JP2007209251A - Coenzyme q10-containing composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a coenzyme Q10-containing composition coenzyme Q10 in which is easily dispersed to water and is prevented from crystallization so as to simultaneously solve the following two problems which interfere with its utilization while being an essential component for a living body and being in demand of application to food and drink, cosmetics, drugs and/or feed; and coenzyme Q10 has poor dispersibility in water and is easily crystallized. <P>SOLUTION: The coenzyme Q10-containing composition comprises the coenzyme Q10 and polyglyceryl fatty acid ester where polyglyceryl having ≤1,200 hydroxyl value and ≥50 wt.% of a primary hydroxy group in all the hydroxyl groups, and fatty acid are esterified. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a coenzyme Q10-containing composition that has high storage stability and is easily and uniformly dispersed in water.

  Coenzyme Q10 (hereinafter referred to as CoQ10) is also called ubidecalenone, ubiquinone-10, and the like, and is used in pharmaceuticals as a metabolic cardiotonic agent and the like due to its specific physiological action. In Japan, it is possible to use it for food applications due to the review of the category of medicines, which is expected to be applied in the health food field. In particular, the recent research results of CoQ10 are remarkable, in addition to the myocardial protective action, cancer prevention, anti-aging action, blood LDL oxidation inhibition, and blood pressure increase inhibition, and oxygen utilization efficiency in ischemic myocardium derived from CoQ10's antioxidant action Improvement, activation of ATP synthesis in cardiac mitochondria, improvement of cardiac function, etc. have been reported. However, CoQ10 is a yellow-orange solid at room temperature, hardly dissolves in water and alcohol, and hardly dissolves in oil. Therefore, it is extremely low in versatility for use in food applications, and is particularly useful for beverage applications. There was a drawback of being restricted.

As a method for formulating CoQ10 for the purpose of dispersing in water, a method for preparing an aqueous solution of a fat-soluble substance by mixing CoQ10, an emulsifier, a polyhydric alcohol, and water and then treating with high pressure (for example, Patent Document 1) And a method for solubilization using polyoxyethylene sorbitan monooleate (see, for example, Patent Document 2) has been proposed. However, the aqueous solution prepared by the former method can temporarily make CoQ10 into an aqueous solution by an ultrahigh pressure treatment of 1000 kg / cm ² , but it is poor in stability and becomes cloudy over time or CoQ10 crystals precipitate. . In the latter method, polyoxyethylene sorbitan monooleate is used, and such an ethylene oxide surfactant generates a highly toxic by-product during the synthesis reaction in the production process. It is not preferable for use in food applications.
In addition, as a preparation with an increased bioabsorption rate of CoQ10, CoQ10 obtained by adding heat-dissolved CoQ10 to heated edible oil or by adding CoQ10 to edible oil and dissolving it by heating and then cooling is obtained. A mixture of CoQ10 and edible oil dispersed in (1) is proposed (for example, see Patent Document 3). However, this preparation cannot be added directly to water-based foods.
Several reports have been proposed as an emulsified composition containing a high concentration of CoQ10 (see, for example, Patent Documents 4, 5, 6, and 7).
To explain in sequence, a composition in which an oil phase part in which CoQ10 is dissolved and a polyhydric alcohol phase part are mixed and emulsified, and a composition in which the average particle system is reduced using CoQ10, two types of polyglycerin fatty acid esters and a solubilizing aid. A composition comprising CoQ10, monoglycerin fatty acid ester and condensed ricinoleic acid ester. And there exists a composition characterized by containing CoQ10, medium chain fatty acid triglyceride, and propylene glycol fatty acid ester. In any proposal, in order to obtain a high-concentration composition, two liquid phases were mixed, or a composition was obtained by using 2-3 kinds of emulsifiers and solubilizing aids.
In addition, CoQ10 has a melting point of about 50 ° C. and is easily crystallized, which contributes to the difficulty of the preparation method. When CoQ10 is applied to pharmaceuticals, foods, and cosmetics, if crystallization progresses in the product, the content will become non-uniform, the absorption to the living body will be impaired, the texture will be deteriorated, and the appearance will be deteriorated. It will end up.

JP 2000-212066 A (pages 2 to 11) JP-T-2001-504343 (pages 2 to 11) JP 2003-125734 A (pages 2 to 13) JP 2003-238396 A (pages 2 to 18) JP 2004-196781 A (pages 2 to 18) JP-A-2005-43 (pages 2-18) Japanese Patent Laying-Open No. 2005-47851 (pages 2 to 18)

As described above, CoQ10 is an essential component for living bodies, and there is a great demand for applying this to foods, beverages, cosmetics, pharmaceuticals, and feeds. The hindrance to its use is that it is poorly dispersible in water and easily crystallized.
Accordingly, an object of the present invention is to provide a CoQ10 composition that can easily and uniformly disperse CoQ10 in water, suppress crystallization, and simultaneously solve these two points.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have used a special polyglycerin fatty acid ester that has an effect of suppressing crystallization of CoQ10 and also has an effect of emulsification and solubilization. CoQ10 content that is excellent in acid resistance, heat resistance and salt resistance required when added to cosmetics, pharmaceuticals and feeds, maintains a stable emulsification / solubilization state even during long-term storage, and can be expected to have physiological effects It has been found that a CoQ10-containing composition containing can be obtained.

