JP4694778B2 - Purification method of marigold oleoresin - Google Patents

Description

  The present invention relates to a method for purifying marigold oleoresin, and a purified product of marigold oleoresin obtained thereby.

  A recent study of lutein, a carotenoid, has been reported in recent studies to show an association with reduced risk of age-related Macular Degeneration (AMD) caused by oxidative degeneration of the retinal macular region (eg, non- (See Patent Document 1) and reports that it is effective for prevention of arteriosclerosis, prevention of cataracts or suppression of carcinogenesis (for example, see Non-Patent Documents 2, 3 and 4). Thus, lutein is useful as a health food, a dietary supplement, a food coloring, a pharmaceutical coloring, and a pharmaceutical, and its use is expected.

  Lutein is contained in fruits such as orange, peach, papaya, prune and mango in the form of lutein fatty acid ester, and is also present in many flowers and vegetables, but is particularly prominent in marigold petals. Marigold oleoresin is obtained by extracting the dried and pulverized marigold flowers with a hydrocarbon-based solvent such as hexane or petroleum ether, or a chlorinated hydrocarbon-based solvent such as dichloromethane, and removing the solvent from the extract. can get. Most commercially available marigold oleoresin is a solid or highly viscous paste at room temperature, and the content of lutein fatty acid ester in oleoresin is usually 14-20% as an ester (for example, , See Patent Document 1).

  In order to use lutein as a health food or a dietary supplement, a soft capsule in which the marigold oleoresin is wrapped in a gelatin film is produced. Especially when the contents are oily, it is superior to soft capsules in terms of convenience of handling by solidification of liquid, protection and stabilization of contents, uniformity of contents, masking of taste and odor, high added value feeling, etc. (For example, see Non-Patent Document 5). Soft capsules are usually manufactured by a punching method in which a certain amount of content is injected between two gelatin sheets and punched, but the content is a viscosity that can be fed by a metering pump, for example, 20,000 cps in the rotary die method. Since the liquid must be the following (for example, see Non-Patent Document 5), when making the marigold oleoresin soft capsule, it is necessary to heat and melt the marigold oleoresin into a liquid.

  However, in the production of soft capsules, gelatin, which is the raw material of soft capsules, loses moldability at 40 ° C. or higher, so there is usually no heating / heating process at 40 ° C. or higher (for example, see Non-Patent Document 5) It is difficult to heat, melt and fill the marigold oleoresin.

  Therefore, a method is adopted in which edible vegetable oil is added to the marigold oleoresin, diluted and dissolved, and made liquid at room temperature. However, this method has a disadvantage that the number of capsules to be taken once or per day is increased because the lutein content per capsule is reduced.

Further, a product in the form of a slurry at room temperature, which is obtained by suspending lutein fatty acid ester extracted and separated from marigold flowers in edible vegetable oil and containing 15% or more as a total carotenoid ester, is commercially available. However, this product has a low content of lutein fatty acid ester, and once it is heated and melted at about 80 ° C. for sterilization and then cooled to room temperature, the whole becomes solid and cannot be filled into soft capsules. is there.
International Publication No. 99/54408 pamphlet (p.2, line 24) “Food and Development”, Health Industry Newspaper Co., Ltd., 2000, Vol. 35, No. 4, p. 70 Co-authored by Tsubasa Nishino and Frederick Katik, “Why Multi-Carotene Suppresses Cancer”, Metamol Publishing, 1998, p. 80 “FOOD Style 21”, Food Chemical Newspaper, 1999, Vol. 3, No. 3, p. 52 “FFI Journal (FOODS & FOOD INGREDIENTS JOURNALOF JAPAN)”, FFI Journal Editorial Committee, March 2001, Vol. 191, p.75-76. “Food and Development”, Health Sangyo Shimbun, 1995, Vol. 30, No. 2, p. 16, 17, 18

  The present invention has been made to provide a method for obtaining marigold oleoresin which can be filled into a soft capsule and has a high lutein content.

