JPH10165139A - Production of vitamin k supplement composition for food and method for extracting vitamin k - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a process for producing a vitamin K supplement compsn. for food having a high vitamin K content without the occurrence of problems in safety and palatability in spite of addition of this vitamin to the food by a relatively simple processing method using natural materials as raw materials and a method for extracting the vitamin K having no possibility of remaining and forming (denaturation) of harmful materials. SOLUTION: The leaf parts of dark green and yellow vegetables having green leaf blade parts are used as the materials to be treated and are heated to soften the plant tissues and, thereafter, the leaf parts are subjected to a solid liquid sepn. of liquid mesophyll parts, solid petile parts and veinparts, thereby the compsn. consisting of the mesophyll parts and having the high vitamin K content is obtd. According to another method for production, the dry matter of the leaf parts is pulverized and the pulverized matter is classified to the mesophyll parts, the petiole parts and the vein parts to separate the dry matter of the mesophyll parts. The vitamin K content of the resulted compsn. is >=1000μm per 100g. The selective extraction of the vitamin K is made possible if the dark green and yellow vegetables are extracted by using liquid carbon dioxide existing in a supercritical state.

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 vitamin K supplement composition for food comprising a mesophyll portion containing a high concentration of vitamin K contained in green-yellow vegetables, and a method for extracting vitamin K. It is. The above vitamin K
The replenishing composition can be used as a food form by adding it to, for example, breads, noodles, confectioneries, beverages, and the like. In addition, vitamin K can be used as a medicine other than food.

[0002]

BACKGROUND OF THE INVENTION Vitamin K is required in the liver for the production of pronthrombin, an important factor involved in blood coagulation, and its deficiency is deficient intracranial hemorrhage in newborns and infants, especially in infants up to two months after birth. Often breastfeeding infants. Although humans can use vitamin K produced by intestinal bacteria, they are said to be susceptible to deficiency because they do not produce vitamin K in the intestines of newborns and infants. For this reason, vitamin K-added formula milk powder is also commercially available so that vitamin K can be replenished directly to newborns and infants by feeding. On the other hand, by ingesting natural vitamin K from the daily food for the mother, vitamin K in breast milk
It is desirable to increase the content. Recent advances in medical technology,
Due to the enhancement of social welfare, Japan is rapidly becoming an aging society compared to other countries. Among them, there is a disease called osteoporosis that causes abnormal bone metabolism as a social problem. In bone tissue, bone resorption by osteoclasts and bone formation by osteoblasts are repeated, and this balance is disrupted by aging, menopause, etc., and bone resorption exceeds bone formation, resulting in a decrease in bone weight and osteoporosis. It is thought to lead. In addition, there is a shortage of calcium due to a lack of energy intake such as dieting of young people in recent years, and there is a concern that the age of osteoporosis will decrease in the future.

[0003] Current treatments for these diseases include calcium preparations that suppress bone resorption, vitamin D, estrogens, parathyroid hormone, calcitonin, etc. Treatments that promote bone formation have not been known so far. Not. Recent studies have shown that vitamin K promotes bone formation when used in combination with calcium, and the importance of vitamin K has been further recognized. Vitamin K is contained at relatively high concentrations in vegetable oil, natto natto, green-yellow vegetables, seaweed and the like. However, it is difficult to ingest a large amount of these foods at once, and cooking the above-mentioned specific foods daily imposes a dietary burden on nursing women, elderly people, postmenopausal women, etc. It is not preferable even on balance.

[0004]

In order to supplement vitamin K to foods, it is preferable to add a natural material having a high vitamin K content. At present, vegetable oils and deodorized distillates generated in the step of refining vegetable oils Techniques for extracting vitamin K from inside are known. Conventional techniques for extracting vitamin K from vegetable oil include i) column chromatography, i.
There are methods such as i) distillation method and iii) solvent fractionation method. i) As a column chromatography method, a method is known in which silica gel, chemically modified silica gel, or the like is used as a stationary phase, and an organic solvent such as alcohol, acetone, or n-hexane is used as a mobile phase. In the column chromatography method, the target substance can be separated and purified fairly accurately, so that the concentration of natural vitamin K is high, but a large amount of expense is required to maintain the stationary phase and the mobile phase. ii) The distillation method is a simple distillation type in which molecules move in one direction from an evaporation surface to a concentration surface, and is called vacuum distillation or molecular distillation. Molecular distillation can be concentrated relatively inexpensively as compared with the column chromatography method, but has disadvantages such as a low concentration ratio, a decrease in natural vitamin K at a high temperature, and a risk of organic solvent remaining. iii) In the solvent fractionation method, the vegetable oil or the deodorized distillate is
Or a method of dissolving in a lower monohydric alcohol or the like and cooling to precipitate impurities, or after dissolving the above deodorized distillate in a lower monohydric alcohol, adsorbing natural vitamin K to activated carbon, and having 5 to 5 carbon atoms. A method of separating and purifying with a low-polarity solvent, which is an aliphatic or aromatic hydrocarbon, is known.
This solvent fractionation method can be inexpensively concentrated, but has a low concentration ratio, as compared with the above two methods. Moreover, since extraction is performed using harmful organic solvents such as methanol and n-hexane,
A great deal of thermal energy is required to remove and recover the solvent from the extract. In addition, similarly to the above distillation method ii), not only is there a fear that natural vitamin K is decomposed by heat, but also there remains a problem of residual extraction solvent.
Strict quality control is required.

