JP2000044474A - Water-soluble vitamin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a water-soluble vitamin composition useful for foods, pharmaceuticals and cosmetics, capable of stably preserving a water-soluble vitamin therein for a long time and superior in taste by including the water-soluble vitamin, a glycerin fatty acid ester and a neutral lipid. SOLUTION: This composition is obtained by including (A) a water-soluble vitamin (e.g. L-ascorbic acid) in the form of solid particles with an average diameter of pref. <=1 μm, (B) a glycerin fatty acid ester (e.g. polyglycerin condensed ricinoleic acid ester) pref. <=4 in HLB number and (C) a neutral lipid (e.g. medium chain fatty acid triglyceride)(with a melting point of pref. <=45 deg.C in the ratios of A to the whole composition of pref. 15 to 50 wt.% and of B/C of 1 to 100 wt.%. The composition, when dispersed in an aqueous food of e.g. palatable beverage or processed milk product or in an aqueous cosmetic of e.g. cosmetic emulsion, forms a stable W/O/W emulsion system without eluting the water-soluble vitamin contained therein through an emulsification inversion.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a composition containing a water-soluble vitamin and a derivative thereof as a physiologically active ingredient,
And foods, medicines and cosmetics using the composition.

[0002]

2. Description of the Related Art Water-soluble vitamins and derivatives thereof have been used in a wide range of applications as nutrients for pharmaceuticals, cosmetics and foods or as antioxidants due to their physiological actions. However, since these compounds have a unique taste, they are disadvantageous in that they are restricted in use in food applications and are unstable to oxidation, heat, and light as represented by L-ascorbic acid.

As a method for stabilizing a water-soluble vitamin, there are some functionalities of vitamin molecules such as esterification with a fatty acid (Japanese Patent Publication No. 55-45546, etc.), phosphoric esterification and complexation (Japanese Patent Laid-Open No. 7-53581, etc.). A method has been proposed in which a group is replaced with an appropriate substituent, or a method in which an amino acid or an organic acid is used in combination as a stabilizer (Japanese Patent Publication No. 57-48050). Problems remain.

When an amino acid or an organic acid is used in combination as a stabilizer, the oxidation of water-soluble vitamin itself or the pH conditions may cause ammonia or the like, or the taste of the stabilizer itself may have an adverse effect on use. There are problems such as the effect.

[0005] In addition, a method of mixing and coating a simple substance of a vitamin and a salt thereof with a mixture of an oil and a fat having a melting point of 50 to 80 ° C and an emulsifier (Japanese Patent Publication No. 57-48050), or a method of preparing an aqueous solution of a vitamin and a salt thereof from a lipophilic sorbitan fatty acid ester,
A method of emulsifying fats and oils to which a sucrose fatty acid ester and a polyglycerin condensed ricinoleate ester and the like are added to obtain a water-in-oil (W / O) emulsified fat and oil composition (Japanese Patent Publication No. Sho 63)
-96727, JP-A-6-343400, etc.).

However, in the former method, a W / O dispersed solid / solid interface is formed by coating the crystal surface of a water-soluble vitamin with a solid oil having a high melting point. The application range is limited because the vitamin crystals used are coarse crystals of several tens of μm or more, and are in a granular form of about 0.2 to 2 mm coated with a high melting point solid fat, especially for liquid products. Application becomes extremely difficult.

In the latter, the internal aqueous phase is 0.2 to 5 μm.
m / W emulsified composition of about m is obtained, and the range of application is widened, but the physical strength of the emulsified interface is weak because vitamins are in an aqueous solution state, and decomposition and the like are likely to occur after a heating step such as sterilization. In addition, since it is a W / O emulsified liquid / liquid interface, there is a disadvantage that the emulsified state is liable to undergo phase inversion destruction when exposed to physical stress such as stirring or pumping.

[0008]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a water-soluble vitamin composition which keeps the water-soluble vitamin stable for a long period of time and which is excellent in taste.

[0009]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the object of the first period, and as a result, have found that a water-soluble vitamin composition containing a water-soluble vitamin, a glycerin fatty acid ester and a neutral lipid can be obtained. The present inventors have found that it is possible to mask a peculiar taste peculiar to a water-soluble vitamin and to have excellent stability, and have completed the present invention.

