JP4265878B2 - Deterioration preventing agent for functional processed oils and fats containing carnosol and / or carnosic acid, and fats and oils containing the same - Google Patents

Description

【０００８】
（上記式中、−Ｃ（＝Ｏ）Ｒ１ 、−Ｃ（＝Ｏ）Ｒ２ は、炭素数１４〜２４の脂肪酸残基、Ｒ３ は水素または炭素数６〜１２の脂肪酸残基を表す。）
【０００９】
【発明の実施の形態】
本発明で用いられる油脂は、下記の一般式（３）で表される構造を有する。
【００１０】
【化４】

【００１１】
上記式中、−Ｃ（＝Ｏ）Ｒ１ 、−Ｃ（＝Ｏ）Ｒ２ は、炭素数１４〜２４の脂肪酸残基、Ｒ３ は水素または炭素数６〜１２の脂肪酸残基を表す。従来の天然油脂は、−Ｃ（＝Ｏ）Ｒ１ 、−Ｃ（＝Ｏ）Ｒ２ 及びＲ３ は、通常、炭素数１４〜２４の長鎖脂肪酸残基であるが、本発明で使用される油脂は、Ｒ３ の部分が、水素または中鎖脂肪酸残基であることに特徴がある。−Ｃ（＝Ｏ）Ｒ１ 、−Ｃ（＝Ｏ）Ｒ２ は、炭素数２０〜２４の脂肪酸残基であることが好ましい。又、−Ｃ（＝Ｏ）Ｒ１ 、−Ｃ（＝Ｏ）Ｒ２ 、Ｒ３ は不飽和脂肪酸の残基であることが好ましい。本発明の油脂は、通常、天然物由来の油脂、例えばサフラワー油、オリーブ油、綿実油、ナタネ油、コーン油、大豆油、パーム油、又、ひまわり油、ごま油等の植物油から加工精製されて得られる。加工精製とは、食用天然油脂中のクロロフィルを除去し、その後エステル交換したり、食用天然油脂の分解・再エステル化、その後の分別、蒸留又は吸着等を行うことである。具体的に説明すると、エステル交換法としては、例えば、油脂同士、あるいは油脂とグリセリン又は脂肪酸の混合物に触媒としてナトリウムメチラート等のアルカリ触媒又はリパーゼ等の酵素を用いて反応させる方法が挙げられる。また、再エステル化法としては、例えば、グリセリンと脂肪酸を酸触媒、リパーゼ触媒又は無触媒で反応させる方法が挙げられる。反応後の精製法としては、例えば、分子蒸留、ウィンターリング、溶剤分別及びカラム分別等が挙げられる。
【００１２】
本発明で用いられる劣化防止剤は、下記式（１）で表される化合物（慣用名；カルノソール）または／及び下記式（２）で表される化合物（慣用名；カルノジック酸）を含有する。
【００１３】
【化５】