[0005] Vitamin K is more stable to heat than other vitamins, but has the property of being easily decomposed by light, oxygen and alkali. Vegetable oils and deodorized distillates contain a large amount of polyunsaturated fatty acids, and have the disadvantage that the deodorized distillate is a natural material that is easily oxidized. As another natural vitamin K material, natto natto has a unique fermentation odor and contains a large amount of a viscous substance, which is not preferable in terms of palatability and processability. Green-yellow vegetables are not so problematic in terms of palatability and processability, but they are bulky for their content, and there are still problems in ingesting large amounts of fresh leaves. Further, when trying to extract vitamin K, which is abundantly contained in the leaves of green and yellow vegetables, with an organic solvent such as acetone, n-hexane, or ethanol, a gum-like substance is formed, and it is difficult to completely remove the organic solvent. Master. Further, when a monohydric alcohol is used as the extraction solvent, there is a problem that a part of chlorophyll, which is a pigment contained in the leaves, is denatured to a harmful substance called pheophorbide. Therefore, an object of the present invention is to solve the above-described problems, and a relatively simple processing method using a natural material as a raw material causes problems in safety and taste even if added to food. Another object of the present invention is to provide a method for producing a vitamin K supplement composition for foods having a high vitamin K content. Another object of the present invention is to provide a method for extracting vitamin K which does not cause harmful substances to remain and to be formed (denatured).

[0006]

Means for Solving the Problems The present inventors have intensively studied a simple processing method of a natural material suitable for enriching vitamin K in foods.
Among the raw materials, we focus on green-yellow vegetables whose leaf medicament contains vitamin K exclusively, and utilize the difference in strength between the mesophyll of the plant tissue and other organs to use vitamin E and β in addition to vitamin K.
-By separating the carcass-rich mesophyll,
In addition, the present inventors have found that the above object can be achieved by extracting vitamin K from green-yellow vegetables using liquefied carbon dioxide as an extraction solvent, thereby completing the present invention. That is, the method for producing a vitamin K supplement composition for food of the present invention comprises heating at least the leaves of a green-yellow vegetable having a green leaf blade to soften the plant tissue, and then solidifying the liquid leaf with the liquid leaf. Solid-liquid separation into the petiole and vein of the shape, and separation of the solid matter of the leaf part having a high vitamin K content from the obtained liquid leaf part, or pulverization of the dried substance of the leaf part, and crushing The product is classified into a mesophyll, a petiole, and a vein, and a dried product of the mesophyll is separated. Further, the method for extracting vitamin K of the present invention is characterized in that green-yellow vegetables having green leaf blades are extracted using liquefied carbon dioxide in a supercritical state.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. In the present invention, green-yellow vegetables having green leaf blades include asagi, asuka, Osaka Chinese cabbage, okahijiki, kaiware radish, mustard greens, kyona, komatsuna, nashin, yamato greens, shiso, spring chrysanthemum, sardine greens, seri, Body vegetables, bok choy, vines, vine purple, nazuna, leek, nozawana, parsley, daily vegetables, hiroshima greens, spinach, three leaves, moroheiya, yonayana, bride vegetables,
Artemisia, scallions and the like are mentioned. These are vegetables grown and marketed as food materials. In addition, the above-ground parts of root vegetables not originally intended for cultivation, ie, turnip leaves, sweet potato leaves, potato leaves, carrot leaves, radish leaves, waste leaves, etc.
It can be used as a raw material of the vitamin K supplement composition of the present invention.

The green-yellow vegetables used in the present invention are:
Botanically, it is composed of stems and green leaves. The stem is a transmission organ that attaches leaves and reproductive organs, increases the number of individuals, mechanically supports the aerial parts, and establishes roots and conducts nutrients and water between them. The stem has a thick epidermis to protect internal tissues and a vertical rod-like cell inside for the purpose of mechanical support, that is, fibers mainly composed of cellulose and hemicellulose that are strong against physical external forces. Inside it is made up of vascular bundles for transmitting nutrients. The leaf is an organ that performs photosynthesis, conversion of nutrients, transpiration of water, and the like, and usually comprises a leaf blade and a petiole. The leaf blade is composed of an epidermis for protecting a relatively soft surface, a leaf blade containing chlorophyll that performs photosynthesis and conversion of nutrients, and a leaf vein. The leaf vein and petiole are tissues for mechanically supporting the leaf like the stem, and also serve to transmit nutrient water.
In the chlorophyll in the above-mentioned mesophyll, carbohydrates such as starch and sugars are synthesized by utilizing solar energy from carbon dioxide in the air and moisture absorbed from the roots. These carbohydrates are decomposed into amino acids and the like, and are combined with fertilizer components (mainly nitrogen components) absorbed from soil to synthesize proteins. At that time, fat-soluble vitamin K, vitamin E, β-carotene and the like are synthesized together and stored in the mesophyll. Heretofore, green-yellow vegetables have only been treated with fresh leaves and dried products, and it has been difficult to obtain only the leaf portion containing a large amount of fat-soluble vitamin K, vitamin E, β-carotene and the like.