  The present invention has been completed based on these findings, and the gist of the present invention is that polyglycerin and fatty acid having CoQ10 and a hydroxyl value of 1,200 or less and primary hydroxyl groups of 50% or more of all hydroxyl groups. The present invention provides a CoQ10-containing composition comprising, as an essential component, a polyglycerin fatty acid ester in which is esterified.

  The present invention also provides an oil-in-polyhydric alcohol type (O / D type) CoQ10-containing composition.

  According to the present invention, CoQ10 can be easily and stably dispersed in water, so that high-value foods, beverages, cosmetics, pharmaceuticals, and feeds can be produced.

  Hereinafter, the present invention will be described in detail.

CoQ10 is a benzoquinone derivative having an isoprenoid chain composed of 10 isoprene units as a side chain, and is widely distributed in nature. In animals and plants, it is involved in the electron transport system of oxidative phosphorylation in mitochondria. CoQ10 used in the present invention is not particularly limited as long as it is ingestible by a living body, for example, a mammal, especially a human. Examples of the CoQ10 include commonly used industrial synthetic products, cell extracts such as yeast extract obtained by fermentation, sardines, pigs, cows, chickens, broccoli, eggplant, garlic, cabbage, etc. Extracts from animals and plants are included, and each can be used alone or in admixture of two or more. Preferably, it is better to use a yeast extract obtained by fermentation from the viewpoint of product image or production efficiency.
In addition, since there are those having an isoprenoid chain consisting of 1 to 12 isoprene units as side chains (CoQ1 to 12) in nature, the CoQ10 composition of the present invention inhibits the expression of the desired effect of the present invention. Unless otherwise specified, analogs having different lengths of their isoprenoid chains may be included.

  The technique of the present invention can be applied even when the length of the isoprenoid chain is changed. In particular, when the isoprenoid chain is used for animal feed, the isoprenoid chain may be selected according to the target animal. Further, CoQ10 is easily reduced by other substances having a reducing action, and the structure changes from an oxidized quinone body to a reduced alcohol body. This reduced CoQ10 is also called ubiquinol, but its action on the living body is the same for both oxidized and reduced forms. Therefore, this patent recognizes both CoQ10 without distinguishing between oxidized and reduced types.

  The polyglycerol fatty acid ester used in the CoQ10 composition is obtained by esterifying a polyglycerol having a hydroxyl value of 1,200 or less and a primary hydroxyl group of 50% or more of all hydroxyl groups and a fatty acid. It has a great feature.

  By having such characteristics, the polyglycerol fatty acid ester used in the CoQ10 composition is excellent in imparting water dispersibility of CoQ10 and can be used as a surfactant that suppresses crystallization.

  The polyglycerin in the polyglycerin fatty acid ester means a substance having a hydroxyl group and an ether bond in the molecule obtained by dehydrating condensation of glycerin.

  The polyglycerol in the polyglycerol fatty acid ester has a primary hydroxyl group of 50% or more of all the hydroxyl groups, and from the viewpoint of further improving the solubilization performance and emulsion stability of the resulting polyglycerol fatty acid ester, the primary hydroxyl group is preferred. It is 55% or more, more preferably 60% or more of polyglycerol. Further, the upper limit value is not particularly limited, but is desirably 90% or less in order to maximize the effect. The proportion of primary hydroxyl groups out of the total hydroxyl groups of polyglycerin changes according to the degree of condensation of polyglycerin, and the types of polyglycerin that are generally distributed are tetra, penta, hexa, and deca. If the upper limit value is exemplified in consideration, tetraglycerin is 70% or less, preferably 65% or less, pentaglycerin is 75% or less, preferably 70% or less, and hexaglycerin is 80% or less, preferably 75% or less. In decaglycerin, a numerical value such as 85% or less, preferably 80% or less can be shown. Furthermore, the hydroxyl value of polyglycerol is 1,200 or less, and from the viewpoint that the hydrophilicity (HLB) of the polyglycerol fatty acid ester can be adjusted according to the use, 1,100 or less is more preferable, and 1,000 or less is more preferable. preferable. Further, from the viewpoint of workability and ease of esterification with a fatty acid, the hydroxyl value is preferably 770 or more.

  The proportion of primary hydroxyl groups among all hydroxyl groups is measured using a method of measuring a nuclear magnetic resonance spectrum (NMR) for carbon atoms. The hydroxyl value can be measured by a method known in the art.

In addition, the nuclear magnetic resonance spectrum (NMR) with respect to a carbon atom can be measured as follows. Polyglycerin 500 mg is dissolved in 2.8 mL of heavy water, and after filtration, a ¹³ C-NMR (125 MHz) spectrum is obtained by gated decoupling. The peak intensity is proportional to the carbon number by the gate decoupled measurement method. The ¹³ C chemical shifts indicating the presence of primary hydroxyl groups and secondary hydroxyl groups are about 63 ppm for methylene carbon (CH ₂ OH) and about 71 ppm for methine carbon (CHOH), respectively. The abundance ratio of the primary hydroxyl group and the secondary hydroxyl group is calculated. However, the methine carbon (CHOH) indicating the secondary hydroxyl group overlaps with the methylene carbon peak further adjacent to the methine carbon bonded to the methylene carbon indicating the primary hydroxyl group, and the integral value of itself cannot be obtained. The integrated value is calculated from the signal intensity around 74 ppm of methylene carbon (CH ₂ ) adjacent to (CHOH).