【００１４】
（上記式中、−Ｃ（＝Ｏ）Ｒ１ 、−Ｃ（＝Ｏ）Ｒ２ は、炭素数１４〜２４の脂肪酸残基、Ｒ３ は水素または炭素数６〜１２の脂肪酸残基を表す。）
カルノソール及びカルノジック酸は、天然酸化防止剤として知られるローズマリー抽出物の成分である。カルノソールとカルノジック酸が一般式（３）の油脂の劣化防止に特に効果がある理由は明らかではないが、以下の様に推定される。まず、一般式（３）で表される油脂は、Ｒ３ が水素または中鎖脂肪酸残基であるので、Ｒ３ 部分が長鎖脂肪酸である従来の油脂より親水性が増すため、両親媒性を有し、油脂が気液界面に配列し易くなる。その結果、一般式（３）で表される油脂は、従来の天然油脂より酸化され易くなる。これに対し、カルノソール及びカルノジック酸は、一般式（３）で表される油脂より親水性が高いため、油脂と空気の間に配列して、油脂が空気と接触するのを防止できる。また、カルノソール及びカルノジック酸が、油脂の酸化されやすい部分（主に、構成脂肪酸の二重結合部分）を立体的にブロックして、酸化を抑制するものと考えられる。
【００１５】
カルノソール及びカルノジック酸は、通常、ロ−ズマリ−より抽出して得られる。ローズマリー抽出物には、抽出溶媒や抽出液の処理方法により、水溶性または非水溶性のものが得られるが、カルノソール及びカルノジック酸は、非水溶性の抽出物中に含まれる。非水溶性抽出物は、例えば、含水率２０〜７０％、好ましくは４０〜６０％のエタノールで処理し、この抽出液に水を加えて非水溶性成分を析出させ、更にこれに活性炭を加えて撹拌した後、この溶液から非水溶性成分と活性炭成分との混合物をろ取し、この混合物をエタノールで処理抽出し、この抽出液から溶媒を留去して得られる（特公昭５９−４４６９号公報）。抽出には、ローズマリーの全草、または、その葉、根、茎、花、果実、種子の何れを使用してもよいが、好ましくは葉を使用する。ローズマリーを刻んでから抽出した方が抽出効率が高くて好ましい。カルノソール及びカルノジック酸は、ローズマリー非水溶性抽出物から単離精製して使用してもよいが、精製せずにそのまま使用してもよい。本発明の劣化防止剤中には、カルノソールまたはカルノジック酸のいずれか一方のみを含有させてもよいし、両方含有させてもよい。劣化防止剤中のカルノソール及びカルノジック酸の含有量は、カルノソールとカルノジック酸の合計で通常１％以上、好ましくは３％以上、更に好ましくは１０％以上、更に好ましくは４０％以上である。本発明の劣化防止剤には、本発明の効果を損なわない範囲で、他の成分を含有することができる。例えば、ショ糖脂肪酸エステル、有機酸モノグリセリド、ポリグリセリン脂肪酸エステル、リン脂質等の乳化剤が挙げられる。また目的に応じては、各種の風味付与剤（フレーバー）、栄養強化剤、減粘剤、ビタミンＥ等の他の酸化防止剤なども添加できる。
【００１６】
本発明の劣化防止剤は、通常、油脂中にカルノソール及びカルノジック酸の合計量が0.05ppm 以上、1000ppm以下、好ましくは10ppm以上、500ppm以下、特に好ましくは50ppm以上、200ppm以下となるように添加する。
本発明の劣化防止剤が添加された油脂は、野菜炒め等の炒め物調理、天ぷら、唐揚げ等の揚げ物調理に好適に利用される。
【００１７】
【実施例】
以下、本発明を実施例により詳細に説明するが、本発明は、特にこれらに制限されるものではない。
ローズマリー抽出物sample１の製造
ローズマリー１ｋｇに５０％含水エタノール１０Ｌ加えて３時間加熱還流し、温時ろ過してろ液を得た。残さを５０％含水エタノール６Ｌで同様に処理抽出する操作をさらに二回繰りかえしてろ液を得た。これらのろ液を合わせ、水５Ｌを加えると沈殿が析出した。このろ液に活性炭１００ｇを加えて１時間攪拌し、一夜冷所放置した後、ろ過して沈殿と活性炭との混合物を得た。この混合物にエタノール４Ｌを加えて３時間加熱還流し、温時ろ過してろ液を得た。残さをエタノール２．４Ｌで同様に処理抽出する操作をさらに二回繰り返してろ液を得た。これらのろ液を合わせ、減圧濃縮し、エタノールを留去し、粉末状のローズマリー抽出物（三菱化学フーズ（株） 商品名；ＲＭ２１Ｂｂａｓｅ）を得た。
ローズマリー抽出物sample２の製造
ローズマリー５００ｇにｎーヘキサン１．２Ｌ加え、室温で一夜攪拌し、抽出を行った。吸引ろ過により、ろ液を分離後、残さに１．２Ｌのｎ−ヘキサンを加えて同様に処理した。この操作を３回行い、抽出ろ液を集め、減圧下で溶媒を留去し、濃縮してｎ−ヘキサン抽出物１９．７１ｇを得た。次にこの抽出物について水蒸気蒸留を行い、揮発成分２．７５ｇを除き、１６．９５ｇのローズマリー抽出物を得た。
ローズマリー抽出物sample３の製造
sample１のローズマリー抽出物１重量部に対し、中鎖トリグリセリン（花王（株）製 商品名：ココナート）３．５重量部を加え、６０℃で３時間撹拌し、常温になるまで放置して、ローズマリー抽出物を得た。
【００１８】
製造されたローズマリー抽出物sample１〜３のカルノソール及びカルノジック酸の含有量を表−１に示す。
【００１９】
【表１】