Next, the method for producing the vitamin K supplement composition of the present invention will be described in detail. In the present invention, as an object to be treated, at least the leaves of green-yellow vegetables are targeted, but from the viewpoint of cost and the like, the leaves and stems without removing the stems in advance, and further the roots connected to the stems. And may be subjected to the following processing steps. In the following processing steps, a case in which the leaves and the stem are treated will be described as an example. First, in order to facilitate the softening of the plant tissue by heating performed in this step, each piece is cut into pieces of 4 to 40 mm, preferably 6 to 25 mm using a kitchen knife, a rotary cutter, a guillotine cutter or the like. Further, in order to remove dust, mud, and the like adhering to the fresh leaf surface, the leaf is washed with natural flowing water, high-pressure jet jet, ultrasonic irradiation, or the like. Either of the cutting step and the washing step may be performed first. Then, the water adhering to the surface of the cut and washed green-yellow vegetable is dehydrated by centrifugation or gravity flow so that the amount of adhering water is 10% by weight or less.

[0010] In this step, in order to easily separate the mesophyll part containing a large amount of vitamin K from the petiole, leaf vein and stem, a temperature of 80 to 120 ° C (pressurized) is used. A hot water treatment or direct contact steaming is performed for 10 minutes, preferably at 85 to 100 ° C. for 2 to 7 minutes, to sufficiently soften the leaf portion among the leaves. At that time, the pH of the boiling water
It is desirably in the range of 6.0 to 8.5, preferably 6.5 to 8.0. In direct contact cooking, it is desirable to perform a pretreatment of immersing in a solution having a pH of 6.0 to 8.5 for 20 to 120 minutes, preferably in a solution having a pH of 6.5 to 8.0 for 30 to 60 minutes. In the softening step, any of a batch method and a continuous method may be employed. This heating not only softens the plant cells, but also deactivates enzymes that can fade the bright green chlorophyll pigment of green-yellow vegetables. That is, the heat treatment is an effective means also for deactivating enzymes such as chlorophyllase and oxidase that degrade chlorophyll into phyophytin and fade from green to yellow and then brown. After heating, immediately cool with cold water, and remove the water attached to the surface of the cut green-yellow vegetables by centrifugation or gravity flow
Dehydration is performed so that the amount of water adhered after cooling is 10% by weight or less.

[0011] Then, heat-treated green-yellow vegetables 100
10 to 100 parts by weight of water are added to parts by weight,
It is desirable to stir at ５０50 ° C. for 2 to 20 minutes. This stirring is performed for 20 to 7 parts per 100 parts by weight of the green-yellow vegetable.
It is preferable to add 0 parts by weight of water and carry out at 10 to 40 ° C. for 5 to 10 minutes. By adding water to green and yellow vegetables,
Improve the flowability of green and yellow vegetables in the stirrer, loosen,
Crushing and dispersion are promoted. If the amount of water at the time of stirring is less than 10 parts by weight, the fluidity in the stirrer is poor, and it is difficult to loosen, crush, and promote dispersion. Meanwhile, 1
If more than 00 weight is added, the fluidity in the stirrer is increased, and crushing cannot be performed sufficiently. Therefore, not only the liquefaction of the leaf portion becomes difficult, but also the amount of dehydration treatment increases, which is disadvantageous in cost. It is. Examples of the stirrer used at this time include a stirrer with a vertical axis or a horizontal axis for jam, ann, confectionery and baking. When the vertical axis or the horizontal axis of the stirring shaft is operated at a rotation speed of 20 to 400 rpm, preferably 50 to 200 rpm, the stem, petiole, and leaf vein composed of strong tissue maintain the original shape, but the mesophyll softened by heating is Liquefies. Here, at a rotation speed of less than 20 rpm,
The leaf portion softened by heating is not sufficiently liquefied, and the amount of leaf portion obtained in the solid-liquid separation step is reduced. On the other hand, when rotated at a speed higher than 400 rpm, the petiole, leaf veins and stems are also loosened and crushed, and the mesophyll and petiole, veins and stems are separated by the following solid-liquid separation step. It becomes difficult to separate.

