JPH06181725A - Agent for solidifying easily oxidizable oily substance - Google Patents

Abstract

PURPOSE:To provide an easily handleable, powdery or granular solidifying agent used for preventing the oxidation of an easily oxidizable oily substance such as an unsaturated fatty acid and for masking its unpleasant smell and taste. CONSTITUTION:The objective agent is characterized by adding a stabilizing agent to an easily oxidizable oily substance, replacing air in a porous carrier with the oily substance under a reduced pressure, and subsequently covering the oily substance-adsorbed porous carrier with an amphiphatic substance.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a solidifying agent for oily substances that are easily oxidized, and more specifically, it solidifies unsaturated fatty acids and vitamins that are oily substances that can be used in foods, pharmaceuticals and the like. It is related to agents.

[0002]

2. Description of the Related Art Conventionally, as a method for stabilizing docosahexaenoic acid (hereinafter referred to as DHA), which is an unsaturated fatty acid that is an easily oxidizable oil, a catechin-containing tea extract preparation is used for 100 oils containing DHA. About 0.2% by weight and about 0.3% by weight of vitamin E (these percentages are the same below) are added and mixed to prevent oxidation, or D is added to the porous body.
There is a method of adsorbing the HA-containing oil by allowing the HA-containing oil to naturally permeate (Japanese Patent Application No. 62-264015). As a method for masking the unpleasant odor and taste of fish oil, a method of inclusion with dextrin or cyclodextrin (JP-A-59)
No. 41395), and a method of burying in egg white and spray-drying have been proposed or implemented.

[0003]

The method of adding about 0.2% of catechin-containing tea extract preparation and about 0.3% of vitamin E to DHA as described above is insufficient in antioxidant. , I was not satisfied with the use.
Further, in the method of naturally permeating into the porous body, the amount of oil adsorbed was not sufficient, and the unsaturated fatty acid was oxidized by oxygen in the air remaining in the pores of the porous body, which became a destabilizing factor. In addition, the method of inclusion with dextrin etc. dissolves immediately when there is water, so the fish oil is exposed in the mouth and the smell and taste come out, and the technology of processing with egg white causes a return phenomenon over time and fish odor occurs. There are drawbacks such as increasing.

The present invention has been made in view of the above-mentioned problems of the prior art, and its object is to prevent the oxidation of an oily substance composed of an easily oxidizable substance such as unsaturated fatty acid and mask an unpleasant odor or taste. And to provide a granular or powdery solidifying agent which is easy to handle.

[0005]

Means and Actions for Solving the Problems The present inventors have
As a result of diligent studies on the solution to the above-mentioned problems, it was noted that a substance obtained by adding a stabilizer to an oxidizable oil was replaced with air contained in the porous carrier to be adsorbed and supported.

The present invention is based on the above idea,
The gist is a structure in which an oily substance to which a stabilizer is added and which is easily oxidized is replaced with air in a porous carrier to be adsorbed and carried, and the porous carrier carrying the oily substance is coated with an amphipathic substance. It is a solidifying agent for easily oxidizable oily substances.

The oily substance which is easily oxidized according to the present invention is derived from, for example, fish oil and contains DHA containing a large amount of unsaturated bonds, eicosapentaenoic acid (hereinafter referred to as EPA), vitamin A, vitamin E and the like. It is a waste.
These substances contain a large amount of unsaturated fatty acids and are extremely unstable to oxidation, but they play an important role for the living body and are oily substances that can be used for foods, pharmaceuticals and the like. In particular, DHA and EPA are derived from fish oil and cause an offensive odor due to oxidation, so stabilization by preventing oxidation is desired. The oily substance used in the present invention is stored after cooling under nitrogen substitution, and it is preferable to provide a fresh one having a POV (peroxide value) of 5 meq / kg or less.