【００２０】
市販の加工油脂Ａ、Ｂに製造したローズマリー抽出物を１６０ｐｐｍ添加し、１２０℃に保持して、これに空気をバブリングし、出てくる揮発成分を脱塩水の溶液にトラップした。このトラップした溶液の伝導度を測定する方法により、加工油脂の劣化を調べた。ローズマリー抽出物を添加しなかったブランクを比較例３とした。
＊加工油脂の劣化解析
１２０℃でバブリング開始後、時間とともに一定の揮発成分が出てくる時期を誘導期とする。その後、急激に酸化劣化のために揮発成分が時間とともに増大していく時期を劣化期とする。誘導期まだの伝導度を０として、劣化期に入った初期の伝導度の増加速度（ｕＳ／ｓｅｃ）を測定し、劣化の目安とした。
【００２１】
劣化防止試験の結果を表−２に示す。
【００２２】
【表２】

【００２３】
加工油脂Ａ；一般式（３）の−Ｃ（＝Ｏ）Ｒ１ 、−Ｃ（＝Ｏ）Ｒ２ はエルカ酸残基、Ｒ３ は水素
加工油脂Ｂ；一般式（３）の−Ｃ（＝Ｏ）Ｒ１ 、−Ｃ（＝Ｏ）Ｒ２ はエルカ酸残基、Ｒ３ はＣ６ 〜Ｃ１２の中鎖脂肪酸残基
表−２より、カルノソール及びカルノジック酸を添加すると、油脂の劣化が抑制されることがわかる。
【００２４】
【発明の効果】
本発明の劣化防止剤は、健康によい機能性加工油脂の劣化防止に大変優れた効果を発揮する。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an agent for preventing deterioration of functional processed oils and fats used for cooking. In detail, it is related with the fats and oils containing this which are used for deep-fried foods and fried foods, and the deterioration prevention agent of the processing oils and fats which are good for health.
[0002]
[Prior art]
Cooking oils used for fried foods and fried foods cause problems such as decomposition and polymerization when heated during cooking, resulting in volatilization of volatile substances and unpleasant odors peculiar to oil. There is. In particular, when oil is used repeatedly for deep-fried foods, the smell becomes tight. In order to solve this problem, various oil and fat deterioration inhibitors have been developed.
[0003]
On the other hand, due to the recent health boom, functional processed fats and oils that are good for health are being marketed. A representative of these functional processed fats and oils is that glycerin triesters of long chain fatty acids are used in the conventional natural fats and oils, while glycerin diesters of long chain fatty acids and one of the constituent fatty acids are medium chain fatty acids. Is a glycerin triester. These processed fats and oils are known to be healthy because their bioabsorption mechanisms are different from conventional natural fats and oils.
[0004]
[Problems to be solved by the invention]
However, these functional processed oils and fats have a problem that they are more easily oxidized than conventional natural oils and fats due to the difference in structure. Moreover, it is necessary to enhance the product image by suppressing the generation of degradation products and polymerization products that are less healthy than conventional fats and oils, and suppressing unpleasant odors.
[0005]
Therefore, research on degradation inhibitors for functional processed oils and fats has been conducted. However, vitamin E is only added as an antioxidant to functional processed fats and oils that are currently on the market. Development of a high degradation inhibitor was demanded.
[0006]
[Means for Solving the Problems]
Therefore, as a result of intensive investigations, the present inventors obtained a rosemary extract known as an antioxidant, which is obtained by extraction using a specific solvent, particularly for preventing deterioration of functional processed oils and fats. The inventors have found that an excellent effect is exhibited, and have reached the present invention.
That is, the gist of the present invention, the rosemary using ethanol moisture content 20% to 70%, the total amount of carnosic acid represented by Karunoso Le及 beauty formula represented by the formula (1) (2) 40 It exists in the deterioration prevention agent of fats and oils represented by General formula (3) consisting of the extract obtained by extracting so that it may become more than% .
[0007]
[Chemical 3]

