノール濃度５０質量％の水溶液には少し吸光度が高くなってしまった。一方、比較品１はエタノール濃度８０〜９０質量％の水溶液には透明に溶解するが、エタノール濃度７０質量％以下の水溶液については透明に溶解せず、吸光度が高くなってしまうことが示された。   From the results of Table 3, the product 1 of the present invention was transparently dissolved in an aqueous solution having an ethanol concentration of 60 to 90% by mass, but the absorbance was slightly increased in an aqueous solution having an ethanol concentration of 50% by mass. On the other hand, Comparative Product 1 was transparently dissolved in an aqueous solution having an ethanol concentration of 80 to 90% by mass, but the aqueous solution having an ethanol concentration of 70% by mass or less was not transparently dissolved, and the absorbance was increased. .

実施例５：オレンジ精油の***試験
本発明品１および比較品１〜４の熱***および光***試験を行った。まずは、本発明品１および比較品１〜４をエタノール７０質量％の水溶液に溶解させた。エタノール水溶液に本発明品１は０．４質量％、比較品１は２０質量％、比較品２は６質量％、比較品３は５質量％、比較品４は０．５質量％溶解させた。比較品１〜３については炭化水素の割合が高く炭化水素が溶解されないため、不溶部を除去してエタノール水溶液とした。このエタノール水溶液の溶解品を表４の処方により飲料に賦香した。Example 5: Orange Essential Oil Abuse Test The heat abuse and light abuse tests of the invention product 1 and comparative products 1 to 4 were conducted. First, the product 1 of the present invention and the comparative products 1 to 4 were dissolved in an aqueous solution of 70% by mass of ethanol. The present invention product 1 was dissolved in an ethanol aqueous solution by 0.4 mass%, the comparative product 1 was 20 mass%, the comparative product 2 was 6 mass%, the comparative product 3 was 5 mass%, and the comparative product 4 was 0.5 mass%. . Comparative products 1 to 3 had a high proportion of hydrocarbons and did not dissolve the hydrocarbons, so the insoluble portion was removed to obtain an ethanol aqueous solution. The dissolved product of this ethanol aqueous solution was flavored to beverages according to the formulation shown in Table 4.

Figure 0006371863
Figure 0006371863

この賦香した飲料について***試験を行った。熱***の条件は５０℃に保たれた容器に１０日間放置した。光***の条件は２０，０００ルクスの部屋に１００時間放置した。これらの***品について、***前の飲料をコントロール品（コントロール品は冷暗所にて保管）として、よく訓練されたパネラー１０名で香気評価を行った。香気評価は以下の基準により５段階で行った。５：コントロール品と差なし、４：少し劣化臭あり、３：オレンジ感は残るものの劣化臭あり、２：劣化臭あり、１：強い劣化臭あり。１０名のパネラーの評価の平均を表５に示す。   An abuse test was conducted on the flavored beverage. The condition of heat abuse was left for 10 days in a container kept at 50 ° C. The condition of light abuse was left in a room of 20,000 lux for 100 hours. About these abused goods, the beverage before the abuse was used as a control product (the control product was stored in a cool and dark place), and fragrance evaluation was conducted by 10 well-trained panelists. The fragrance evaluation was performed in five stages according to the following criteria. 5: No difference from the control product, 4: Slightly deteriorated odor, 3: Orange remains but deteriorated odor, 2: Deteriorated odor, 1: Strongly deteriorated odor. Table 5 shows the average evaluation of 10 panelists.

Figure 0006371863
Figure 0006371863

表５の結果より、本発明品１は比較品１〜４と比較して***したときの香気劣化が最も少ないことが分かった。比較品１はテルペンレス処理をしていないオレンジ精油であるが、エタノール水溶液にはテルペン炭化水素が溶解しており、また、不揮発性成分も存在するため、***した際にオフフレーバーが多く生成したものと考えられる。また、比較品４は、少し劣化臭が生じていることが示された。   From the results of Table 5, it was found that the product 1 of the present invention had the least fragrance degradation when abused compared to the comparative products 1 to 4. Comparative product 1 is an orange essential oil that has not been subjected to terpene-less treatment, but terpene hydrocarbons are dissolved in the ethanol aqueous solution, and non-volatile components also exist, so that a lot of off-flavor was generated when abused. It is considered a thing. Moreover, it was shown that the comparative product 4 has a slightly deteriorated odor.