Next, as the stabilizer used in the present invention, according to the studies by the present inventors, for the most unstable DHA-containing oil, for the DHA-containing oil as in the above-mentioned prior art. It has been found that stabilization is not satisfactory in a method for preventing oxidation by using a mixture of a catechin-containing tea extract preparation of about 0.2% and vitamin E of about 0.3%. Instead, the following Sankatol No. 1 which is a tea extract formulation consisting of catechin and vitamin E
It was found that the addition at a high concentration of 10% or more further contributes to the stabilization of DHA oil. That is, Sankatol No
By adding 1 or more 1%, the stability is remarkably increased, and the stability is improved in proportion to the concentration in the range up to about 2%, but the stability is slightly increased at 2 to 3%.
Considering economical efficiency and secondary effects, addition of up to about 2% is preferable. When the solid agent of the easily oxidizable oily substance according to the present invention is used for foods and pharmaceutical preparations, a catechin-containing extract extracted from tea leaves (Taiyo Kagaku Co., Ltd. Sankatol) may be used as a stabilizer. preferable. That is,
Fig. 1 shows that oil containing 25.6% of DHA and 0 to 0 of sancatol
The results of examining the change with time of the peroxide value in the case of mixing at a ratio of 2% are shown. As is clear from FIG. 1, when 2% of Sancatol is added, the change in peroxide value with time is extremely small.

Examples of the porous carrier used in the present invention include grain foams such as hail and popcorn made from rice, porous starch or dextrin, protein foams such as malt, foams of chitin and chitosan, and silicon dioxide. Is used.
The rice hail, which is a typical example of a grain foam, is obtained by foaming rice grains in which starch particles are densely solidified, so that fine voids are formed inside. Then, as will be described later, under reduced pressure, the above-mentioned oily substance penetrates deeply, and the amount of adsorption can be significantly increased.

Porous starch or dextrin has hitherto been commercially available as an oil and fat adsorbent (Asahi Kasei QS1,
(Sterley Micropore Parts). These apparently adsorb 2 to 8 times the adsorbent's own weight of oil, but the adsorbent particles gather around the oil to form secondary particles more than the amount adsorbed in the voids of the particles themselves, and apparently oil is Although it seems to be pulverized, it has a drawback that oil is easily exuded and oxidized when pressure is applied. Secondly, the malt, which is a protein foam, has large voids, so that the amount of oil adsorbed under reduced pressure increases, but there is a drawback that exudation after adsorption increases. And chitin and chitosan have the advantage that the size of the voids can be adjusted freely depending on the foaming method. However, since it is not digested in vivo, it cannot be used depending on the use of oil.

Further, in silicon dioxide, some molecules are aggregated to form a spherical cluster. Since many lipophilic groups are lined up inside the spherical cluster, the oil absorption capacity is extremely high. Further, unlike starch and dextrin, the internal oil hardly exudes even when a pressure is applied, and it is extremely preferable as the physical property of the oil adsorbent, but it cannot be used in food because it is an inorganic substance. As described above, the porous carrier used in the present invention has different properties depending on each material, and therefore it is necessary to select and use it according to the purpose.

Next, the step of replacing the oily substance with air in the above porous carrier under reduced pressure and adsorbing it will be described. Since the above porous carrier has small pores and a complicated structure, it is difficult to completely absorb the oil into the particles by the method of adsorbing the oil by utilizing only the capillary phenomenon. A substance such as DHA that is extremely susceptible to oxidation may be oxidized even by a small amount of oxygen in the air present in the porous carrier. In the present invention, first, the porous carrier is immersed in the above-mentioned oily substance, and the air present in the voids inside the porous carrier is discharged under reduced pressure. When the generation of air bubbles stops, the degree of pressure reduction is gradually relaxed, and the oily substance penetrates into the voids of the porous carrier. As a result, for example, when the above-mentioned rice bran is used as the porous carrier, the oil is adsorbed 8 times as much as that in the natural adsorption method.