As a means for solid-liquid separation of the petiole, leaf vein and stem from the liquefied mesophyll while keeping the original form, a filter having an appropriate mesh is used. No, but preferably a scrubber is used. The strainer has a rotating stirrer in the cylindrical screen, and separates the petioles, leaf veins, stems and stems from the original shape by passing the liquefied mesophyll from the tip of the cylindrical screen. be able to. A mesh of any size can be mounted on the cylindrical screen, and a mesh having a gap of 0.5 to 3.0 mm is usually used. The filtrate passing through the strainer contains leaf-fat tissues rich in fat-soluble vitamin K, vitamin E and β-carotene, and oxalic acid, tartaric acid, succinic acid, glyoxylic acid, glycolic acid, etc. contained in green and yellow vegetables. Organic acids and polyphenols such as chlorogenic acid, catechin and tannin are contained as aqueous solutions. The mesophyll tissue is surrounded by an epidermis rich in organic acids and polyphenols, and is composed of a shelf-like tissue and a spongy tissue. Shelf-like and spongy tissues contain chlorophyll and undergo photosynthesis and nutrient conversion. Oxalic acid and polyphenols contained in green-yellow vegetables after such synthesis and substance conversion exhibit an astringent taste and astringency. Therefore, separation of the leaf portion containing vitamin K from an aqueous solution containing organic acids and polyphenols is a favorite. This is an effective means from the viewpoint of gender.

Various methods utilizing centrifugal force and pressure can be used to separate the aqueous solution from the leaf portion suspended in the filtrate passed through the strainer. For example, centrifugal separation and centrifugal filtration are roughly classified into separation methods using centrifugal force. Centrifugal separators generally consist of a continuously reduced or enlarged cylindrical bowl and screw conveyor,
The solid particles settled on the outer wall of the bowl by centrifugal force are discharged outside the machine by a screw conveyor, and the liquid overflows and is discharged outside the machine. As such a centrifuge, a decanter-type centrifuge capable of separating solids in the mesophyll part containing vitamin K and liquid containing organic acids and polyphenols is suitable. A centrifugal filter is a device that separates solid particles in a liquid, which are difficult to separate, from the liquid.
With a centrifugal force of 0 G, the leaf portion containing vitamin K can be separated from the liquid containing organic acids and polyphenols as a solid.

The squeezing separation using pressure is an operation of squeezing a liquid by applying a high pressure to a mixture of a liquid and solid particles, and includes a batch type and a continuous type. In batch squeeze separation,
The liquid passed through the strainer obtained in the previous step is placed in a bag-shaped filter cloth, and the liquid is squeezed by applying pressure only in one direction, leaving only solid particles in the filter cloth. Thereafter, by removing the solid particles from the filter cloth, it is possible to collect the solid matter of the leaf portion containing vitamin K. In the continuous squeeze separation, a liquid passed through a strainer is supplied between two band-shaped filter cloths,
By wrapping around several rolls and applying a squeezing pressure, the liquid can be separated into solid particles containing vitamin K. Specifically, a filter press and a belt press can be used. The vitamin K supplement composition for food produced by the above steps is a paste containing 20 to 50% of water and can be used as it is for practical use. It is desirable to perform treatment, drum drying treatment, and freeze vacuum drying treatment.

Further, the method for producing the vitamin K supplement composition for food of the present invention will be described in detail, taking as an example the case where the leaves and stems of dried green-yellow vegetables are treated.
In order to easily dry the plant tissue, cut, wash and dehydrate in the same manner as described above, and then naturally dry by sunlight, ventilation drying at a temperature of 40 to 80 ° C, preferably 50 to 70 ° C,
By a drying treatment such as freeze vacuum drying under reduced pressure, the water content of the green-yellow vegetable is reduced to 3 to 18% by weight, preferably 5 to 14% by weight.
It is desirable to reduce to. In this step, in which the dried material of the leaves is treated,
By utilizing the change of sedimentation speed in the air and the difference in density between the cut dry matter and the air, the leaf blade, stem and petiole having different specific gravities are separated. In the first-stage separation step, it is difficult to separate the petiole part from the leaf blade part by cutting or the like in advance, so it is difficult to completely separate the part of the petiole part connected to the leaf blade part. is there. Therefore, a little petiole mixed in the leaf blade is supplied to the next second-stage separation step. In addition, some leaf blades connected to the stem are separated together with the stem in the first-stage separation step. In the second separation step, the leaves are pulverized, and the finely pulverized leaf meat is classified into coarsely pulverized petiole and leaf veins. When only the dried leaves are treated, the first-stage separation step is omitted.

It is preferable to employ gravitational field classification as the first-stage separation step, and the classification can be roughly classified into a horizontal flow type and a vertical flow type. In the horizontal flow type, the mixture of the leaf blade, petiole and stem is dropped from the raw material inlet into a uniform horizontal air flow, causing a difference in the sedimentation velocity in the air and the air in the horizontal direction. And a density difference occurs. The leaf blade having a low specific gravity falls near the outlet, and the petiole and stem having a high specific gravity fall near the input portion, so that both can be easily classified. In the vertical flow type, a mixture of the leaf blade, petiole and stem enters the lower part of a wind sieve having a cylindrical empty tube or a zigzag-shaped empty tube with enhanced classification efficiency in a state of being dispersed in the airflow. . Due to the updraft of these mixtures, the leaf blade with a low specific gravity is
The petiole and stem having a large specific gravity are discharged out of the air sieve from the outlets at the lower side of the air sieve, respectively, so that both can be classified.

