JPH0258310B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing an antioxidant. For more details, grind the dried leaves of herbs such as rosemary and sage to less than 20μ, and use tocopherol of 0.01~
Extract with oil containing 5%, then heat the extracted oil at 50℃
After cooling to remove precipitated impurities, the extracted oil is steam distilled to remove aroma components, and then molecularly distilled to obtain a fraction containing antioxidant substances that distills at 180 to 280°C. The present invention relates to a method for producing an antioxidant, which comprises collecting the antioxidant.

Foods, feeds, cosmetics, containing fats and oils,
It is widely known that pharmaceutical products produce harmful peroxides when oxidized.

In order to prevent the oxidation of these oils and fats, BHT and
BHA was previously used, but problems such as toxicity have arisen in recent years, so there has been a desire to develop a natural antioxidant to replace it.

One such method is to extract antioxidant substances from herbal spices, especially rosemary and sage, using an organic solvent or a water-containing organic solvent (Japanese Unexamined Patent Publication No. 18436-1989,
-8668, JP-A-56-74177).

Among these methods, when extracting antioxidant substances with polar solvents such as methanol, ethanol, or their water-containing substances, water-soluble sugars and glycosides are also extracted at the same time, so it is necessary to remove them. It is necessary to use a large amount of water, and the costs for treating the waste liquid and recovering the solvent are higher than expected.

Furthermore, when a non-polar solvent such as n-hexane or petroleum ether is used, it has the disadvantage that antioxidant substances cannot be extracted sufficiently.

The inventors of the present invention have conducted extensive research in order to overcome these drawbacks, and as a result, have discovered a production method in which antioxidant substances are extracted using fats and oils containing tocopherols.

The method of the present invention does not use organic solvents, so there is no danger associated with the use of organic solvents, and it is extremely safe. Furthermore, since sugars and glycosides are not extracted, there is no need for large amounts of water to remove them. ,
Moreover, since there is no need for the cost of recovering the solvent, an extremely economical manufacturing method is provided.

The herbal antioxidant extract raw materials used in the present invention include one or more of rosemary, sage, marjoram, thyme, basil, oregano, and the like. In order to efficiently extract antioxidant substances from these herbal ingredients, it is necessary to grind the dried leaves into smaller pieces than 20 microns. If the particle size is larger than 20μ, the extraction rate will decrease. Dry grinding and wet grinding can be used to grind dry leaves to a particle size of 20μ or less, but
Preferably, wet grinding is used. Suitable examples of these grinding devices include a colloid mill, a super fiber blade (manufactured by Hasegawa Iron Works), and a Supraton (manufactured by Suplaton, Germany).

Tocopherol used for extraction in the present invention 0.01~
Examples of oils and fats containing 5% include soybean oil, corn oil, rice sugar oil, rapeseed oil, cottonseed oil, and vegetable oils.
Palm oil, coconut oil, peanut oil, etc. Animal fats and oils include lard, beef tallow, chicken fat, mutton fat, milk fat,
Fish oil is good, but vegetable oil with a melting point of 40°C or lower is preferred. In particular, vegetable oils and fats contain about 0.01 to 0.3% tocopherol in unrefined crude oil.
The tocopherol content does not decrease much in purification processes such as degumming, deacidification, and decolorization, but is removed in the deodorization process. Therefore, by using undeodorized vegetable oil, an extracted oil suitable for the present invention can be obtained.

When using vegetable oils and fats with low tocopherol content, completely sugar-processed vegetable oils, and animal oils, natural mixed tocopherols, dl-α-tocopherols, etc. are added within the range suitable for the present invention to prepare extracted oils. It can be done.

In the present invention, oils and fats containing tocopherols are used to extract antioxidant substances from the finely ground dried leaves of herbal spices in order to prevent losses such as thermal decomposition of antioxidant substances during the production process of the present invention. The final recovery rate of antioxidant substances when using fats and oils that do not contain tocopherols is approximately 70%, whereas the final recovery rate when using fats and oils containing 0.01 to 5% tocopherols of the present invention is approximately 70%. The yield can be significantly improved to over 90%. If the tocopherol content is less than 0.01%, the recovery rate will not be as high as expected, and if it is more than 5%, it will be uneconomical. Practically 0.05
It is preferable to use an oil or fat containing about 3% tocopherol.