As described above, by adsorbing the oily substance inside the voids of the porous carrier, the oily substance can be blocked from the air to prevent the oxidation of the oil. In order to prevent the oxidation of the oil existing on the surface or in the shallow portion of the voids, it is preferable to coat the surface of the porous carrier on which the oil is adsorbed with an amphipathic substance. It is essential that the amphipathic substance has a lipophilic group that is compatible with the adsorbed oil, is soluble in water or ethanol, and has the property of solidifying after drying. Examples thereof include organic acid monoglyceride, propylene glycol fatty acid ester, polyglycerin fatty acid ester, polyglycerin condensed linoleic acid ester, solid or semi-solid surfactant such as diglycerin monostearate, soybean oil as a crystalline fat, and rapeseed oil. Special hardened oil (TP-9 manufactured by NOF CORPORATION), water-soluble cellulose ether, ethyl cellulose, hydroxypropylmethyl cellulose phthalate, and zein can be used. And as for its usage,
These amphiphiles should be added at concentrations of 1-10% (ethanol 100
W / v% or less) to an ethanol solution, and immersing the porous carrier adsorbing the oily substance in this solution,
If necessary, it can be further adsorbed under reduced pressure, and then dried to complete the coating step, and the solid agent of the oxidizable oily substance according to the present invention can be obtained.

The main steps in the present invention are as described above, but the surface of the solid agent of the above-mentioned oxidizable oil is coated with a commonly used cellulose-based enteric coating film according to the needs of the application. Thus, for example, it is possible to prevent fish odors from appearing in the burp after taking the solid agent in which DHA is adsorbed. It is also possible to coat the surface with chocolate or sugar to make it easier to take.

[0015]

EXAMPLES Next, the present invention will be described in more detail by way of examples. Example 1 1,000 g of purified fish oil containing 28% DHA in a container,
The above-mentioned catechin-containing tea extract preparation was added thereto at a rate of 2% in advance, and 100 g of rice foam was completely immersed in the refined fish oil to avoid contact with air, and this container was placed under reduced pressure. Then, the air in the rice foam is gradually discharged as bubbles in the oil. Put it under reduced pressure for about 15 minutes, confirm that the generation of air bubbles has stopped, and gradually loosen the reduced pressure,
Oil penetrates into the voids of the rice foam. Five minutes after returning to normal pressure, unadsorbed oil and oil adhering to the surface of the rice foam are removed. Next, the rice foam adsorbing this oil was treated with organic acid monoglyceride Sunsoft 621B (Sunsoft 621B manufactured by Taiyo Kagaku Co., Ltd.) 2.5% and water-soluble cellulose ether (Metroze manufactured by Shin-Etsu Chemical Co., Ltd.) 2. After immersing in an ethanol solution containing 5% for a few seconds, it was taken out and dried. The yield of the oil-adsorbed rice foam obtained in Example 1, that is, the solidifying agent of the easily oxidizable oil of the present invention was 450 g. Then, for this product, the results of examining the daily change of the peroxide value were shown to be 2 for DHA.
It is shown in FIG. 2 in comparison with refined fish oil containing 8% and not treated according to the invention. As is clear from FIG. 2, the product of the present invention shows almost no change with time in peroxide value.

Example 2 300 g of purified fish oil containing 20% EPA in a container was taken, and the above-mentioned catechin-containing tea extract preparation was added in advance thereto in a proportion of 2%, and a protein foam (mouse) 12. When 2 g is completely immersed in the purified fish oil so that it is not exposed to air, and the container is placed under reduced pressure, the air in the foam is gradually discharged as bubbles in the oil. This is put under a reduced pressure for a while, it is confirmed that the generation of bubbles has stopped, and when the degree of reduced pressure is gradually loosened, oil penetrates into the voids of the foam. Then, after returning this to normal pressure, unadsorbed oil and oil adhering to the surface of the foam are removed. Next, the foam adsorbed with this oil was added to a water: ethanol (1: 9) solution containing 5% of zein (% indication is w / 100 parts of water and ethanol).
(v%) and soaked in it for several seconds, and then taken out and dried. The yield of the oil-adsorbed protein foam obtained in Example 2, ie, the solidifying agent of the easily oxidizable oil of the present invention, was 117 g, and the amount of oil contained therein was It was 89.6%. Then, the results of examining the change with time of peroxide value of this product are shown in FIG. 3 in comparison with those of the refined fish oil containing 20% of EPA which was not treated according to the present invention. As is clear from FIG. 3, the product of the present invention shows a slight increase in the peroxide value with time.