  As a result of intensive research to solve the above-mentioned problems, the present inventor has conducted a process of supercritical extraction of oleoresin and cooling it after dissolving in a ketone solvent, and a component insoluble in a ketone solvent such as phospholipid. It was found that marigold oleoresin having a low viscosity and a high lutein content can be obtained by combining with a process excluding the above, and the present invention was made based on this finding.

That is, the method of the present invention comprises the following 1 to 14.
1. A method for purifying marigold oleoresin, comprising: a step of supercritical extraction of marigold oleoresin; and a step of cooling after dissolving in a ketone solvent to remove the solvent-insoluble component.
2. The step of supercritical extraction of marigold oleoresin and the step of cooling after dissolving in a ketone solvent and removing the solvent-insoluble component are carried out to obtain a purified marigold oleoresin having a low viscosity and a high lutein content. 2. The method for purifying marigold oleoresin as described in 1 above.
3. 3. The method for purifying marigold oleoresin according to any one of 1 to 2 above, wherein the supercritical extraction treatment step is carried out in the presence of a diluent.
4). 4. The method for purifying marigold oleoresin according to any one of the above 1 to 3, wherein a supercritical fluid selected from the group consisting of carbon dioxide, ethane, ethylene, propane, toluene and nitrous oxide is used.
5. 2. The method for purifying marigold oleoresin, wherein the ketone solvent according to 1 is acetone, methyl ethyl ketone or diethyl ketone.
6). The process of supercritical extraction is carried out using carbon dioxide supercritical fluid under the conditions where the pressure of carbon dioxide is (980 to 2940) × 10 ⁴ Pa (= N / m ² ) and the temperature is critical temperature to 80 ° C. The method for purifying marigold oleoresin according to any one of the above 1 to 5, which is carried out.
7). The supercritical extraction process is carried out using carbon dioxide supercritical fluid under conditions where the pressure of carbon dioxide is (1470 to 2450) × 10 ⁴ Pa (= N / m ² ) and the temperature is 40 to 60 ° C. The method for purifying marigold oleoresin according to any one of 1 to 5 above.
8). The refined marigold oleoresin obtained by the method according to any one of 1 to 7 above.
9. A purified marigold oleoresin having a low viscosity and a high lutein content obtained by the method according to any one of 1 to 7 above.
10. A purified marigold oleoresin having a lutein fatty acid ester content of 20% or more and a viscosity at 30 ° C. of 20,000 millipascal seconds or less.
11. A purified product of marigold oleoresin having a lutein fatty acid ester content of 30% or more and a viscosity at 30 ° C. of 20,000 millipascal seconds or less.
12. Purified marigold oleoresin according to 11 above, having a viscosity of 10,000 millipascal seconds or less at 30 ° C.
13. Purified marigold oleoresin according to 11 above, having a viscosity of 5,000 millipascal seconds or less at 30 ° C.
14 A soft capsule containing the purified marigold oleoresin according to any one of 8 to 13 above.
15. A method for producing purified marigold oleoresin, comprising the steps of supercritical extraction of marigold oleoresin and cooling after dissolving in a ketone solvent to remove the solvent-insoluble component.

  According to the present invention, the combination of the step of supercritical extraction of marigold oleoresin and the step of cooling after dissolving in a ketone solvent and removing components insoluble in ketone solvents such as phospholipids, In addition, marigold oleoresin having a high lutein content is obtained. The purified marigold oleoresin obtained according to the present invention can be filled into soft capsules and is useful as health foods, dietary supplements, food dyes, pharmaceutical dyes, and pharmaceuticals.

  The marigold oleoresin used in the present invention is dried from an Asteraceae marigold (Tagetes erecta WILLD.) Flower, crushed and processed into a pellet if necessary, and then extracted with an organic solvent, usually hexane. It was obtained by removing the solvent from Its properties are solid or paste at normal temperature and have a characteristic odor. Its main component is lutein fatty acid ester, but usually contains fatty acid esters of zeaxanthin and cryptoxanthin. Accordingly, the lutein fatty acid ester referred to in the present invention refers to a total carotenoid ester containing all of these.