The amount of oil and fat containing tocopherol to be used is 4 to 10 parts by weight per 1 part by weight of the crushed dry leaves, and although extraction may be performed once, the recovery rate is preferably improved by extracting twice. In the case of two extractions, the amount of extracted oil used is 4 to 6 parts by weight in the first extraction and 2 to 5 parts by weight in the second extraction.

The extraction temperature and time are 100 to 150°C and 30 minutes to 4 hours. When extracting twice, the extraction time is 1~
It will be 7 hours. The resulting extract has a dark green color, containing coloring components such as chlorophyll, and aromatic components. Therefore, activated carbon is added to remove coloring components such as chlorophyll. Activated carbon may be added to the oil after extraction, or may be added at an appropriate step during extraction. Treatment time with activated carbon is 20~
It takes full effect in 30 minutes. The extracted oil is clear orange in color and has a pleasant aroma.

Next, the extracted oil is cooled to below 50°C, and precipitated impurities are removed using a vacuum filtration machine, centrifugal separator, or pressure filtration machine pre-coated with a supernatant. A preferred filter for the purpose of the present invention is a pressure filter such as a filter press, but is not particularly limited.

The resulting extracted oil is steam distilled to remove the essential oil, which is the aromatic component unique to spices. The components distilled by steam distillation can be used as antibacterial agents.

The steam distillation conditions in the present invention are a distillation temperature of 130 to 180
℃, a pressure of 2 to 20 mmHg, and a distillation time of 20 to 60 minutes are sufficient. The extracted oil is pale orange in color and odorless after steam distillation. The extracted oil that has undergone steam distillation is then subjected to molecular distillation.

The molecular distillation machine used in the present invention may be either a centrifugal type or a thin film falling type. Antioxidant substances contained in herbs such as rosemary and sage are molecularly distilled at 180 to 280℃ (pressure 1 to 3 x 10 ^-2 to ^{10 -3} mmHg).
It is concentrated into a fraction of The fats and oils containing antioxidants obtained by this method are quite viscous, dark brown in color, and almost odorless. The concentration ratio of antioxidant substances is 10 to 25 times, and the recovery rate is 90% as mentioned above.
That's all.

Rosemary, sage, etc. are natural products that have been eaten as spices since ancient times, and are highly safe.
Moreover, since an organic solvent is not used for extraction and oil is used for extraction, it is safe and provides an economical production method.

The fats and oils containing antioxidants obtained according to the present invention can be used as is or in combination with other antioxidants or chelate compounds to prevent oxidation of fats and oils or foods, feeds, cosmetics, pharmaceuticals, etc. containing fats and oils. shows a remarkable effect on

In addition, fats and oils containing antioxidants can be made into powder or emulsion using conventional methods, and in this case, they can be used from the water side, expanding their use to salted and dried seafood products, water-based livestock products, etc. can do.

Next, the present invention will be explained with reference to Examples.

Example 1 5 kg of corn oil containing 0.3% natural misc tocopherol (Riken E Oil 700) added to 1 kg of fine powder obtained by crushing dried rosemary leaves to 20 μm or less
is added and pulverized in a colloid mill to form an oil with almost no grain. This was heated to 120°C and extracted while stirring for 2 hours. 200 g of activated carbon was added to this, and after stirring at 120°C for 30 minutes, the extraction residue was collected using a vacuum filtration machine. Furthermore, 3.4 kg of the above-mentioned corn oil was added to the extraction residue and heated at 120℃ for 30 minutes.
Extract for 1 minute, cool the mixture with the first extracted oil to 30℃, remove the extraction residue, activated carbon, and precipitated impurities using a vacuum filtration machine pre-coated with activated clay, and turn the oil into a transparent pale orange oil. Got Kg. This oil liquid was steam distilled for 30 minutes at 150°C and 5 to 10 mmHg to remove aroma components, and then molecularly distilled using a thin film falling molecular distillation machine (pressure 2 x 10 ^-3 mmHg).
Upon distillation at 180 to 270°C, 507 g of a viscous clear light brown fraction was obtained. This fraction contained 190 g of antioxidant substances, and the recovery rate of antioxidant substances from the raw materials was 98.2%.