Example 3 1 kg of refined oil containing 60% or more of α-tocopherol, which is the most easily oxidizable among vitamin E, was taken in a container, and the above-mentioned catechin-containing tea extract preparation was added thereto at a rate of 2%. Further, 200 g of silicon dioxide was completely immersed in the refined oil so as not to come into contact with air. When this container was placed under reduced pressure, the air contained in the silicon dioxide gradually became bubbles in the oil. Is discharged. This was placed under reduced pressure for a while, and when it was confirmed that the generation of air bubbles had stopped, the degree of reduced pressure was gradually loosened and the oil was adsorbed on silicon dioxide. Then, after returning to normal pressure, 100 g of the above special rapeseed oil special hardened oil separately heated to 90 ° C. was sprayed while heating the whole to 50 ° C. and stirring, and cooled to obtain 1,270 g of stabilized powder. . With respect to the stabilized powder having the oil adsorbed therein obtained in Example 3, the results of examining the change with time of the peroxide value are shown in FIG. 4 in comparison with those without the treatment according to the present invention. As is clear from FIG. 4, the product of the present invention shows a slight increase in peroxide value with time.

[0018]

INDUSTRIAL APPLICABILITY According to the present invention, a stabilizer is added to an oil that is easily oxidized, and this oil is adsorbed by substituting it with air in a porous carrier under reduced pressure. Is a solidifying agent for easily oxidizable oils, which consists of coating an organic carrier with an amphipathic substance, and is extremely effective for preventing the oxidation of oils made of easily oxidizable substances such as unsaturated fatty acids. It is possible to conceal the unpleasant odor and taste derived from. The unsaturated fatty acids and vitamins that exist as oily substances can be used as a solidifying agent in the form of granules or powder that can be easily handled when they are used in foods, pharmaceuticals, etc., and are therefore practically convenient. Furthermore, under reduced pressure, the above oily substance enters the deep part of the porous carrier, and the amount of adsorption can be remarkably increased, and the product of the present invention is an extremely excellent preparation with almost no change in peroxide value over time. Become.

[Brief description of drawings]

FIG. 1 shows a case where a stabilizer (sancatol) is mixed in an oil containing 25.6% DHA at a ratio of 0 to 2%.
It is a graph which shows the result of having investigated the change with time of the peroxide value.

FIG. 2 is a graph showing the results of examining the change with time in peroxide value of the product according to Example 1.

FIG. 3 is a graph showing the results of examining the change with time in peroxide value of the product according to Example 2.

FIG. 4 is a graph showing the results of examining the change with time in peroxide value of the product according to Example 3.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location A61K 9/18 7329-4C C11B 5/00 2115-4H

Claims (5)

[Claims] 1. A oxidizable oily substance to which a stabilizer is added is replaced with air under reduced pressure in a porous carrier to be adsorbed and supported, and the porous carrier bearing the oily substance is coated with an amphipathic substance. A solidifying agent for an easily oxidizable oil, which is characterized by having the above structure. 2. An easily oxidizable oil is docosahexaenoic acid, eicosapentaenoic acid, vitamin A or vitamin E.
The solidifying agent for an easily oxidizable oil according to claim 1, which comprises at least one selected from the group consisting of: 3. A porous carrier, hail, popcorn,
The solidifying agent for an easily oxidizable oil according to claim 1, wherein one or more kinds selected from foams of cereals, porous starch, dextrin, malt, chitin, chitosan, and silicon dioxide are used. 4. The solidifying agent for an easily oxidizable oil according to claim 1, wherein a tea extract preparation comprising catechin and vitamin E is added as a stabilizer in an amount of 1 to 2% with respect to the oil. 5. An amphipathic substance is an organic acid monoglyceride, propylene glycol fatty acid ester, polyglycerin fatty acid ester, polyglycerin condensed linoleic acid ester, diglycerin monostearate, crystalline oil / fat, water-soluble cellulose ester, ethyl cellulose, hydroxypropyl. The solidifying agent for an easily oxidizable oil according to claim 1, which is one or more selected from methyl cellulose phthalate and zein.