That is, the present invention relates to a method for converting water-soluble vitamins, which have been ultrafinely divided into particles having an average particle diameter of 1 μm or less by physical crushing, into HLB.
The present invention relates to a vitamin composition dispersed in W / O in a neutral lipid having a glycerin fatty acid ester of 4 or less and a melting point of 45 ° C. or less.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The water-soluble vitamin in the present invention is not particularly limited, but vitamin C and its derivatives ascorbic acid-2-phosphate, ascorbic acid-2-glucosides, vitamin B ₁ and Derivatives such as thiamine propyl disulfide, thiamine tetrafurfuryl disulfide, thiamine-8-methyl-
6-acetyldihydrothioctoate disulfide, O,
S- dicarboethoxy thiamine hydrochloride, S- benzoyl thiamine -O- monophosphate, O- benzoyl thiamine disulfide, is vitamin B ₂ and its derivatives 5-deaza-7,8 Jidemechiru -8-hydroxy riboflavin like Ya flavin mononucleotide, coenzyme riboflavin such as flavin adenine dinucleotide, pyridoxine, pyridoxal, free-form vitamin of B ₆ and its phosphoric acid ester type or a glucoside type derivatives such as pyridoxamine, vitamin B _12, niacin, pantothenic acid and folic acid, the It is a selected one or a mixture of two or more, but is preferably insoluble in neutral lipids and has an average particle size of 1 μm as measured by laser diffraction particle size distribution by physical crushing.
It is a water-soluble vitamin with the following properties that can be converted to ultrafine particles. Regarding the physical crushing method, use of a wet crusher such as a co-ball mill, a dry crusher such as a jet mill, or freeze crushing using liquid nitrogen, etc. is mentioned, but the average particle size is 1 μm or less by laser diffraction type particle size distribution measurement. Any material can be used as long as it has a performance capable of forming ultrafine particles. If the average particle size is larger than 1 μm, the dispersion stability in neutral lipids will be reduced, and fine particles of vitamins will precipitate and separate.

Although the content of the water-soluble vitamin of the present invention is not particularly limited, it is preferably from 1 to 70% by weight, more preferably from 15 to 50% by weight in the composition. When the amount of vitamin is less than 1% by weight, the amount of vitamin as a main ingredient becomes very small, so that it is not used as a vitamin composition. On the other hand, if the amount of vitamin is more than 70% by weight, the structural viscosity becomes extremely high and the fluidity is lost, so that the subsequent processing characteristics and application range are significantly narrowed.

The glycerin fatty acid ester used in the present invention is not particularly limited. However, organic acid monoglyceride having an HLB of 4 or less, polyglycerin fatty acid ester and polyglycerin condensed ricinoleate, preferably citrate glyceride, malate glyceride, glyceride acetate Succinic acid glyceride, diacetyltartaric acid glyceride, polyglycerol having an average degree of polymerization of 2 to 10 and carbon number of 6 to 6
A mixture of at least one fatty acid ester of 22 and an ester of polyglycerol having an average degree of polymerization of 2 to 10 and polyricinoleic acid having a degree of condensation of 2 to 4; 1-100
However, if the amount added is less than 1% by weight, it is impossible to sufficiently disperse the vitamin microparticle crystals,
When the content is more than 100% by weight, when the composition is newly dispersed in an aqueous system, the included water-soluble vitamin fine particles are easily eluted due to emulsification phase inversion, which hinders the formation of a stable W / O / W emulsion system. Come.

The neutral lipid used in the present invention is not particularly limited, but is generally a vegetable oil obtained from synthetic oils such as medium-chain fatty acid triglyceride and oil seeds such as soybean, rice, rapeseed, cacao, and coconut. Fats and beef tallow, milk fat, animal fats such as lard, can be used, and phospholipids, sterols, waxes and oil-soluble vitamins originally contained in them can be used together, Melting point 45
An oil component that can be used in a heating range of not higher than 0 ° C. is preferable, and the melting point is more preferably not higher than room temperature. When a neutral lipid having a melting point higher than 45 ° C. is used, a plurality of heating steps are required at the time of preparing a water-soluble vitamin composition and adding it to foods, etc., so that a strong heat history is given to the water-soluble vitamin. The range will also be extremely narrowed. Hereinafter, the present invention will be described with reference to Examples and Test Examples, but the present invention is not limited thereto.

[0015]

Example 1 50 parts by weight of medium-chain fatty acid triglyceride (melting point -11 ° C,
Taiyo Chemical Co., Ltd.), 10 parts by weight of polyglycerin condensed ricinoleate (Sunsoft 818H; HLB)
1, manufactured by Taiyo Kagaku Co., Ltd.) to prepare an oily suspension containing 40 parts by weight of L-ascorbic acid crystals (average particle size: about 100 μm, manufactured by Nippon Roche Co., Ltd.). And the average particle size of L-ascorbic acid was 0.4 μm as determined by laser diffraction particle size distribution measurement to obtain a W / O dispersion composition.

Example 2 Rapeseed white squeezed oil 70 parts by weight (melting point 12 ° C.), polyglycerin condensed ricinoleate 5 parts by weight (Sunsoft 81)
8H; HLB1, manufactured by Taiyo Chemical Co., Ltd.) and 5 parts by weight of polyglycerin stearate (Sun Fat PS)
-68; HLB3.5, manufactured by Taiyo Kagaku Co., Ltd.), and mixed with 20 parts by weight of riboflavin crystals (average particle size of about 100).
μm, manufactured by Takeda Pharmaceutical Co., Ltd.) was prepared, and the suspension was applied to a Koball Mill (manufactured by Shinko Pantec Co., Ltd.), and the average particle size of the riboflavin crystals was determined to be 0. W / O became 35 μm
A dispersion composition was obtained.