[0008]
(In the above formula, -C (= O ) R1, -C (= O ) R2 represents a fatty acid residue having 14 to 24 carbon atoms, and R3 represents hydrogen or a fatty acid residue having 6 to 12 carbon atoms.)
[0009]
DETAILED DESCRIPTION OF THE INVENTION
The fats and oils used in the present invention have a structure represented by the following general formula (3).
[0010]
[Formula 4]

[0011]
In the above formula, -C (= O ) R1, -C (= O ) R2 represents a fatty acid residue having 14 to 24 carbon atoms, and R3 represents hydrogen or a fatty acid residue having 6 to 12 carbon atoms. In conventional natural fats and oils, -C (= O ) R1, -C (= O ) R2 and R3 are usually long-chain fatty acid residues having 14 to 24 carbon atoms, but the fats and oils used in the present invention are , R3 is characterized by being hydrogen or a medium chain fatty acid residue. -C (= O ) R1 and -C (= O ) R2 are preferably fatty acid residues having 20 to 24 carbon atoms. Moreover, it is preferable that -C (= O ) R1, -C (= O ) R2, R3 is a residue of an unsaturated fatty acid. The fats and oils of the present invention are usually obtained by processing and refining from natural oils and fats such as safflower oil, olive oil, cottonseed oil, rapeseed oil, corn oil, soybean oil, palm oil, sunflower oil, sesame oil and other vegetable oils. It is done. Processing refinement is to remove chlorophyll in edible natural fats and oils and then transesterify them, to decompose and re-esterify edible natural fats and oils, to perform subsequent fractionation, distillation or adsorption. Specifically, as the transesterification method, for example, a method of reacting fats and oils or a mixture of fats and oils with glycerin or fatty acids using an alkali catalyst such as sodium methylate or an enzyme such as lipase as a catalyst can be mentioned. Moreover, as a re-esterification method, the method of making glycerol and a fatty acid react with an acid catalyst, a lipase catalyst, or a non-catalyst is mentioned, for example. Examples of the purification method after the reaction include molecular distillation, wintering, solvent fractionation, and column fractionation.
[0012]
The deterioration inhibitor used in the present invention contains a compound represented by the following formula (1) (common name: carnosol) or / and a compound represented by the following formula (2) (common name: carnosic acid).
[0013]
[Chemical formula 5]

