JP3272072B2 - Method for producing vegetable oil containing lignans - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a vegetable oil containing a water-insoluble, antioxidant lignan, and the vegetable oil is used in the food, cosmetics and pharmaceutical industries. .

[0002]

2. Description of the Related Art Oxidation or peroxidative degradation during the processing and storage of fats and oils products not only lowers the commercial value of foods and other products utilizing fats and oils, but also is harmful to living organisms such as lipid peroxides and free radicals. Means that a suitable substance is produced. Therefore, research on components for preventing the oxidation or peroxidation of such fats and oils and their activities has been regarded as important, and development of antioxidants having excellent activity and fats and oils products containing them has been attracting attention.
Also, in recent years, development of safer antioxidant active substances using natural products as raw materials has become a very important issue due to increasing concerns about synthetic antioxidants by consumers.

[0003] It is known that fats and oils obtained from sesame seeds have higher oxidative stability than fats and oils produced from other oil seeds. This is because sesame seeds or their fats and oils contain sesamin (tetrahydro-1,4-di [3,4- (methylenedioxy) phenyl] -1H, 3H-flo [3, a type of phenolic lignan. 4-
C] furan) and sesamoline (tetrahydro-1- [3,
4- (methylenedioxy) phenoxy] -4- [3,4
There are so-called lignan analogues such as-(methylenedioxy) phenyl] -1H, 3H-furo [3,4-C] furan, which, together with tocopherol, are closely related to the antioxidant properties of sesame seeds and their fats and oils. It is said to be related.

[0004] That is, during the refining process of sesame salad oil, in the decolorizing step, by heat treatment using acid clay, a part of sesamolin contained in the fat and oil undergoes chemical intermolecular transfer, and sesame sulphate having an antioxidant activity. Nol (tetrahydro-1- [6-hydroxy-3,4- (methylenedioxy) phenyl] -4- [3,4- (methylenedioxy)
Phenyl] -1H, 3H-furo [3,4-C] furan)
Is converted to Therefore, although the content of sesame salad oil refined through such a process varies depending on the production conditions, it is present as sesaminol in an amount of about 100 to 1400 ppm, which contributes to the remarkable oxidative stability of sesame salad oil. It is considered (Mitsuo Namiki, Sadasaku Kobayashi, edited by Sesame Science, Asakura Shoten, 1989).

However, as in the case of the above-mentioned sesame salad oil production, in the method of producing sesaminol-containing fats and oils by heating using acid clay in the decolorizing step, sesame saliva obtained by the chemical transfer reaction of sesamolin is used. Most of the knols are epi isomers (2α- or 6α-sesaminol) or dia isomers (2α- and 6α-sesaminol) of the structural isomers. It is a substance that does not naturally exist in sesame seeds as a natural product. By the way, in sesame salad oil treated with acid clay or activated clay,
Sesaminol: 2α-epi form: 6α-epi form: di
It is known that the isomer is contained at a ratio of 4: 4: 4: 1. The decolorizing treatment of fats and oils requires heating (at least 60 ° C. or more) in the presence of acid clay, and has problems such as requiring a large amount of energy.

Incidentally, sesame seeds contain a characteristic antioxidant, pinoresinol (tetrahydro-1,4-di (3-methoxy-4-hydroxyphenyl) -1H, 3H).
H-furo [3,4-C] furan), P-1 (tetrahydro-1- (3-methoxy-4-hydroxyphenyl)-
4- [3,4- (methylenedioxy) phenyl] -1
H, 3H-furo [3,4-C] furan), sesamolinol (tetrahydro-1- [3-methoxy-4-hydroxyphenoxy] -4- [3,4- (methylenedioxy)
Phenyl] -1H, 3H-furo [3,4-C] furan)
And sesaminol are known to be contained. However, most of these are present as lignan glycosides, and thus are removed from fats and oils as defatted lees in a normal oil-making process. Therefore, although they are powerful antioxidants specific to sesame seeds, they have not been utilized with fats and oils.