実施例６：レモン精油精製物の製造
市販のレモン精油（比較品５）１９９１．６ｇを、分子蒸留装置を用いて、圧力５００Ｐａ、加熱温度８０℃、ワイパー回転速度３００ｒｐｍにて薄膜蒸留処理を行い、留出物１８５７．３ｇ、残渣１２２．５ｇを得た。再度残渣を同じ条件で薄膜蒸留処理を行い、留出物６４．７ｇ、残渣５８．４ｇを得た。前記薄膜蒸留処理で得られた留出物を合わせた１９２２．０ｇを、スルーザーパッキン充填蒸留塔を用い、１．５ｋＰａで、留出温度４３〜６５℃、加熱温度６５〜１０１℃の条件により精密蒸留し、テルペン炭化水素を留出させることにより、レモン精油精製物１９０．１ｇが得られた。さらに、テルペン炭化水素を留出させるために、スルーザーパッキン充填蒸留塔を用い、５００Ｐａ、留出温度４０〜５５℃、加熱温度７０〜１１０℃の条件により再度精密蒸留し、テルペン炭化水素を留出させることにより、レモン精油精製物１０６．２ｇ（本発明品２）が得られた。Example 6: Manufacture of purified lemon essential oil 1991.6 g of commercially available lemon essential oil (Comparative Product 5) was subjected to thin-film distillation using a molecular distillation apparatus at a pressure of 500 Pa, a heating temperature of 80 ° C., and a wiper rotation speed of 300 rpm. , 1857.3 g of distillate and 122.5 g of residue were obtained. The residue was again subjected to thin-film distillation treatment under the same conditions to obtain 64.7 g of a distillate and 58.4 g of a residue. A total of 1922.0 g of the distillate obtained by the thin-film distillation treatment is 1.5 kPa at a distillation temperature of 43 to 65 ° C. and a heating temperature of 65 to 101 ° C. using a distillation column filled with a sulzer. By refined distillation to distill terpene hydrocarbons, 190.1 g of a purified lemon essential oil was obtained. Furthermore, in order to distill terpene hydrocarbons, a distillation column packed with a sulzer packing was used and precision distillation was again performed under the conditions of 500 Pa, a distillation temperature of 40 to 55 ° C., and a heating temperature of 70 to 110 ° C. to distill the terpene hydrocarbons. As a result, 106.2 g of a refined lemon essential oil (Product 2 of the present invention) was obtained.

参考例２：レモンテルペンレス精油の製造
比較品５の４００．２ｇを、マクマホンパッキン充填蒸留塔を用い、１．５ｋＰａで、留出温度５２〜６０℃、加熱温度５７〜６５℃の条件により減圧蒸留し、テルペン炭化水素を留出させることにより、レモンテルペンレス精油１００．１ｇ（比較品６）が得られた。Reference Example 2: Manufacture of lemon terpeneless essential oil 400.2 g of Comparative Product 5 was depressurized under conditions of 1.5 kPa, distillation temperature 52-60 ° C, heating temperature 57-65 ° C using a McMahon packing packed distillation column. Distillation and distilling terpene hydrocarbons yielded 100.1 g of lemon terpeneless essential oil (Comparative Product 6).