In the second separation step, the mesophyll part is separated from the petiole and leaf vein using, for example, a high-speed rotary mill capable of pulverizing and classifying. In other words, by controlling the grinding and classification conditions of the high-speed rotating mill, the weakly mesophyll part can be finely pulverized finely, and the systemically strong petiole and leaf vein part can be coarsely pulverized. By using and separating, only the mesophyll portion can be obtained. FIG. 1 is an explanatory view of a high-speed rotating mill used in a pulverizing and classifying step as an example of the present invention. The high-speed rotating mill shown in FIG. 1 includes a raw material supply unit 1, a crushing unit 2, a classification unit 3, and an air intake unit 4.
And an air discharge unit 5. A horizontally provided cylindrical raw material supply unit 1 is connected to an outer peripheral portion of the crushing unit 2 and supplies dried defoliated products mainly composed of leaf blades of green and yellow vegetables to the crushing unit 2 therein. A screw feeder 6 is provided. The pulverizing section 2 and the classifying section 3 are provided with an inverted conical guide ring 7.
The pulverizing section 2 is disposed below and below the outer peripheral portion of the guide ring 7, and the inside of the guide ring 7 serves as the classifying section 3. The pulverizing section 2 and the classifying section 3 are respectively provided with a first rotating blade 8 and a second rotating blade 9 of variable rotation speed. The rotating blades 8 and 9 are driven by two motors 10 installed at the center of the lower portion of the mill body via a transmission mechanism such as a belt and a rotating shaft and a rotation speed control mechanism. An air intake unit 4 is provided at the lower part of the mill body, and the air sucked from the duct of the intake unit 4 by the rotation of the second rotary blade 9 passes through the crushing unit 2 and the classification unit 3 and passes through the classification unit 3.
Along with the finely ground mesophyll while classifying the leaf tissue with
The air is discharged out of the machine from a cylindrical air discharge portion 5 provided at the center of the upper portion of the mill body.

In the above high-speed rotating mill, the leaves of the green-yellow vegetables separated from the stem and most of the petiole by the gravitational field classification are supplied into the high-speed rotating mill from the raw material supply unit and pulverized in the pulverizing unit. . The pulverized leaf part rises on the airflow from the downstream, and the fine powder is discharged outside the machine by the balance between the centrifugal force and the suction power of the airflow in the classification part, and the coarse particles are removed from the lower part of the guide ring. It is returned to the crushing section and crushed again. The rotation speed of the rotor in the pulverizing section is 3000
７7500 rpm, preferably 4000 to 6000 rpm
In addition, the number of revolutions of the rotor in the classifier is 700 to 1400
rpm, preferably controlled at 800 to 1200 rpm, the mesophyll is usually finely pulverized to 100 μm or less, and the petiole and veins having strong tissue are 100 to 1000 μm.
Coarsely crushed in the range of These coarse pulverized materials are discharged and removed outside the machine after the operation is stopped. Such a high-speed rotary mill is called an impact-type pulverizer, and a hammer mill and a pin mill are used. Almost 100% of particles with a particle size of 100 μm or less
The particles in the range of more than 100 μm and less than 1000 μm are composed of almost 100% of petiole and vein, although the leaf is slightly contained. The pulverized material discharged from the high-speed rotary mill through the air discharge port is separated into particles and air by a conventional method using a cyclone for a dust collector. Then, using a square shifter, a plan shifter, a morgen sensor, a vibrating sieve, etc.
If the following particles are accurately separated, a mesophyll portion containing a large amount of fat-soluble vitamins such as vitamin K, vitamin E, and β-carotene can be easily obtained.

As described above, the plant tissue of the green-yellow vegetable having a green leaf blade is softened and then subjected to solid-liquid separation.
Alternatively, a vitamin K supplement composition for food can be produced by crushing and classifying a dried green-yellow vegetable. Such a vitamin K supplement composition for food contains 100
Contains at least 1000 μg of vitamin K per gram. Vitamin K has the property of being easily oxidized, but the composition obtained according to the present invention contains α-tocopherol (vitamin E) and β-carotene which have natural antioxidant effects. There is no problem with gender. The vitamin K supplement composition for food of the present invention comprises:
For example, it can be processed into various food forms such as breads, noodles, confectioneries, frozen desserts, flour mixes, paste products, ice creams, drinks, etc., and can easily supplement vitamin K in a normal diet.