[0007]

In view of such circumstances, the present inventors have conducted intensive studies on a method for producing an oil or fat containing a lignan analog, and have completed the present invention.
That is, the present invention relates to a method for easily producing a vegetable oil containing water-insoluble and antioxidant lignans present in sesame seeds.

[0008]

Means for Solving the Problems One of the present invention is characterized in that ground sesame seeds are dispersed in water having a pH of 3 to 7, and after stirring, the oil is extracted with an organic solvent. Another feature of the present invention is characterized in that ground sesame seeds and / or pressed oil cake are dispersed in water having a pH of 3 to 7 to which cellulase has been added, and treated similarly.

First, the former method will be described in detail below. In this method, sesame seeds can be used irrespective of their type and locality. However, sesame seeds that have not been subjected to high-temperature treatments such as roasting or extreme chemical treatments, which cause the enzyme activity in the seeds to be lost, are used. This is coarsely or finely pulverized at a temperature of 60 ° C. or lower, preferably at a normal temperature or lower by using a general-purpose pulverizer to obtain a raw material. If the temperature exceeds 60 ° C., enzymes in the seeds may be deactivated. Then, the raw material is mixed with 1 to 20 times volume / weight (hereinafter abbreviated as v / wt) of water or pH 3 to
7, preferably dispersed or dissolved in a buffer solution having a pH of 4.5 to 6, and the space in the reaction vessel as it is or in a sealed state is replaced with nitrogen, desirably at 10 to 60 ° C for 1 to 72 hours, preferably 24 to 40 hours. While slowly stirring or shaking for a time, the sugar chain is hydrolyzed using the enzyme in the raw material. After the reaction, residues composed of cell tissue fragments and the like are removed by using an appropriate means such as centrifugation or filtration, and an appropriate amount of a water-insoluble solvent such as ethyl acetate, n-butanol or hexane is added to the reaction solution. By extracting and removing the solvent, it is possible to obtain a vegetable oil containing lignans such as sesaminol having the desired antioxidant activity.

Next, the second method of the present invention is performed as follows. Raw sesame seeds, regardless of their origin or type,
Further, any material may be used as long as it is coarse or finely pulverized while the oil and fat remains, as exemplified by the pulverized material and / or the compressed oil cake. That is, as used in the first method described above,
Sesame seeds having enzyme activity remaining therein, or those subjected to heat treatment such as roasting or chemical treatment can be used in the present method. Such a raw material is added to the raw material for 1
~ 20 times (v / wt) water or pH 3-7, preferably p
Disperse or dissolve in H4.5-6 buffer. In this method, it is essential to add 0.1 to 30% (wt / wt), preferably 1 to 10% (wt / wt) of cellulase to the raw material at this time. Cellulase may be any as long as it has an activity of hydrolyzing long-chain and short-chain sugar chain bonds, and can be used regardless of its origin and degree of purification.In particular, commercially available products derived from microorganisms are inexpensive and preferably used. Can be used. Further, the carrier may be immobilized on a suitable carrier and may be used repeatedly. In this method, the mixture of the raw material and the cellulase is subjected to a hydrolysis reaction, residue removal and solvent extraction treatment under the same operating procedures and conditions as those in the first method, and the desired antioxidant activity of sesaminol is obtained. Thus, vegetable oils containing lignans can be obtained.

The lignans in the fats and oils thus obtained are:
It is a mixture of sesaminol as a main component, sesamorinol, pinoresinol, P-1 and the like, and these are known as oil-soluble antioxidant components. Therefore, fats and oils rich in these have excellent stability against oxidative or peroxidative degradation. In addition, since the fats and oils of the present invention have not undergone a radical chemical change in the production process, they do not contain any structural isomers such as epi-forms which are not originally present in sesame seeds. Furthermore, according to this method, it is possible to prepare fats and oils containing a large amount of lignans having antioxidant power without requiring a large amount of energy or expensive drugs.