実施例７：レモン精油のＧＣ−ＭＳ測定
本発明品２、前記比較品５〜６、市販のレモンオイル液々抽出品（比較品７）および市販のレモンオイル液々抽出テルペンフリー品（比較品８）、以上計５品についてＧＣ−ＭＳを用いて揮発性成分の測定を行った。化合物の存在割合は、マススペクトル全体のトータルイオンクロマト面積値に対する、化合物のトータルイオンクロマト面積値の割合計算した。その存在割合の結果を、モノテルペン炭化水素、含酸素揮発性成分、セスキテルペン炭化水素、その他揮発性成分に分類した。ＧＣ−ＭＳ測定は実施例と同様の条件で測定した。Example 7: GC-MS Measurement of Lemon Essential Oil Invention Product 2, Comparative Products 5-6, Commercial Lemon Oil Liquid Extract (Comparative Product 7) and Commercial Lemon Oil Liquid Extract Terpen Free Product (Comparative Product) 8) The volatile component was measured using GC-MS for a total of 5 products. The proportion of the compound was calculated by calculating the ratio of the total ion chromatogram area value of the compound to the total ion chromatogram area value of the entire mass spectrum. The results of the existence ratio were classified into monoterpene hydrocarbons, oxygen-containing volatile components, sesquiterpene hydrocarbons, and other volatile components. The GC-MS measurement was performed under the same conditions as in the examples.

それぞれの分類における存在割合の結果を表６に示す。   Table 6 shows the results of the existence ratio in each classification.

Figure 0006371863
Figure 0006371863

表６の結果より、本発明品２はモノテルペン炭化水素の割合が３．０７％であり、実施例６の操作を行うことにより、モノテルペン炭化水素を除去することができた。また、比較品８は、液々抽出により炭化水素を除去した一般的にテルペンフリー品と呼ばれる製品であり、炭化水素を除去したため、モノテルペン炭化水素およびセスキテルペン炭化水素の存在割合が低い。   From the results shown in Table 6, the product 2 of the present invention had a monoterpene hydrocarbon ratio of 3.07%, and the monoterpene hydrocarbon could be removed by performing the operation of Example 6. Comparative product 8 is a product generally called a terpene-free product from which hydrocarbons have been removed by liquid-liquid extraction. Since hydrocarbons have been removed, the proportion of monoterpene hydrocarbons and sesquiterpene hydrocarbons is low.

実施例８：レモン精油の不揮発性成分の割合
本発明品２、比較品５、８の計３品についてのレモン精油を、実施例６に示す条件で薄膜蒸留処理した際の残渣と薄膜蒸留処理に供したレモン精油との割合を計算し、これを不揮発性成分の割合とした。本発明品２、比較品５、８の不揮発性成分の割合を表７に示す。Example 8: Ratio of non-volatile components of lemon essential oil The residue and thin film distillation treatment of the lemon essential oil of a total of three products of the present invention product 2 and comparative products 5 and 8 under the conditions shown in Example 6 The ratio with the lemon essential oil subjected to 1 was calculated, and this was defined as the ratio of the nonvolatile component. Table 7 shows the ratio of non-volatile components of the product 2 of the present invention and the comparative products 5 and 8.

Figure 0006371863
Figure 0006371863

表７の結果より、本発明品２はすでに薄膜蒸留処理を行っているため、不揮発性成分は存在しない。一方で、液々抽出テルペンフリー品である比較品８は、不揮発性成分が含まれていることが示された。   From the result of Table 7, since the product 2 of the present invention has already been subjected to the thin film distillation treatment, there is no non-volatile component. On the other hand, it was shown that the comparative product 8 which is a liquid-extracted terpene-free product contains a non-volatile component.

実施例９：レモン精油の溶解性試験
本発明品２および比較品５の有機溶媒に対する溶解性試験を行った。溶媒は、プロピレングリコールおよびエタノール５０〜１００質量％の水溶液を用い、溶媒に対してレモン精油を１質量％溶解させ、レモン精油溶液の吸光度を実施例４と同様の濁度測定法にしたがって評価した。結果を表８に示す。Example 9: Lemon Essential Oil Solubility Test The solubility test of the present invention product 2 and comparative product 5 in an organic solvent was conducted. The solvent used was an aqueous solution of 50 to 100% by mass of propylene glycol and ethanol, 1% by mass of lemon essential oil was dissolved in the solvent, and the absorbance of the lemon essential oil solution was evaluated according to the same turbidity measurement method as in Example 4. . The results are shown in Table 8.