  In the process of the present invention, marigold oleoresin is processed by supercritical extraction using high pressure carbon dioxide. When carbon dioxide exceeds a critical point (temperature 31.3 ° C., pressure: 72.9 atm) or more, it becomes a supercritical state and exhibits excellent solubility. In addition, since such a supercritical fluid can adjust the dissolving power by changing the pressure or temperature, selective extraction can be performed by adjusting the pressure of the supercritical fluid supplied to the extraction tank. Can do. As the extraction tank used in the supercritical extraction process of the present invention, those known per se in the art can be used. For example, JP-A-63-112659, p. 6. The extraction tank described in FIG. 2 can be mentioned.

Specifically, marigold oleoresin is charged into an extraction tank as it is or with edible oils and fats added. Examples of edible oils and fats used here include vegetable oils such as rapeseed oil, corn oil, soybean oil, cottonseed oil, sunflower oil, safflower oil, palm oil, palm oil, animal oils such as fish oil, or medium-chain saturated fatty acid triglycerides. Can be mentioned. By adding edible fats and oils, the viscosity of the extractables decreases and foaming is less likely to occur, which facilitates the extraction operation. As a diluent for adjusting the viscosity of the extract, for example, ethanol, hexane, acetone, glycerin, propylene glycol and the like are used in addition to the edible fats and oils.
These diluents can be added in an amount of about 10 to 100 parts by weight, preferably about 15 to 50 parts by weight, based on 100 parts by weight of marigold oleoresin.

  Carbon dioxide is generally used as the supercritical fluid supplied to the extraction tank, but ethane, ethylene, propane, toluene, nitrous oxide, and the like can also be used. The component extracted by the supercritical carbon dioxide is reduced in pressure in the separation tank, and is recovered and removed by vaporizing the carbon dioxide.

The method of supercritical extraction is not particularly limited, but carbon dioxide is (980-2940) × 10 ⁴ Pa (= N / m ² ), preferably (1470-2450) × 10 ⁴ Pa (= N / m ² ). After extraction at a critical temperature of -80 ° C., preferably 40-60 ° C., the solvent is separated at (490-588) × 10 ⁴ Pa (= N / m ² ), 40-60 ° C. Is preferred. In addition to the odor components, the extracted components include residual organic solvents, free fatty acids, and the remainder including incidental substances that can only be identified to some extent. The edible oil and fat added as a diluent is almost completely extracted and removed under the conditions of 1176 × 10 ⁴ Pa (= N / m ² ) and 40 ° C. or higher. The extraction time is not particularly limited, and examples thereof include about 1 hour to about 30 hours, preferably about 3 hours to about 20 hours.

  The end point of extraction is determined by using the extraction rate as a guide because it is difficult to identify the component that affects the viscosity of marigold oleoresin. The extraction rate is the ratio of the extract to the extract, and varies depending on the quality of the extract and is not uniform, but is usually 10% or more, preferably 15% or more, more preferably 20% or more. Is done.

  The supercritical extraction-treated marigold oleoresin is then dissolved in a ketone solvent. Examples of the ketone solvent used here include acetone, methyl ethyl ketone, and diethyl ketone, and acetone is preferable. The quantity of acetone is 0.5-10 mass parts with respect to 1 mass part of oleoresin, Preferably it is 2-3 mass parts.

  The mixed solution of oleoresin and acetone is stirred for 0.5 to 1 hour while maintaining a gentle reflux at 40 to 55 ° C, preferably 45 to 50 ° C. Next, the mixed solution is gradually cooled to 10 to 30 ° C., preferably 15 to 25 ° C., usually over 2 to 4 hours. The cooled mixture is filtered through filter paper or filter cloth, if necessary, using a filter aid such as diatomaceous earth. The filtrate is concentrated under reduced pressure, and purified marigold oleoresin is obtained by removing acetone. The purified marigold oleoresin is freed of residual solvent under reduced pressure at a temperature not exceeding 50 ° C., preferably in an atmosphere of nitrogen gas.