  The polyglycerol preparation method of the polyglycerol fatty acid ester used for CoQ10 composition is not limited. For example, it can be obtained by devising a synthetic method or by fractional purification from commercially available polyglycerol.

  For example, a polyglycerin synthesized as described above or a commercially available polyglycerin is reacted with a reagent that selectively binds to a primary hydroxyl group, that is, a reagent that serves as a protective group for the primary hydroxyl group. Then, since the number of protective groups increases as the number of primary hydroxyl groups in one molecule of polyglycerol increases, the polarity of the polyglycerol decreases as a result. On the other hand, since a protective group is difficult to be introduced into polyglycerin containing a lot of secondary hydroxyl groups, the polyglycerin maintains its original high polarity. It is possible to separate the two using this difference in polarity. The polyglycerin after the separation can be subjected to a protecting group elimination treatment to obtain polyglycerin containing a large amount of primary hydroxyl groups.

  In this case, examples of the reagent that selectively reacts with the primary hydroxyl group include chlorotriphenylmethane, isobutene, 1-trimethylpyridinium tetrafluoroborate, and the like. As for polyglycerin having no secondary hydroxyl group other than 1,2-diol, a compound that forms acetonide with polyglycerin (for example, methyl isopropenyl ether, 2,2-dimethoxypropane, 2,2-diethoxypropane, Acetone etc.) can also be used. Of these, chlorotriphenylmethane is preferred because of the ease of introduction and elimination of primary hydroxyl groups.

  The reaction ratio of polyglycerin and the reagent is appropriately adjusted according to the desired number of primary hydroxyl groups in polyglycerin, but it is preferable to use an excessive amount of the reagent in order to surely proceed the reaction. For example, the reagent is preferably used in an amount of 2 to 10 mol, more preferably 3 to 7 mol, per 1 mol of polyglycerol.

  The reaction between polyglycerin and the reagent is preferably performed at 5 to 30 ° C, more preferably 10 to 25 ° C, from the viewpoint of the progress of the reaction and the certainty of protection.

  After the reaction, post-treatment may be performed in the same manner as a normal chemical reaction. Organic solvents such as pyridine can be removed by distillation under reduced pressure.

  A method for fractionating the desired polyglycerol from the obtained reaction product can be achieved by utilizing the chemical and physical differences of the polyglycerol into which a protecting group has been introduced. For example, the target polyglycerin can be fractionated by a method such as distillation, vacuum distillation, molecular distillation or the like using the difference in boiling point, or the target polyglycerin can be separated using the difference in solubility in water or an organic solvent. It can also be fractionated. For example, the target polyglycerin is fractionated by dispersing the reaction product in water and extracting it with an organic solvent immiscible with water (eg, chloroform, dichloromethane, petroleum ether, hexane, benzene, toluene, ether, ethyl acetate, etc.). can do. When this fractionation method is used, a solution of an inorganic salt such as water-containing ethanol, saline, or sodium sulfate solution can be used instead of water. It is preferable to fractionate the desired polyglycerol using water and ethyl acetate.

By removing the solvent after solvent extraction, a low-polarity polyglycerin derivative, that is, polyglycerin in which many protective groups are introduced in one molecule is obtained. Removal of the protecting group from this derivative can be carried out by a method used in general organic synthesis. For example, the removal of the protecting group can be achieved by a method of allowing p-toluenesulfonic acid to act in methanol, a method of heating and stirring in an acetic acid aqueous solution, or the like. As an example, when a triphenylmethyl group is introduced into polyglycerin, a protective group is obtained by adding 2 to 3 times the amount of acetic acid aqueous solution to the obtained reaction product and stirring at 55 to 60 ° C. for 10 hours. Can be released.
Furthermore, the polyglycerin is prepared by condensing a glycerin derivative such as glycidol or epichlorohydrin to prepare a polyglycerin containing a large amount of primary hydroxyl groups, and mixing it with a commercially available polyglycerin to meet the purpose of the present invention. You may adjust the ratio of a secondary hydroxyl group and a secondary hydroxyl group.

  A method for preparing polyglycerol having a hydroxyl value of 1,200 or less is not particularly limited, and for example, it can be achieved by adjusting the polyglycerol reaction step as follows. For example, when preparing using the glycerin polymerization method, the hydroxyl value decreases with the lapse of the polymerization reaction time. Therefore, by confirming the process of decreasing the hydroxyl value of polyglycerol during the reaction, Glycerin can be easily obtained.