Figure 0006371863
Figure 0006371863

表８の結果より、本発明品２はエタノール濃度７０〜９０質量％の水溶液には透明に溶解するが、エタノール濃度６０質量％の水溶液では少し吸光度が高くなってしまった。一方、比較品５はエタノール濃度８０〜９０質量％の水溶液には透明に溶解するが、エタノール濃度７０質量％以下の水溶液については透明に溶解せず、吸光度が高くなってしまうことが示された。また、比較品５については、プロピレングリコール溶液中においても吸光度が高くなってしまうことが示された。   From the results of Table 8, the product 2 of the present invention was transparently dissolved in an aqueous solution having an ethanol concentration of 70 to 90% by mass, but the absorbance was slightly increased in an aqueous solution having an ethanol concentration of 60% by mass. On the other hand, it was shown that the comparative product 5 is transparently dissolved in an aqueous solution having an ethanol concentration of 80 to 90% by mass, but the aqueous solution having an ethanol concentration of 70% by mass or less is not transparently dissolved and the absorbance increases. . Moreover, about the comparative product 5, it was shown that a light absorbency will also become high in a propylene glycol solution.

実施例１０：レモン精油の***試験
本発明品２および比較品５〜８の熱***および光***試験を行った。まずは、本発明品２および比較品５〜８をエタノール７０質量％の水溶液に溶解させた。エタノール水溶液に本発明品２は１質量％、比較品５は２０質量％、比較品６は５質量％、比較品７は５質量％、比較品８は１質量％溶解させた。比較品５〜７については炭化水素の割合が高く炭化水素が溶解されないため、不溶部を除去してエタノール水溶液とした。このエタノール水溶液の溶解品を実施例５の表４に示す処方により飲料に賦香した。Example 10: Lemon Essential Oil Abuse Test The inventive product 2 and comparative products 5-8 were subjected to thermal and light abuse tests. First, the product 2 of the present invention and the comparative products 5 to 8 were dissolved in an aqueous solution of 70% by mass of ethanol. 1% by mass of the product 2 of the present invention, 20% by mass of the comparative product 5, 5% by mass of the comparative product 6, 5% by mass of the comparative product 7 and 1% by mass of the comparative product 8 were dissolved in the ethanol aqueous solution. In Comparative products 5 to 7, the ratio of hydrocarbons was high and the hydrocarbons were not dissolved, so the insoluble part was removed to obtain an ethanol aqueous solution. The dissolved product of this ethanol aqueous solution was flavored to a beverage according to the formulation shown in Table 4 of Example 5.

この賦香した飲料について***試験を行った。熱***の条件は５０℃に保たれた容器に１０日間放置した。光***の条件は２０，０００ルクスの部屋に１００時間放置した。これらの***品について、***前の飲料をコントロール品（コントロール品は冷暗所にて保管）として、よく訓練されたパネラー１０名で香気評価を行った。香気評価は以下の基準により５段階で行った。５：コントロール品と差なし、４：少し劣化臭あり、３：レモン感は残るものの劣化臭あり、２：劣化臭あり、１：強い劣化臭あり。１０名のパネラーの評価の平均を表９に示す。   An abuse test was conducted on the flavored beverage. The condition of heat abuse was left for 10 days in a container kept at 50 ° C. The condition of light abuse was left in a room of 20,000 lux for 100 hours. About these abused goods, the beverage before the abuse was used as a control product (the control product was stored in a cool and dark place), and fragrance evaluation was conducted by 10 well-trained panelists. The fragrance evaluation was performed in five stages according to the following criteria. 5: No difference from control product, 4: Slightly deteriorated odor, 3: Lemon feeling remains but deteriorated odor, 2: Deteriorated odor, 1: Strongly deteriorated odor. Table 9 shows the average evaluation of 10 panelists.