  The method of the present invention comprises a combination of a step of supercritical extraction of oleoresin and a step of cooling after dissolution in a ketone solvent and removing components insoluble in the solvent. Preferably, it is a method in which oleoresin is first subjected to supercritical extraction treatment, then dissolved in a ketone solvent and then cooled to remove components insoluble in the solvent.

  The purified marigold oleoresin obtained by the method of the present invention is a paste that is liquid or low-viscosity at room temperature and has a lutein fatty acid ester content of 20% or more, often more than 30%. A viscosity of 20,000 millipascal second or less, preferably 10,000 millipascal second or less, more preferably 5,000 millipascal second or less is easily obtained. As a result, it has become possible to produce soft capsules containing a high concentration of lutein fatty acid ester.

The soft capsule of marigold oleoresin obtained in the present invention can be produced by a method known per se used in the pharmaceutical field and food field, for example, a dipping method, a punching method, a dropping method and the like. The form of the soft capsule is not particularly limited, and can be any of a football type, an elliptical type, a sphere type, a triangular type, a tear type, and a rhombus type, but a football type is usually preferable. The purified marigold oleoresin of the present invention is filled at about 50 to 5,000 mg, preferably about 250 to 300 mg per soft capsule. Soft encapsulated purified marigold oleoresin is stable for long periods of time.
Marigold oleoresin soft capsules are useful as health foods, dietary supplements, food dyes, pharmaceutical dyes, and pharmaceuticals.

〔Example〕
Hereinafter, the present invention will be specifically described with reference to examples.
[Lutein fatty acid ester content measurement method]
About 0.1 g of sample is accurately weighed and dissolved in hexane to make 100 ml. This is diluted with hexane so that the absorbance is 0.3 to 0.7, the absorbance at the maximum absorption around 445 nm of this diluted solution is measured with a spectrophotometer, and the content is calculated by the following formula. .
Content (%) = {(absorbance / sample mass) × dilution ratio} / 1,394 × 100
* 1,394 is the extinction coefficient at 445 nm

[Viscosity measurement method]
It was measured based on “Second Method Rotational Viscosity Measurement Method” in “28. A No. 4 rotor was used for the measurement, and the number of rotations was selected according to the assumed viscosity. The measurement time was unified to 30 seconds.

100 g of marigold oleoresin (lutein fatty acid ester: 16.9% by mass) is charged into a 1 L extraction tank, and supercritical carbon dioxide at 1764 × 10 ⁴ Pa (= N / m ² ) and 50 ° C. is supplied to the extraction tank. Extraction was performed. The extract was separated in a separation tank at a reduced temperature of 490 × 10 ⁴ Pa (= N / m ² ) and 60 ° C. to obtain 24.4 g of extract.
Next, about 75 g of the extraction residue and 190 ml of acetone are mixed and heated to 50 ° C. to dissolve. The solution is slowly cooled to 20 ° C. over about 3 hours, and the resulting insoluble matter is removed by filtration. The filtrate is concentrated under reduced pressure to obtain about 71 g of purified marigold oleoresin (lutein fatty acid ester: 23.8% by mass). Got.

Marigold oleoresin (lutein fatty acid ester: 23.3% by mass) 100 g and rapeseed oil 30 g are charged into a 1 L extraction tank, and 1764 × 10 ⁴ Pa (= N / m ² ), 50 ° C. supercritical carbon dioxide is extracted. And extracted. The extract was separated in a separation tank at 490 × 10 ⁴ Pa (= N / m ² ) and 60 ° C. under reduced pressure to obtain 50.1 g of extract.
Next, about 79.9 g of the extraction residue and 210 ml of acetone are mixed and heated to 50 ° C. to dissolve. The solution is gradually cooled to 20 ° C. over about 3 hours, and the resulting insoluble matter is removed by filtration. The filtrate is concentrated under reduced pressure to give approximately 76 g of purified marigold oleoresin (lutein fatty acid ester: 30.5% by mass). Got.