Comparative Example Using corn oil to which tocopherols were not added as the extracted oil and fat in Example 1, the same procedure as in Example 1 was carried out to obtain 495 g of a fraction. This fraction contained 75 g of antioxidant substances, and the recovery rate of antioxidant substances from the raw materials was 67.6%.

Example 2 Dried rosemary leaves were frozen and crushed into a fine powder of 5μ or less. Add 9.5 kg of undeodorized soybean oil containing 0.09% tocopherol to 2 kg of this fine powder and add 130
Extraction was carried out at ℃ for 2 hours and 30 minutes with stirring. Add 600g of activated carbon to this, stir at 130℃ for 20 minutes, and then 55℃.
The extraction residue and activated carbon are separated using a centrifuge pre-coated with Celite. Furthermore, 7.3 kg of the above-mentioned undeodorized soybean oil was added to the extracted residue.
and extracted with stirring at 120℃ for 1 hour, and then extracted at 35℃.
The extraction residue, activated carbon, and precipitated impurities were centrifuged. The first and second extracted oils were a clear orange liquid weighing 15.1 kg. This liquid was steam distilled for 40 minutes at 140°C and 20 mmHg to remove aroma components, and then molecularly distilled using a centrifugal molecular distillation machine (pressure 1 x 10 ^-2 mmHg) to a concentration of 180 to 250.
Upon distillation at ℃, 973 g of a viscous clear brown fraction was obtained. This fraction contains 215g of antioxidant substances,
The recovery rate of antioxidant substances from raw materials was 96.8%.

Example 3 Dried leaves of sage were coarsely ground to give a coarse powder of 250 μm. 1 kg of this coarse powder dl-α-tocopherol
0.3%, natural tocopherol (RIKEN E Oil 600)
7 kg of chicken fat added with 0.2% was added and pulverized using a super fiber blade to give it a particle size of 5μ or less with almost no graininess. Next, extraction was performed at 140°C for 1 hour and 30 minutes with stirring. 230 g of activated carbon and 100 g of diatomaceous earth were added to this, stirred for 30 minutes while maintaining the temperature at 140°C, and then cooled to 40°C. The extraction residue, activated carbon, diatomaceous earth, and precipitated impurities were filtered under pressure using a filter press. Clear light brown oil liquid 6.2
Got Kg. Apply this oil solution at 160℃ and 10mmHg for 50 minutes.
After removing aroma components by steam distillation, molecular distillation is carried out using a thin film falling molecular distillation machine (pressure: 1 x 10 ^-3 mm).
Hg) and distilled at 185-260°C to obtain 742 g of a viscous clear brown fraction. This fraction contained 110 g of antioxidant substances, and the recovery rate of antioxidant substances from the raw materials was 91.8%.

Example 4 To 100 g of the fraction obtained in Example 2, 2 g of emulsifier (Emulgy Y-61, manufactured by Riken Vitamin), 200 g of lactose,
After 50 g of sodium caseinate was added to 1 water and emulsified using a homomixer, the emulsion was spray-dried to obtain 318 g of a powdered water-dispersible antioxidant preparation.

Example 5 100g of the fraction obtained in Example 2 was mixed with 350g of a 20% gum arabic solution dissolved in water,
7.5 g of Span 20 (sorbitan monolaurate, manufactured by Kao Atlas) was added and emulsified using a homogenizer to obtain a stable o/w emulsion having antioxidant properties.

[Brief explanation of the drawing]

The drawing is a chart showing the effects of the antioxidant component obtained in the present invention. The oil and fat used is lard and AOM test (Japan Oil Chemists' Association, Standard Oil and Fat Analysis Test Method, 2.4.28.1)
-81), the time required for the peroxide value (pov) to reach 50 is shown in the chart.

Claims (1)

[Claims] 1. Dried leaves of herbs such as rosemary and sage are crushed to 20μ or less, and tocopherols are 0.01 to 5.
%, the extracted oil is cooled to below 50°C to remove precipitated impurities, the extracted oil is steam distilled to remove aroma components, and then subjected to molecular distillation at 180 to 280°C. 1. A method for producing an antioxidant, which comprises collecting a fraction containing an antioxidant substance distilled out in .