[0020] The present invention also relates to a method for extracting vitamin K from the green-yellow vegetable having green leaf blades using liquefied carbon dioxide in a supercritical state. The green-yellow vegetable to be extracted is not particularly limited because it has a high ability to extract vitamin K of carbon dioxide, but in terms of extraction efficiency, for example, green-yellow vegetable itself or its leaf tissue is destroyed in advance. Is preferred. Among them, a solid or dried mesophyll portion having a high vitamin K content separated by the above-described method is preferable. FIG. 2 is a diagram illustrating a process of extracting vitamin K in the supercritical extraction device. In the figure, by opening the valve 13 and closing the valve 17, the carbon dioxide gas released from the gas cylinder 11 is cooled by the first heat exchanger 14, and is further cooled by the compressor 15 and the second heat exchanger 16. It is pressurized and heated or cooled to adjust the temperature to an appropriate level, and liquefied into supercritical carbon dioxide. Next, the valve 17 is opened to introduce the liquefied carbon dioxide kept in the supercritical state into the extraction tank 18. At this time, the amount of carbon dioxide is measured by a balance 12 attached to the gas cylinder 11, and after measuring a predetermined amount, the valve 13 is closed. Above and below the extraction tank 18, support screens 18a,
b is arranged, and green and yellow vegetables are previously charged in the tank. The liquefied carbon dioxide from which vitamin K has been extracted in the extraction tank 18 is opened by opening a valve 19 to separate the separation tank 2.
The extraction residue introduced at 0 and not passing through the filter paper is removed. Thereafter, the pressure in the separation tank 20 is reduced by closing the valve 17 and opening the valve 21, carbon dioxide is gasified and discharged from the exhaust port 22 to the outside of the tank, and the natural vitamin K extract is separated from the outlet 23. .

According to the extraction method of the present invention using carbon dioxide in a supercritical state as an extraction solvent, for example, 10 to 100 parts by weight, preferably 20 to 60 parts by weight of liquefied carbon dioxide is added to 1 part by weight of leaf meat. To extract. If the weight ratio of liquefied carbon dioxide is less than 10 parts by weight, extraction of vitamin K is insufficient. Also, even if it is used more than 100 parts by weight,
The extraction effect is not significantly improved and the cost of carbon dioxide increases.
At this time, the temperature is 10 to 60 ° C., preferably 20 to 50 ° C., and the pressure is 100 to 350 kg / cm ^2, preferably 150 to 30 kg.
When extraction is performed under the condition of 0 kg / cm ² , natural vitamin K can be selectively extracted from green and yellow vegetables. If the temperature and pressure conditions are not satisfied, undesired organic acids and polyphenols, which are astringent components, are extracted in addition to the green chlorophyll pigment. According to the above extraction processing,
By reducing the pressure after completion of the extraction, carbon dioxide as an extraction solvent is gasified and removed from the extract. Therefore, unlike the conventional column chromatography, distillation method and solvent fractionation method, much heat energy and equipment are not required for separating the organic solvent. Moreover, since the chlorophyll pigment contained in the mesophyll is not denatured into the harmful substance, highly safe natural vitamin K can be obtained. Vitamin K obtained by the above extraction method can be used as a medicine for preventing the aforementioned deficiency and promoting bone formation, in addition to food.

The vitamin K concentration is measured by an absorption spectrophotometric method for measuring and quantifying the absorbance at the maximum absorption wavelength of vitamin K, a colorimetric method for reacting with sodium alcoholate and performing colorimetry, a gas chromatography method, and a high performance liquid chromatography. There is a law. In recent years, a high-performance liquid chromatography method that is simpler and has higher quantification accuracy than other analysis methods has been widely used as a trace amount quantification method for vitamin K. In the present invention, the vitamin K analysis is briefly described first.
Add to the mixed solvent of water (8: 2) and shake for 5 minutes. Next, n-hexane is added, and after shaking and centrifugation, a crude extract is obtained. Furthermore, after purifying through a column filled with silica gel, analysis is performed by high performance liquid chromatography. High-performance liquid chromatography includes ultraviolet detection and fluorescence detection. To detect vitamin K with high precision, chemical reduction using sodium borohydride, electrical reduction, or platinum black column reduction After reducing to fluorescent hydroquinone K by using the method described above, fluorescence detection is preferable for quantification.

[0023]

EXAMPLES The present invention will be described below in more detail with reference to examples, but the present invention is not limited to these examples. FIG. 3 is a flowchart of the method for producing the vitamin K supplement composition for foods shown in Examples 1 to 5 below. Example 1 Komatsuna, a kind of green-yellow vegetable (vitamin K concentration 290μ)
g / 100 g) 1 kg was washed with running water to remove dust and mud. Washed Komatsuna with a rotary type slicer (New Sanitary ESA: manufactured by Emura Corporation)
It was cut to a length of 0 mm. This was placed in 5 liters of hot water at 98 ° C. and treated with hot water for 3 minutes to soften the leaves. afterwards,
After cooling with hot water and cooling with running water, the water was drained by natural flow to obtain 1.05 kg of softened komatsuna. Next, 250 g of water was added to the softened product in a bread making mixer (AM-20: manufactured by Aikosha Seisakusho), and 8
The leaf portion was liquefied by stirring at 0 rpm for 5 minutes. The liquefied Komatsuna was filtered using a strainer equipped with a 1 mm mesh screen to separate the petiole, leaf vein and stem from the mesophyll. The obtained filtrate was treated with a batch centrifuge at 3000 rpm for 10 minutes to settle solids, and 200 g of a vitamin K-containing composition was obtained from Komatsuna. The resulting composition had a vitamin K concentration of 1,220 μg / 100 g,
The concentration ratio of vitamin K was 4.2 times.