[0012]

EXAMPLES Example 1 1 kg of sesame seeds was roughly crushed with a blender to obtain a raw material of 0.1 kg.
Add 10 liters of N acetate buffer (pH 4.5) for 24 hours,
Shake at 50 ° C. Then, 10 l of ethyl acetate was added to the reaction solution, and extraction was performed twice. After separating the aqueous layer and the residue, the ethyl acetate layer was washed with distilled water two to three times.
After drying over anhydrous sodium sulfate, the desiccant was removed, and the solvent was distilled off to obtain 500 g of the oil and fat of the present invention. According to the result of analysis by high performance liquid chromatography in the fat and oil, it was found that the content of sesaminol was 1500 ppm. Also, ep
The i-form and the dia-form were not present. On the other hand, the sesame salad oil obtained by subjecting the oil extracted from the same sesame seed to a decolorizing step (addition of 2% of acid clay, heating temperature of 105 ° C) had a sesaminol content of 1400 ppm.
More than 70% were epi- and dia-forms.

[0013]

[Table 1]

Further, 10 g of this fat and oil is mixed with silica gel 150
g (Wako Gel C-100, manufactured by Wako Pure Chemical Industries, Ltd.) as a carrier to purify lignans. Hexane / ether mixed solvent (90 / 10-70 / 30,
After eluting lipids such as triglyceride by volume ratio, the main fraction eluted with ethanol was collected. From the results of analysis and identification of this product by gas chromatography and mass spectroscopy, the ratio of lignans in the fraction was determined to be sesaminol: sesamolinol: P-1: pinoresinol = 10.3: 1.8: 1.8: 2.7
Met.

Example 2 5 kg of sesame seeds were roasted by a conventional method, and squeezed with a pressing machine at room temperature. 3 kg of pressed pressed oil cake containing 20% by weight of oil and cellulase (Boehringer Mannheim Yamanouchi, 5
100 units / g) 0.15N phosphate buffer (pH6.8)
In addition to 20 liters, shaken at 35 ° C. for 48 hours. Then, using ethyl acetate / hexane (1: 1, volume ratio),
The same treatment as in Example 1 was carried out to obtain 600 g of the fat and oil of the present invention.
As a result of analyzing the lignans in the fat and oil in the same manner as in Example 1, it was found that sesaminol was the main component (1300 ppm), and that other ingredients such as pinoresinol, P-1 and sesamolinol were contained.

[0016]

Industrial Applicability According to the present invention, vegetable oil containing lignans such as sesaminol, which is known as an antioxidant active substance, can be easily and inexpensively prepared without using expensive chemicals by using crushed sesame seeds as a raw material. Can be manufactured. In addition, the lignans contained in the fats and oils have not undergone any chemical change during the production process, and therefore include only lignans present in sesame seeds, including structural isomers of lignans not occurring in nature. No, it is also excellent in safety.

──────────────────────────────────────────────────の Continued on the front page (58) Fields investigated (Int. Cl. ⁷ , DB name) C11B 1/10 C07D 493/04 101 C11B 3/00 C11B 5/00 C09K 15/06

Claims (4)

(57) [Claims] 1. A pulverized untreated sesame seed having a pH of 3-7.
A method for producing vegetable oil, comprising extracting a vegetable oil containing water-insoluble and antioxidant lignans from a treated sesame seed with an organic solvent after dispersing in water and stirring. 2. The crushed unrefined sesame seeds and / or crushed sesame seeds having at least about 20% by weight of oil remaining therein are dispersed in water having a pH of 3 to 7 to which cellulase has been added. Manufacturing method. 3. The oil of at least about 20 which is derived from ground roasted sesame seeds and / or roasted sesame seeds.
The production method according to claim 1, wherein the pressed oil cake of sesame seeds remaining by weight% is dispersed in water having a pH of 3 to 7 to which cellulase is added. 4. The process according to claim 1, wherein the lignans having antioxidant activity are at least sesaminol.