Figure 0006371863
Figure 0006371863

表９の結果より、本発明品２は比較品５〜８と比較して***したときの香気劣化が最も少ないことが分かった。比較品５はテルペンレス処理をしていないレモン精油であるが、エタノール水溶液にはテルペン炭化水素が溶解しており、また、不揮発性成分も存在するため、***した際にオフフレーバーが多く生成したものと考えられる。また、比較品８のテルペンフリー品は、油の劣化臭が生じている。   From the results in Table 9, it was found that the product 2 of the present invention had the least fragrance degradation when abused compared to the comparative products 5-8. Comparative product 5 is a lemon essential oil that has not been treated with terpene, but terpene hydrocarbons are dissolved in the aqueous ethanol solution, and there are also non-volatile components, so a lot of off-flavor was produced when abused. It is considered a thing. Moreover, the terpene free product of the comparative product 8 has a deteriorated odor of oil.

以上の結果より、不揮発性成分を含有せず、かつモノテルペン炭化水素が５％以下である本発明品１および２は、プロピレングリコールやエタノール水溶液に容易に溶解し、また、高温の条件や光照射の条件でも香気がほとんど損なわれないことが示された。   From the above results, the products 1 and 2 of the present invention which do not contain a non-volatile component and have a monoterpene hydrocarbon content of 5% or less can be easily dissolved in propylene glycol or an aqueous ethanol solution, It was shown that the aroma is hardly impaired even under irradiation conditions.

Claims (6)

不揮発性成分を含有せず、かつモノテルペン炭化水素が５％以下である柑橘精油精製物であって、
エタノール濃度５０質量％水溶液に１質量％溶解させた場合の６８０ｎｍの吸光度が０．５以下である、柑橘精油精製物。 A citrus essential oil refined product containing no non-volatile components and having a monoterpene hydrocarbon content of 5% or less ,
A purified citrus essential oil having an absorbance at 680 nm of 0.5 or less when dissolved in an aqueous solution containing 50% by mass of ethanol at 1% by mass . プロピレングリコールに１質量％溶解させた場合の６８０ｎｍの吸光度が０．１以下である、請求項１に記載の柑橘精油精製物。 The purified citrus essential oil according to claim 1, wherein the absorbance at 680 nm when dissolved in 1% by mass in propylene glycol is 0.1 or less. 請求項１または２に記載の柑橘精油精製物を配合した香料組成物。 A fragrance composition containing the purified citrus essential oil according to claim 1 or 2 . 請求項１または２に記載の柑橘精油精製物、ならびにエタノール水溶液、イソプロパノール水溶液およびプロピレングリコールからなる群から選ばれる１種以上を含有する香料組成物。 A fragrance composition containing the purified citrus essential oil according to claim 1 or 2 and at least one selected from the group consisting of an ethanol aqueous solution, an isopropanol aqueous solution and propylene glycol. 以下の（１）および（２）の工程を含む、柑橘精油精製物の製造方法。
（１）柑橘精油または柑橘精油を減圧蒸留してモノテルペン炭化水素の含量を減らした精油を、圧力を１００〜１０００Ｐａ、温度を１０〜１００℃の条件で薄膜蒸留した留出物を得る工程、
（２）前記留出物を、圧力を２００〜２０００Ｐａ、加熱温度を２０〜１２５℃、留出温度を２０〜９０℃の条件で少なくとも１回以上の精密蒸留をして蒸留残渣を得る工程。 A method for producing a purified citrus essential oil comprising the following steps (1) and (2):
(1) A step of obtaining a distillate obtained by thin-film distillation of a citrus essential oil or an essential oil having a reduced content of monoterpene hydrocarbons under reduced pressure by distillation under reduced pressure at a pressure of 100 to 1000 Pa and a temperature of 10 to 100 ° C.,
(2) A step of obtaining a distillation residue by subjecting the distillate to precision distillation at least once under the conditions of a pressure of 200 to 2000 Pa, a heating temperature of 20 to 125 ° C., and a distillation temperature of 20 to 90 ° C. 請求項５に記載の製造方法であって、不揮発性成分を含有せず、かつモノテルペン炭化水素が５％以下である柑橘精油精製物の製造方法。 It is a manufacturing method of Claim 5 , Comprising: The manufacturing method of the citrus essential oil refined product which does not contain a non-volatile component and monoterpene hydrocarbon is 5% or less.
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