Example 2 Moroheiya (a vitamin K concentration of 40), a kind of green-yellow vegetable
(0 μg / 100 g) 1 kg was washed with running water to remove dust and mud. The washed Moroheiya was cut into a length of 10 mm using a rotary type slicer (the above-mentioned New Sanitary ESA). Put this in 5 liters of hot water at 90 ° C.
The leaves were softened by boiling water treatment for a minute. After that,
Cooling with running water was performed, and draining was performed by natural flow to obtain 1.07 kg of a softened Moroheiya product. Next, in a mixer for baking (AM-20), 200 g of water was added to the softened product, and the mixture was stirred at 100 rpm for 7 minutes to liquefy the leaf portion. The liquefied Moroheiya was filtered using a strainer equipped with a 1 mm mesh screen to separate the petiole, leaf vein and stem from the mesophyll. The obtained filtrate was centrifuged with a horizontal decanter to precipitate a solid, and 300 g of a vitamin K-containing composition was obtained from Moroheiya. The resulting composition has a vitamin K concentration of 1,
It was 240 μg / 100 g, and the concentration of vitamin K was 3.1 times.

Example 3 Parsley, a kind of green-yellow vegetable (vitamin K concentration: 730 μm)
g / 100 g) 1 kg was washed with running water to remove dust and mud. The parsley washed with water was cut into a length of 10 mm using a rotary type slicer (New Sanitary ESA). This was steamed with heated steam at 98 ° C. for 5 minutes to soften the leaves. Thereafter, the mixture is cooled with hot water and running water, and drained by natural flow to thereby soften parsley.
5 kg were obtained. Thereafter, the same treatment as in Example 1 was performed to obtain 250 g of a vitamin K-containing composition from parsley. The resulting composition had a vitamin K concentration of 1,680 μg / 100 g and a vitamin K concentration of 2.3 times. Example 4 1 kg of radish leaf (vitamin K concentration 250 μg / 100 g) was subjected to the same treatment as in Example 2 to obtain 150 g of a vitamin K-containing composition from radish leaf. The obtained composition had a vitamin K concentration of 1,050 μg / 100 g and a vitamin K concentration of 4.2 times.

Example 5 Leaves of Simon No. 1 (a vitamin K concentration of 33), a kind of sweet potato
(0 μg / 100 g) 1 kg was washed with an ultrasonic washing machine to remove dust and mud. The washed Simon leaves were cut to a length of 10 mm with a kitchen knife. This was placed in 3 liters of hot water at 95 ° C., and treated with hot water for 4 minutes to soften the leaves. Thereafter, the mixture was cooled with hot water and running water, and drained by natural flow to obtain 1.05 kg of softened leaves of Simon leaves. Then, in a horizontal kneader for producing an oil, the softened material was treated with water 1000
g was added and the mixture was stirred at 100 rpm for 4 minutes to liquefy the mesophyll. The liquefied Simon leaves were filtered using a strainer equipped with a 2 mm mesh screen to separate the petiole, leaf vein and stem from the mesophyll. The filtrate obtained is 300
The mixture was treated with a batch centrifuge at 0 rpm for 10 minutes to settle solids, and the vitamin K-containing composition 23 was removed from Simon leaves.
0 g was obtained. Further, 120 g of the above composition from which water was removed was obtained by performing a freeze-vacuum drying treatment at 30 ° C. The resulting composition has a vitamin K concentration of 2,350 μg / 100 g,
The concentration ratio of vitamin K was 7.1 times.

Examples 1 to 5 are summarized in Table 1 below.

[Table 1]

Examples 6 to 10 Leaves (vitamin K concentration of 33), which is the above-ground part of Simon 1
0 μg / 100 g) and 1 kg of stem were washed with running water to remove dust and mud adhering to the surface. The water-washed Simon leaves and stems were cut to a length of 10 mm using a rotary slicer (New Sanitary ESA), and then drained by a gravity flow method. Then 70 ° C
Was dried for 12 hours with a multi-stage hot-air drier set as described above, to obtain 120 g of a dried product of Simon ground part. At that time, 2
Stirring was performed every .about.3 hours to promote drying. Then
Leaves and stems were separated from the dried Simon aerial parts dried to a moisture content of 8% using a wind threshing machine for threshing to obtain 50 g of dried leaf parts. Each of the dried leaves was used for the rotating blades (8, 9) in the pulverizing section (2) and the classifying section (3) using a high-speed rotary mill (ACM Pulverizer: Hosokawa Micron Corp.) shown in FIG. The crushed material discharged from the discharge unit (5) was collected by a cyclone while changing the rotation speed. Each of the obtained pulverized materials was passed through a nylon 100 μm mesh vibrating sieve to obtain pulverized mesophyll particles having a particle size of 100 μm or less.