[0014]
(In the above formula, -C (= O ) R1, -C (= O ) R2 represents a fatty acid residue having 14 to 24 carbon atoms, and R3 represents hydrogen or a fatty acid residue having 6 to 12 carbon atoms.)
Carnosol and carnosic acid are components of rosemary extract known as natural antioxidants. The reason why carnosol and carnosic acid are particularly effective in preventing deterioration of the oil and fat of the general formula (3) is not clear, but is estimated as follows. First, the fat and oil represented by the general formula (3) has an amphipathic property because R3 is hydrogen or a medium-chain fatty acid residue, so that the hydrophilicity of the fat and oil increases compared to conventional fats and oils in which the R3 portion is a long-chain fatty acid. In addition, oils and fats are easily arranged at the gas-liquid interface. As a result, the oil and fat represented by the general formula (3) is more easily oxidized than the conventional natural oil and fat. On the other hand, since carnosol and carnosic acid are more hydrophilic than the oil and fat represented by the general formula (3), they can be arranged between the oil and fat and prevent the oil and fat from coming into contact with air. In addition, it is considered that carnosol and carnosic acid sterically block a portion of oil and fat that is easily oxidized (mainly a double bond portion of a constituent fatty acid) to suppress oxidation.
[0015]
Carnosol and carnosic acid are usually obtained by extraction from rosemary. A rosemary extract can be either water-soluble or water-insoluble depending on the method of treating the extraction solvent or the extract. Carnosol and carnosic acid are contained in the water-insoluble extract. The water-insoluble extract is treated with, for example, ethanol having a water content of 20 to 70%, preferably 40 to 60%, water is added to the extract to precipitate water-insoluble components, and activated carbon is further added thereto. After stirring, the mixture of the water-insoluble component and the activated carbon component is filtered from this solution, this mixture is treated and extracted with ethanol, and the solvent is distilled off from this extract (Japanese Patent Publication No. 59-4469). Issue gazette). For the extraction, the whole plant of rosemary or its leaves, roots, stems, flowers, fruits and seeds may be used, but leaves are preferably used. It is preferable that the extraction is performed after chopping rosemary because the extraction efficiency is high. Carnosol and carnosic acid may be isolated and purified from a rosemary water-insoluble extract, or may be used as they are without purification. Only one or both of carnosol and carnosic acid may be contained in the deterioration preventing agent of the present invention. The content of carnosol and carnosic acid in the deterioration inhibitor is generally 1% or more, preferably 3% or more, more preferably 10% or more, and further preferably 40% or more in total of carnosol and carnosic acid. The deterioration preventing agent of the present invention can contain other components as long as the effects of the present invention are not impaired. For example, emulsifiers such as sucrose fatty acid ester, organic acid monoglyceride, polyglycerin fatty acid ester, phospholipid and the like can be mentioned. Depending on the purpose, various flavoring agents (flavors), nutrient enhancers, viscosity reducers, other antioxidants such as vitamin E, and the like can also be added.
[0016]
The deterioration preventing agent of the present invention is usually added so that the total amount of carnosol and carnosic acid in the oil and fat is 0.05 ppm to 1000 ppm, preferably 10 ppm to 500 ppm, particularly preferably 50 ppm to 200 ppm. .
The fats and oils to which the deterioration preventing agent of the present invention is added are suitably used for cooking fried foods such as stir-fried vegetables, and fried foods such as tempura and fried chicken.
[0017]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not restrict | limited in particular to these.
Production of Rosemary Extract sample 1 10 L of 50% aqueous ethanol was added to 1 kg of rosemary, heated under reflux for 3 hours, and filtered while warm to obtain a filtrate. The residue was similarly treated and extracted with 6 L of 50% aqueous ethanol in the same manner twice to obtain a filtrate. When these filtrates were combined and 5 L of water was added, a precipitate was deposited. To this filtrate, 100 g of activated carbon was added, stirred for 1 hour, allowed to stand overnight in a cool place, and then filtered to obtain a mixture of precipitate and activated carbon. 4 L of ethanol was added to this mixture, and the mixture was heated to reflux for 3 hours and filtered while warm to obtain a filtrate. An operation of treating and extracting the residue with 2.4 L of ethanol in the same manner was further repeated twice to obtain a filtrate. These filtrates were combined, concentrated under reduced pressure, and ethanol was distilled off to obtain a powdered rosemary extract (Mitsubishi Chemical Foods, Inc., trade name: RM21Bbase).
Production of Rosemary Extract sample 2 To 500 g of rosemary, 1.2 L of n-hexane was added, and the mixture was stirred overnight at room temperature for extraction. The filtrate was separated by suction filtration, and 1.2 L of n-hexane was added to the residue to perform the same treatment. This operation was performed 3 times, and the extract filtrate was collected, the solvent was distilled off under reduced pressure, and the residue was concentrated to obtain 19.71 g of an n-hexane extract. Next, this extract was subjected to steam distillation, and 2.75 g of volatile components were removed to obtain 16.95 g of rosemary extract.
Production of rosemary extract sample 3
To 1 part by weight of sample 1 rosemary extract, add 3.5 parts by weight of medium chain triglycerin (trade name: Coconut, manufactured by Kao Corporation), stir at 60 ° C. for 3 hours, and let stand until it reaches room temperature. , Rosemary extract was obtained.
[0018]
Table 1 shows the contents of carnosol and carnosic acid in the produced rosemary extract samples 1-3.
[0019]
[Table 1]