  Fatty acids used in the present invention are particularly limited as long as they contain a carboxylic acid as a functional group obtained by hydrolyzing and extracting oils extracted from natural animals and plants and purifying them with or without separation. is not. Alternatively, it may be a fatty acid obtained by chemically synthesizing petroleum or the like as a raw material. Alternatively, the fatty acid may be reduced by hydrogenation or the like, a condensed fatty acid obtained by condensation polymerization of a fatty acid containing a hydroxyl group, or a polymerized fatty acid obtained by heat polymerization of a fatty acid having an unsaturated bond. The selection of these fatty acids may be appropriately determined in consideration of the desired effect. Specific examples of fatty acids used in the present invention include saturated or unsaturated fatty acids having 6 to 22 carbon atoms, that is, caproic acid, caprylic acid, octylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmito Examples include oleic acid, stearic acid, isostearic acid, oleic acid, linoleic acid, linolenic acid, behenic acid, erucic acid, ricinoleic acid having a hydroxyl group in the molecule, 12-hydroxystearic acid, and condensates thereof. Of these, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, oleic acid, and condensed ricinoleic acid are preferred in view of stabilization of plant sterols. More preferably, myristic acid, palmitic acid, stearic acid, and oleic acid are desirable.

  Esterification of polyglycerol and fatty acid is performed according to a method known in the art. For example, the esterification can be carried out under normal pressure or reduced pressure in the presence of an alkali catalyst, an acid catalyst or no catalyst. Moreover, the polyglycerol fatty acid ester which has various properties can be prepared by changing the mixing amount of polyglycerol and a fatty acid. For example, when obtaining a polyglycerin fatty acid ester for use in a hydrophilic surfactant, the polyglycerin and the fatty acid are charged by calculating the weight so as to be equimolar by calculation from the hydroxyl value of the polyglycerin and the molecular weight of the fatty acid. What is necessary is just to increase the number-of-moles of a fatty acid, when obtaining the polyglyceryl fatty acid ester for using for lipophilic surfactant. The resulting polyglycerol fatty acid ester may be further purified according to the usage requirements of the product used. The purification method may be any known method and is not particularly limited. For example, adsorption treatment with activated carbon, activated clay, etc., deodorization treatment under reduced pressure using water vapor, nitrogen, etc. as a carrier gas, washing with acid or alkali, or molecular distillation. And may be purified.

  The polyglycerin fatty acid ester used in the CoQ10-containing composition may be used alone or as an emulsifier composition mixed with other surfactants from the viewpoint of improving the emulsion stability. For example, the surfactant to be mixed includes glycerin fatty acid ester, propylene glycol fatty acid ester, sucrose fatty acid ester, sorbitan acid ester, polyglycerin fatty acid ester (excluding polyglycerin fatty acid ester used in CoQ10 composition), etc. Examples include nonionic surfactants, amphoteric surfactants, anionic surfactants, cationic surfactants, surfactants derived from natural products such as lecithin, enzymatically decomposed lecithin, and saponin.

  In the CoQ10-containing composition of the present invention, the composition is uniformly and stably dispersed in the food and drink for a long period of time. By using a polyhydric alcohol, the handling property is improved. Improves stability and stability when dispersed in water. In this case, the polyhydric alcohol is a generic term for compounds having two or more hydroxyl groups in one molecule, and is not particularly limited, but is a generic term for compounds having two or more hydroxyl groups in one molecule. Glycerin, diglycerin, triglycerin, polyglycerin, sorbitol, xylitol, maltitol, lactitol, sorbitan, xylose, arabinose, mannose, lactose, sugar, coupling sugar, glucose, enzyme starch syrup, acidified starch syrup, maltose starch syrup, maltose Examples thereof include isomerized sugar, fructose, reduced maltose starch syrup, reduced starch sugar syrup, honey, fructose-glucose liquid sugar, and solutions thereof, which may be used alone or in combination of two or more. Among these, propylene glycol, glycerin, diglycerin, triglycerin, and polyglycerin can be preferably used from the viewpoint of ease of preparation and stability, and further, from the viewpoint that propylene glycol and glycerin can be used in foods.

  Furthermore, by using the CoQ10-containing composition of the present invention as a polyhydric alcohol-in-oil (O / D) emulsion, CoQ10 can be blended at a high concentration, and the stability when used in beverages is particularly improved. Composition.

  The oil-in-polyol (O / D-type) emulsification in the present invention is a fine emulsion having a uniform particle size by mixing a polyhydric alcohol and a surfactant and dispersing an oil component therein. Refers to an emulsification method in which O / D type emulsification is excellent because it can be finely emulsified without requiring a large amount of mechanical force, and it can be used to various surfactants to maximize the effectiveness of the surfactant. It can be said that this is an emulsion method. O / D type emulsification is recommended for the preparation of the present composition because it has been found in the present invention to be effective in suppressing crystallization together with fine emulsification of CoQ10.

  By making the CoQ10-containing composition of the present invention into an O / D type emulsification, it has excellent acid resistance, salt resistance, and heat resistance, which are necessary when added to water-based foods such as beverages. Therefore, it is possible to add a large amount of CoQ10 to foods and drinks without reducing the commercial value.