Examples 6 to 10 are summarized in Table 2 below.

[Table 2]

As shown in Table 2, in Example 9, since the rotation speed of the pulverizing part was relatively small at 3000 rpm and the pulverizing effect of the dried leaf part was not sufficient, the yield of the pulverized leaf part was low. In addition, since the number of revolutions of the classification portion was increased to 1500 rpm, the petiole and veins other than the mesophyll were partially mixed, and the vitamin K concentration was low. Example 10
In this case, since the rotation speed of the classification portion was as low as 600 rpm, the yield of the pulverized leaf meat was low. In addition, since the number of revolutions of the pulverizing part was relatively high at 7,000 rpm, part of the petiole and leaf vein was pulverized to a particle diameter of 100 μm or less, and the vitamin K concentration was low. On the other hand, the rotation speed of the first rotor in the pulverizing section is in the range of 4000 to 6000 rpm, and the rotation speed of the second rotor in the classification section is 800 to 12
In Examples 6 to 8 in which the control was performed within the range of 00 rpm, favorable results were obtained in both the yield of the ground meat and the vitamin K concentration. Thus, it can be seen that by controlling the number of rotations of the rotor in the pulverizing section and the classifying section to the above range, the yield of the mesophyll and the vitamin K concentration thereof are improved.

Example 11 Using the supercritical extraction device shown in FIG. 2, the ground pulverized mesophyll obtained in Example 7 was extracted to obtain vitamin K. That is, 1 kg of the crushed leaf meat is put into the extraction tank (18), and the carbon dioxide released from the gas cylinder (11) is temperature-adjusted and pressurized by the heat exchangers (14, 16) and the compressor (15), and the pressure is increased. The liquefied carbon dioxide which has reached the critical state was introduced into the extraction tank (18). Using the liquefied carbon dioxide in the supercritical state as an extraction solvent, a temperature of 40 ° C. and a pressure of 250 kg
The above-mentioned pulverized material was subjected to an extraction treatment under the condition of / cm ² . Extraction tank
Support screens (18a, 18b) with openings of 50 μm are arranged above and below (18), and No. 2 filter paper (Whatman filter paper: grade 2) is arranged inside. After the extraction treatment, carbon dioxide containing vitamin K was introduced into the separation tank (20) to remove the extraction residue on the filter paper. Thereafter, the pressure in the separation tank (20) was reduced to 50 kg / cm ² to gasify carbon dioxide, and 11.6 g of a natural vitamin K extract was obtained.
I got Vitamin K concentration in the obtained extract is 250,000
μg / 100 g.

[0032]

According to the method for producing the vitamin K supplement composition of the present invention, vitamin K contained in the leaf portion of green and yellow vegetables can be obtained by a relatively simple processing method. Since the obtained vitamin K composition is made from green-yellow vegetables that have been taken for many years in a normal diet, the palatability is good and there is no problem in safety. Also,
According to the method for extracting vitamin K of the present invention, since carbon dioxide is used as the extraction solvent, no harmful substance remains in the obtained vitamin K.

[Brief description of the drawings]

FIG. 1 is an explanatory view of a high-speed rotating mill used in a pulverizing and classifying step as an example of the present invention.

FIG. 2 is a process diagram of a supercritical extraction device for extracting vitamin K in a vitamin K supplement composition for food of the present invention using liquefied carbon dioxide as an extraction solvent.

FIG. 3 is a flowchart of a method for producing a vitamin K supplement composition for food, showing one embodiment of the present invention.

 ──────────────────────────────────────────────────の Continued on the front page (72) Inventor Osamu 1-25-1, Hanazono, Kumamoto City, Kumamoto Prefecture Kumamoto Flour Milling Co., Ltd.

Claims (4)

[Claims] At least the leaves of a green-yellow vegetable having a green leaf blade are heated to soften the plant tissue and then solid-liquid separated into a liquid mesophyll, a solid petiole and a leaf vein. A method for producing a vitamin K supplement composition for foods, comprising separating a solid in a leaf portion having a high vitamin K content from the obtained liquid leaf portion. 2. A green leafy portion of a green-yellow vegetable, in which at least a dried portion of the leaf portion is crushed, and the crushed material is classified into a leaf portion, a petiole portion and a leaf vein portion, and the leaf portion having a high vitamin K content is obtained. A method for producing a vitamin K supplement composition for foods, comprising separating a dried product of vitamin K. 3. A method for producing a vitamin K supplement composition for foods, wherein the vitamin K content of the mesophyll separated by the method according to claim 1 or 2 is 1000 μg or more per 100 g. 4. A method for extracting vitamin K, comprising extracting green-yellow vegetables having green leaf blades with liquefied carbon dioxide in a supercritical state.