100 g of marigold oleoresin (lutein fatty acid ester: 26.9% by mass) and 250 ml of acetone are mixed and heated to 50 ° C. to dissolve. The solution was gradually cooled to 20 ° C. over about 3 hours, the resulting insoluble material was removed by filtration, and the filtrate was concentrated under reduced pressure to obtain 94.8 g of an extract.
Next, about 94.8 g of the extract and 30 g of rapeseed oil were charged into a 1 L extraction tank, and extraction was performed by supplying supercritical carbon dioxide at 1764 × 10 ⁴ Pa (= N / m ² ) and 50 ° C. to the extraction tank. . The extract was 490 × 10 ⁴ Pa (= N / m ² ) in a separation tank and the temperature was raised to 60 ° C. to separate 45.5 g of the extract, and about 79 g of purified marigold oleoresin as lutein (Lutein) Fatty acid ester: 32.9% by mass) was obtained.

＊測定条件 ４号ローター、 ６回転、３０秒
＊＊測定条件 ４号ローター、６０回転、３０秒
Table 1 shows the viscosities of marigold oleoresin (starting material) and purified marigold oleoresin (product of the present invention) of Examples 1 to 3.

* Measurement condition No. 4 rotor, 6 rotations, 30 seconds ** Measurement condition No. 4 rotor, 60 rotations, 30 seconds

Claims (12)

Purified marigold oleoresin for producing soft capsules, obtained by carrying out a process of supercritical extraction of marigold oleoresin and cooling after dissolving in a ketone solvent and removing the solvent-insoluble component . . The purified marigold oleoresin according to claim 1 , wherein the viscosity at 30 ° C is 20,000 millipascal seconds or less and the content of lutein fatty acid ester is 20% or more . The purified product of marigold oleoresin according to claim 2, wherein the content of lutein fatty acid ester is 30% or more. The purified marigold oleoresin product according to claim 2 or 3, wherein the viscosity at 30 ° C is 10,000 millipascal seconds or less. The purified product of marigold oleoresin according to claim 4, wherein the viscosity at 30 ° C is 5,000 millipascal seconds or less. The purified marigold oleoresin according to any one of claims 1 to 5 , wherein the supercritical extraction treatment is carried out in the presence of a diluent. The purified marigold oleoresin according to any one of claims 1 to 6 , wherein a supercritical fluid selected from the group consisting of carbon dioxide, ethane, ethylene, propane, toluene, and nitrous oxide is used. The purified marigold oleoresin according to any one of claims 1 to 7 , wherein the ketone solvent is acetone, methyl ethyl ketone or diethyl ketone. The supercritical extraction process is performed using carbon dioxide supercritical fluid, the pressure of carbon dioxide is (980 to 2940) × 10 ⁴ Pa (= N / m ² ), and the temperature is critical temperature to 80 ⁰ C. The purified marigold oleoresin product according to any one of claims 1 to 8 , wherein The step of treating the supercritical extraction, using carbon dioxide supercritical fluid, the pressure of carbon dioxide ^{(1470~2450) × 10 4 Pa (} = N / m 2), under the conditions of temperature 40 to 60 ⁰ C The refined marigold oleoresin product according to any one of claims 1 to 8 , which is carried out. A soft capsule containing the purified marigold oleoresin according to any one of claims 1 to 10 . Purified marigold for producing soft capsules, characterized in that a step of supercritical extraction of marigold oleoresin and a step of cooling after dissolving in a ketone solvent and removing the solvent-insoluble component are performed. A method for producing oleoresin.