  As the method for preparing the CoQ10-containing composition of the present invention, the above O / D type emulsification method in which a mixture of a polyhydric alcohol and the polyglycerin fatty acid ester of the present invention is prepared and emulsified with CoQ10 is recommended. The mixing method with CoQ10 is not particularly limited, and it can be obtained by emulsification using a stirring and emulsifying apparatus. For example, propeller type, anchor type, paddle type agitator, rotor / stator type emulsifier that can give stronger shearing force, mill type emulsifier with grinding function, high pressure nozzle type emulsifier that generates cavitation at high pressure , High-pressure collision emulsifiers that collide liquids under high pressure, and emulsify by impact force, shear force due to turbulent flow and cavitation, ultrasonic emulsifiers that generate cavitation with ultrasonic waves, membrane emulsification that uniformly emulsifies through pores Examples thereof include a static mixer that repeats a dispersed assembly of liquids in a machine and an element and uniformly mixes them. These can be used alone or in combination of two or more.

The composition of the CoQ10-containing composition is not particularly limited, but CoQ10 is 0.01 wt% to 50 wt%, polyglycerin fatty acid ester is 0.01 wt% to 50 wt%, and polyhydric alcohol is 10 wt%. % To 99.98% by weight, preferably CoQ10 is 1% to 30% by weight, polyglycerol fatty acid ester is 1% to 30% by weight, polyhydric alcohol is 50% to 90% by weight, More preferably, CoQ10 is 5 to 20% by weight, polyglycerol fatty acid ester is 5 to 20% by weight, and polyhydric alcohol is 70 to 80% by weight.
In order to improve the product value of the CoQ10 composition, other additive materials may be added. For example, functional oils and fats such as vitamins and polyunsaturated fatty acids, antioxidants, minerals, and the like in addition to fragrances and pigments.

The CoQ10-containing composition can be used as a supplement to the living body of CoQ10 when taken orally as it is. For example, there are solutions, tablets, powder formulations, capsules and the like for the purpose of supplying CoQ10. Moreover, the food / beverage products containing a CoQ10 containing composition are provided as one aspect | mode of a CoQ10 containing composition.
The food and drink obtained by blending the CoQ10-containing composition is particularly intended for humans, but does not exclude feed such as livestock and domestic pets. Below, the food / beverage products for humans will be described.

It does not specifically limit as food / beverage products, What is necessary is just food / beverage products which mix | blend a CoQ10 containing composition. Examples of such foods and drinks include dairy products such as milk, milk drinks, cheese, prepared powdered milk, soft drinks such as juices, lactic acid drinks, and lactic acid bacteria drinks, coffee drinks such as coffee, tea, green tea, blended tea, and barley tea, and Taste beverages such as tea-based beverages, isotonic beverages, energy drinks, or candy, gum, chocolate, cookies, biscuits, Japanese confectionery, rice confectionery, cake / pie confectionery, bread products, noodles, cake mixes, etc. , Ice cream, ice confectionery, pudding, jelly, yogurt, jam and other desserts, soy sauce, sauce, miso, sweetener, spices, dressing and other seasonings, miso soup, noodle soup, soup and other soups, fish ham Sausages, marine products, marine products such as canned fish, pickles, agricultural products such as agricultural products and canned fruits, livestock ham Sage, processed livestock products such as meat, canned, mention may be made of various other food products.
The content of the CoQ10 composition in the food and drink obtained by blending the CoQ10-containing composition is not particularly limited. What is necessary is just to contain the composition of sufficient quantity for reinforcement | strengthening of CoQ10, and what is necessary is just to determine suitably according to the composition of the food / beverage products to which a CoQ10 containing composition is applied, and the ingestion subject | substance of this food / beverage product. The content of the CoQ10-containing composition is, for example, preferably 0.0001 to 50% by weight, more preferably 0.001 to 20% by weight, and still more preferably 0.002 to 10% by weight in terms of CoQ10 in food and drink. %.
For example, when adding a CoQ10 containing composition with respect to an existing food-drinks, it can add and prepare as it is. When preparing food-drinks and a CoQ10 containing composition, it can prepare by adding to a raw material to use beforehand, or mix | blending together in a preparation process. In addition, when a CoQ10-containing composition is cooked (optionally a beverage), it can be added together with the material to prepare a food containing the CoQ10-containing composition. If the food / beverage products which can express the desired effect of a CoQ10 containing composition are obtained, there will be no limitation in particular about the addition time and addition method to food / beverage products.
A food or drink obtained by blending a CoQ10-containing composition contains a higher amount of CoQ10 than conventional food or drink, but CoQ10 is stably emulsified or solubilized, so there is no cloudiness due to precipitation of CoQ10. In particular, soft drinks and the like are mostly transparent, but the appearance of the beverage formed by blending the CoQ10-containing composition has a transparency comparable to that of the conventional beverage. Thus, according to the CoQ10 containing composition of this invention, CoQ10 can be strengthened to food / beverage products, without deteriorating the external appearance of food / beverage products.

  The cosmetic is not particularly limited, and examples thereof include lotion, milky lotion, shampoo, rinse, cosmetics for hair, foundation, lipstick, and moisturizing cream. The content of the composition is not particularly limited as long as the composition is sufficient for the effect of CoQ10.