[0020]
160 ppm of the rosemary extract produced in commercially available processed fats and oils A and B was added and kept at 120 ° C., air was bubbled into this, and the volatile components coming out were trapped in a solution of demineralized water. By measuring the conductivity of the trapped solution, the deterioration of the processed oil was investigated. A blank to which no rosemary extract was added was designated as Comparative Example 3 .
* Degradation analysis of processed fats and oils After the start of bubbling at 120 ° C, the period when certain volatile components come out with time is the induction period. Thereafter, a period in which the volatile components increase with time due to rapid oxidative deterioration is defined as a deterioration period. The conductivity increase rate (uS / sec) at the beginning of the deterioration period was measured with the conductivity still in the induction period set to 0, and used as a measure of deterioration.
[0021]
Table 2 shows the results of the deterioration prevention test.
[0022]
[Table 2]

[0023]
Processed oil and fat A: —C ( ═O 2 ) R1 and —C ( ═O 2) R2 in the general formula (3) are erucic acid residues, R3 is hydrogen processed oil and fat B; —C ( ═O 2 ) in the general formula (3) R1, -C (= O ) R2 is an erucic acid residue, R3 is a medium chain fatty acid residue of C6 to C12. From Table 2, it can be seen that the addition of carnosol and carnosic acid suppresses the deterioration of fats and oils.
[0024]
【The invention's effect】
The deterioration preventive agent of the present invention exhibits a very excellent effect in preventing deterioration of functional processed oils and fats that are good for health.

Claims (5)

Rosemary is extracted using ethanol with a water content of 20 to 70% so that the total amount of carnosol represented by formula (1) and carnosic acid represented by formula (2) is 40% or more. A fat and oil deterioration preventive agent represented by the general formula (3), comprising the extracted product.

(In the above formula, -C (= O ) R1, -C (= O ) R2 represents a fatty acid residue having 14 to 24 carbon atoms, and R3 represents hydrogen or a fatty acid residue having 6 to 12 carbon atoms.) To the extract obtained by extracting rosemary with ethanol having a water content of 40-60%, water was added to precipitate water-insoluble components, and the filter cake obtained by filtering this was re-recovered with ethanol. 2. The oil and fat deterioration preventing agent according to claim 1, which is obtained by obtaining an extraction step. -C (= O ) R1, General formula (3), -C (= O ) R2 and R3 are residues of unsaturated fatty acids, The prevention of deterioration of fats and oils according to claim 1 or 2 Agent. An oil represented by the general formula (3), comprising the deterioration inhibitor according to any one of claims 1 to 3 .

(In the above formula, -C (= O ) R1, -C (= O ) R2 represents a fatty acid residue having 14 to 24 carbon atoms, and R3 represents hydrogen or a fatty acid residue having 6 to 12 carbon atoms.) The fats and oils according to claim 4 , wherein the deterioration preventing agent according to any one of claims 1 to 3 is contained in an amount of 50 to 200 ppm as a total amount of carnosol and carnosic acid.