  The pharmaceutical is not particularly limited, and examples thereof include a powder type, a tableting type, and a liquid type. Although it contains a high amount of CoQ10, since CoQ10 in the composition is stably emulsified or solubilized, there is no white turbidity due to precipitation of CoQ10, crystallization, precipitation, etc., CoQ10-derived roughness, or oiliness. According to the CoQ10-containing composition of the present invention, CoQ10 can be strengthened into a pharmaceutical product without deteriorating the appearance of the product.

  The feed is not particularly limited, and examples thereof include a powder type, a tableting type, a pellet type, and a liquid type. Unlike seeking for effects on humans such as food, drinks, cosmetics, and pharmaceuticals, the appropriate amount of the effect often corresponds to body weight, so when seeking effects on livestock, etc., many are set. What is necessary is just to determine suitably according to an ingestion object individual | organism | solid when actually using.

  The blending method of the present invention is not particularly limited, but it is recommended that CoQ10 be subjected to O / D type emulsification at a high temperature with a mixture of a polyhydric alcohol and the polyglycerin fatty acid ester of the present invention. Since the melting point and crystal state of CoQ10 change and can have paste-like fluidity even at room temperature, crystallization can be suppressed even when used for food and drink. Further, it is desirable to add a lower alcohol in consideration of fluidity. Although lower alcohol includes methanol, ethanol, isopropyl alcohol, etc., it is desirable to use ethanol when considering use for food and drink.

  Hereinafter, the present invention will be described more specifically with reference to Preparation Examples, Examples, and Test Examples, but the present invention is not limited only to such Preparation Examples, Examples, and Test Examples.

Preparation Example 1 Preparation of polyglycerin Sample: Great oil DE-1 (manufactured by Taiyo Kagaku: decaglycerin)
Great oil DE-2 (manufactured by Taiyo Kagaku: decaglycerin)
Great oil DI-1 (Taiyo Chemical Co., Ltd .: Diglycerin)
Reagents: Pyridine (manufactured by Wako Pure Chemical Industries, Ltd.), chlorophenylmethyl (manufactured by Wako Pure Chemical Industries, Ltd.), ethyl acetate (manufactured by Wako Pure Chemical Industries, Ltd.)
Apparatus: Thermometer, Dimroth, three-necked flask, stirring device, decompression device, reflux device, separatory funnel Method: Polyglycerin and pyridine were added to a three-necked flask equipped with a thermometer, Dimroth and stirring device. To this was added chlorotriphenylmethane, which is a reagent that selectively reacts with a primary hydroxyl group, and the mixture was stirred at 100 ° C. for 1 hour, returned to room temperature, and stirred for 24 hours. Further, most of the pyridine was removed from the reaction solution under reduced pressure. Water was added to the obtained reaction product, transferred to a separatory funnel, and extracted three times with ethyl acetate. The ethyl acetate layers were combined and concentrated. The obtained residue and acetic acid were added to a three-necked flask equipped with a thermometer, a Dimroth and a stirrer, and the mixture was heated to reflux for 8 hours to desorb the trimethylphenyl group. The above steps were repeated and purified polyglycerol was mixed to obtain a certain amount of polyglycerol B. Moreover, the same operation was performed also about Great oil DE-2 and Great oil DI-1, respectively, and polyglycerol C and D were obtained. Table 1 shows the hydroxyl value, primary hydroxyl group, and secondary hydroxyl group of the resulting polyglycerol.

Preparation Example 2
The residue obtained by concentrating the aqueous layer portion of Preparation Example 1 and acetic acid were added to a three-necked flask equipped with a thermometer, a Dimroth, and a stirrer and heated under reflux for 8 hours to desorb the trimethylphenyl group. The above steps were repeated and purified polyglycerol was mixed to obtain a certain amount of polyglycerol E. Table 1 shows the hydroxyl value, primary hydroxyl group, and secondary hydroxyl group ratio of the resulting polyglycerol.

  The hydroxyl value was calculated in accordance with the 7th edition Food Additives Official “Fats and Fats Test Method” or the standard fat and oil analysis test method.

Preparation Example 3 Preparation of polyglycerol fatty acid ester Sample: Polyglycerol, stearic acid, oleic acid, myristic acid, lauric acid described in Table 1 Reagents: sodium hydroxide (manufactured by Wako Pure Chemical Industries), phosphoric acid (manufactured by Wako Pure Chemical Industries, Ltd.) )
Apparatus: Four-necked flask, decompression device with nitrogen gas injection, stirring device Method: Put polyglycerin, fatty acid and sodium hydroxide described in Table 1 into a four-necked flask and remove the generated water under a nitrogen stream at 250 ° C. After the reaction, phosphoric acid was added to obtain a polyglycerol fatty acid ester. The prepared polyglycerol fatty acid ester is as shown in Table 2.

  The acid value was calculated according to the 7th edition Food Additives Official “Fats and Fats Test Method” or the Standard Oil and Fat Analysis Test Method.

Example 1 Preparation of CoQ10 Emulsified Formulation CoQ10-containing compositions were prepared using the polyglycerin fatty acid esters of Preparations 1 to 12 described in Table 2. (Invention Products 1-6 and Comparative Products 1-6) Polyglycerol fatty acid ester is heated and melted. Add polyglycerin fatty acid ester melted in glycerin and heat to 80 ° C or higher. The mixing state is confirmed while stirring at 10,000 rpm using a homomixer (manufactured by Koki Kogyo Co., Ltd.). Add CoQ10 and cool with stirring. When the product temperature drops to 60 ° C., ethanol is added and emulsified for 30 minutes. Emulsion stability was confirmed by storing for 5 days at room temperature (20-30 ° C.).
<Ingredient composition of CoQ10 containing composition> Blending amount (% by weight)
Polyglycerin fatty acid ester 13.1
Glycerin 73.9
CoQ10 10.0
Ethanol 3.0

<Emulsification stability>
◎: No difference from immediately after preparation ○: Crystal precipitation (less than about 1% of emulsion preparation)
Δ: Crystal precipitation (about 1 to 10% of emulsion formulation)
X: Crystal precipitation (over about 10% of emulsion preparation)
XX: Crystal precipitation (over about 50% of emulsion preparation)
◎ and ○ are acceptable products.

Example 2 Preparation of CoQ10 powder formulation 10 g of each of the inventive products 1 to 6 and comparative products 1 to 6 prepared in Example 1 are dissolved in 300 g of water. Then, 90 g of dextrin was added and mixed well, followed by spray drying (Okawara Kako Co., Ltd.) to obtain a CoQ10 powder formulation. (Invention products 7-12 and comparative products 7-12)
Regarding dispersion stability, 0.5 g of CoQ10 powder formulation was dissolved in 200 mL of water, and stored at room temperature (20 to 30 ° C.) for 2 days for confirmation.

<Results of dispersion stability>
◎: Dispersed uniformly, no suspended matter and precipitates are observed ○: Dispersed, but slight precipitates are observed Δ: Dispersed, but slightly suspended matter and precipitates are observed ×: Dispersed, but suspended matter XX: A lot of suspended matters and deposits are recognized. ◎ and ○ are acceptable products.

Test Example 1 Preparation of Acid Sugar Solution While stirring 88.695 g of water, 10.8 g of fructose glucose solution sugar, 0.18 g of citric acid, and 0.04 g of trisodium citrate, 0.285 g of the CoQ10-containing composition of the present invention was added. By mixing, a pale yellow transparent acid sugar solution containing CoQ10 was obtained.
The dispersion stability was stored at 40 ° C. for 7 days and visually confirmed.

<Dispersion stability>
◎: Yellow transparent liquid ○: Some cloudiness is observed (letters can be confirmed through a 100 mL beaker)
Δ: White turbidity observed (characters cannot be confirmed through a 100 mL beaker)
X: Precipitation is recognized. ◎ and ○ are acceptable products.

Test Example 2 Preparation of Milk While stirring 99.715 g of commercially available milk, 0.285 g of the CoQ10 composition of the present invention was mixed to obtain pale yellow milk containing CoQ10.
The dispersion stability was stored at 40 ° C. for 7 days and visually confirmed.

<Dispersion stability>
◎: Yellowish white liquid ○: Slightly yellowish turbidity is observed (ring shape on the liquid surface)
Δ: Yellowish cloudiness is observed (ring shape on the liquid surface)
×: Precipitation is allowed. Note that ◎ and ○ are acceptable products.

Test Example 3 Preparation of Tea Beverage Adds 99.465 g of water to 0.25 g of cha extract powder (trade name “Camelia Extract AS”, Taiyo Kagaku Co., Ltd.) and mixes with 0.285 g of the CoQ10 composition of the present invention. And a pale yellow transparent tea beverage containing CoQ10 was obtained.
The dispersion stability was stored at 40 ° C. for 7 days and visually confirmed.

<Dispersion stability>
◎: Yellow to brown transparent liquid ○: Some cloudiness is observed (letters can be confirmed through a 100 mL beaker)
Δ: White turbidity observed (characters cannot be confirmed through a 100 mL beaker)
×: Precipitation is allowed. Note that ◎ and ○ are acceptable products.

Test Example 4 Preparation of sports beverage Fructose glucose liquid sugar 8.0 g, citric acid (crystal) 0.16 g, trisodium citrate 0.06 g, salt 0.069 g, potassium chloride 0.04 g, calcium lactate 0.03 g, L -0.008 g of sodium glutamate, 1.0 g of the CoQ10 composition of the present invention, perfume preparation (trade name “Naturade Grapefruit JX”, Taiyo Kagaku Co., Ltd.) 0.1 g, appropriate amount of perfume (grapefruit flavor) A pale yellow transparent sports drink containing 100 g of CoQ10 was prepared with exchange water.
The dispersion stability was stored at 40 ° C. for 7 days and visually confirmed.

<Dispersion stability>
◎: Yellow transparent liquid ○: Some cloudiness is observed (letters can be confirmed through a 100 mL beaker)
Δ: White turbidity observed (characters cannot be confirmed through a 100 mL beaker)
X: Precipitation is recognized. ◎ and ○ are acceptable products.

Test Example 5 Preparation of sour milk beverage In 88.5 g of water, 7.2 g of granulated sugar and 0.3 g of pectin were dissolved by heating, and 4.0 g of defatted sweetened milk was mixed with the product cooled to 20 to 30 ° C. While stirring the solution, the pH was adjusted to 3.8 with a 50% aqueous solution of citric acid, and 1.5% of the CoQ10 composition of the present invention obtained in Example 2 was mixed. This beverage was homogenized with a homogenizer (150 kg / cm ² ) and filled into a 350 mL plastic bottle to obtain an acid milk beverage.
The dispersion stability was stored at 37 ° C. for 2 months and visually confirmed.

  Moreover, about the drink preserve | saved similarly, sensory evaluation was carried out by eight panelists who were trained well about the change of the flavor with respect to the sample preserve | saved at 5 degreeC refrigerator as a standard, and the degree of roughness.

In addition, the score of evaluation in Table 7 is a total score of each panel scored on the following reference | standard.
<Sensory evaluation>
Equivalent to refrigerated sample (no change): 3 points Slightly changed compared to refrigerated sample and feels rough: 2 points Remarkably different from refrigerated sample, feels rough: 1 point

<Dispersion stability>
(Double-circle): It disperse | distributes uniformly and does not recognize precipitation, aggregation, and oil floating.
○: Although uniformly dispersed, slight precipitation is observed.
Δ: Although dispersed, precipitation and aggregation are observed.
X: It is non-uniform | heterogenous and precipitation, aggregation, and oil floating are recognized.
◎ and ○ are acceptable products.

Test Example 6 Preparation of emulsion (emollient cream) According to the ratio shown in Table 10, 100 g of emulsion was prepared. Propylene glycol, glycerin and triethanolamine were added to 67.3 g of purified water and mixed by heating to obtain an aqueous phase part. Further, other components were mixed at 70 ° C., and this oil phase part was added to the aqueous phase part for preliminary emulsification. To this, 5.0 g of the CoQ10 composition of the present invention obtained in Example 2 was added, and then uniformly emulsified with a homomixer. After emulsification, the emulsion was cooled to 30 ° C. to obtain an emulsion.
The dispersion stability was stored at 50 ° C. for 1 month and visually confirmed.

<Dispersion stability>
(Double-circle): It disperse | distributes uniformly and does not recognize precipitation, aggregation, and oil floating.
○: Although uniformly dispersed, slight precipitation is observed.
Δ: Dispersed, but precipitation, aggregation, and oil floating are observed.
X: It is non-uniform | heterogenous and precipitation, aggregation, and oil floating are recognized.
◎ and ○ are acceptable products.

Test Example 7 Preparation of Pharmaceutical 15 g CoQ10 composition, 50 g taurine, 20 g vitamin B ₂ , 200 mg vitamin B ₆ , 100 mg vitamin B ₁₂ , 5 g inositol, 2 g anhydrous caffeine were dissolved in distilled water, and 100 g sucrose, D- 300 g of sorbitol and 30 g of citric acid were added and stirred uniformly. Thereafter, the pH was adjusted to 3.0 with sodium citrate and adjusted to 5000 mL with distilled water.
About dispersion stability, it preserve | saved for three months at 40 degreeC, and confirmed visually.

<Dispersion stability>
(Double-circle): It disperse | distributes uniformly and does not recognize precipitation, aggregation, and oil floating.
○: Although uniformly dispersed, slight precipitation is observed.
Δ: Dispersed, but precipitation, aggregation, and oil floating are observed.
X: It is non-uniform | heterogenous and precipitation, aggregation, and oil floating are recognized.
◎ and ○ are acceptable products.

Preparation of Test Example 8 feed CoQ10 composition 5g, iodine 10 g, vitamin E15g, vitamin _B 1 2 g, blended vitamin _B 6 2 g to basal diet 1000 g, to prepare a CoQ10 high content diet.
About storage stability, it preserve | saved for one month at 40 degreeC, and confirmed visually.

<Dispersion stability>
(Double-circle): It disperse | distributes uniformly in feed and does not recognize a yellow oil stain.
○: Although uniformly dispersed in the feed, a slight yellow oil stain is observed.
(Triangle | delta): Although disperse | distributing in feed, a yellow oil stain is recognized.
×: Uneven in the feed, yellow oil stains are observed.
◎ and ○ are acceptable products.

As shown in the above test examples, it was found that the original appearance and properties were not lost by adding a CoQ10-containing composition prepared with a specific polyglycerin fatty acid ester to foods and beverages and cosmetics. It was. This is considered that the CoQ10 containing composition containing specific polyglycerol fatty acid ester as an essential component is stably emulsified or solubilized.
Therefore, when preparing food-drinks, cosmetics, a pharmaceutical, and feed containing this CoQ10 containing composition, it has confirmed that it was widely used without any difficulty.

Claims (6)

Coenzyme Q10 and polyglycerin fatty acid ester in which polyglycerin having a hydroxyl value of polyglycerin of 1,200 or less and primary hydroxyl group of 50% or more of all hydroxyl groups and fatty acid esterified Coenzyme Q10 containing composition characterized. 2. The coenzyme Q10-containing composition according to claim 1, wherein the composition is a polyhydric alcohol-in-oil type (O / D type) composition. Food-drinks containing the composition of Claim 1 or 2. Cosmetics containing the composition of Claim 1 or 2. A pharmaceutical comprising the composition according to claim 1 or 2. A feed containing the composition according to claim 1 or 2.