Example 3 50 parts by weight of medium-chain fatty acid triglyceride (melting point -11 ° C.,
Taiyo Chemical Co., Ltd.), 5 parts by weight of polyglycerin condensed ricinoleate (Sunsoft 818SX; HLB)
0.5, manufactured by Taiyo Kagaku Co., Ltd.) and 5 parts by weight of citrate monoglyceride (Sunsoft 623M; HLB4, manufactured by Taiyo Kagaku Co., Ltd.), and 40 parts by weight of L-ascorbic acid crystals (average particle diameter: about 100 μm, Japan An oily suspension to which L-ascorbic acid was added was prepared using a Koball Mill (manufactured by Shinko Pantech Co., Ltd.), and the average particle diameter of L-ascorbic acid was determined to be 0.4 μm by laser diffraction particle size distribution measurement. The resulting W / O dispersion composition was obtained.

Test Example 1 50 parts by weight of medium chain fatty acid triglyceride (melting point −11 ° C.,
Taiyo Chemical Co., Ltd.), 10 parts by weight of polyglycerin condensed ricinoleate (Sunsoft 818H; HLB)
1, manufactured by Taiyo Kagaku Co., Ltd.) and stirred at high speed with a homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) while adding 40 parts by weight (pH 2.0) of a 10% aqueous solution of L-ascorbic acid, followed by laser diffraction. A W / O emulsion having an average particle size of the internal aqueous phase of 0.4 μm as determined by a mold particle size distribution measurement was prepared. Using this as a control, the oxidation state of L-ascorbic acid in the W / O dispersion composition of Example 1 was compared.

200 g of each of the two was sealed in a pressure bottle and sterilized by heating at 121 ° C. for 30 minutes.
g, 200 ml of a 2% aqueous solution of metaphosphoric acid and 200 ml of n-hexane were added, and the mixture was shaken and extracted at room temperature.
The obtained aqueous layer was collected and filtered through a 0.45 μm membrane filter to obtain a test solution, and H was provided with an amide-bonded reverse-phase column (Amide 80, manufactured by Tosoh Corporation).
The amount of L-ascorbic acid was measured by PLC. The elution solvent used was an acetonitrile / 2.5 mM potassium phosphate solution (50/50), and the detection was measured by the absorbance at 254 nm. Then, both are stored at 50 ° C. for 3 months,
The same measurement as described above was performed every month, and the emulsified state was observed.

L-ascorbic acid easily loses a hydrogen atom from the enol groups at the 2- and 3-positions in the presence of water, and becomes a keto-type isomer, dehydroascorbic acid. To decompose into oxalic acid. Only L-ascorbic acid in these compounds is 25%
Because it has the property of exhibiting specific absorption at a wavelength of 4 nm,
Using this as an index, the residual ratio of L-ascorbic acid was determined, and the stability as vitamin C was compared.

As a result, as shown in Table 1, W
In the / O dispersion composition, the attenuation of L-ascorbic acid hardly occurred, and excellent stability was exhibited.

[0022]

[Table 1]

Test Example 2 70 parts by weight of rapeseed white oil (melting point: 12 ° C.), 10 parts by weight of polyglycerin condensed ricinoleate (Sunsoft 8)
18H; HLB1, manufactured by Taiyo Chemical Co., Ltd.)
% Riboflavin aqueous solution (manufactured by Takeda Pharmaceutical Co., Ltd.) while adding 20 parts by weight of a riboflavin aqueous solution with high-speed stirring using a homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). A W / O emulsion of 0.35 μm was prepared. Using this as a control, a sensory test was conducted on the W / O dispersion composition of Example 2 by 10 panelists to compare the unique flavor masking properties of riboflavin.

As a result, as shown in Table 2, W of Example 2
The / O dispersion composition exhibited excellent taste with little or no unique flavor of riboflavin.

[0025]

[Table 2]

Test Example 3 50 parts by weight of medium-chain fatty acid triglyceride (melting point −11 ° C.,
Taiyo Chemical Co., Ltd.), 10 parts by weight of polyglycerin condensed ricinoleate (Sunsoft 818H; HLB)
1, manufactured by Taiyo Kagaku Co., Ltd.) and stirred at high speed with a homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) while adding 40 parts by weight (pH 2.0) of a 10% aqueous solution of L-ascorbic acid, followed by laser diffraction. A W / O emulsion having an average particle size of the internal aqueous phase of 0.4 μm as determined by a mold particle size distribution measurement was prepared. 5 parts by weight of sucrose fatty acid ester (Ryoto Sugar Ester S-1670, manufactured by Mitsubishi Chemical Corporation)
Was dissolved in 1000 parts by weight of water in which
An O / W emulsion was prepared.

Similarly, the W / O dispersion composition of Example 3 was added to 1000 parts by weight of water in which 5 parts by weight of sucrose fatty acid ester (Ryoto Sugar Ester S-1670, manufactured by Mitsubishi Chemical Corporation) was dissolved. Stir to prepare a W / O / W emulsion, seal 200 g of each with a pressure bottle,
The solution was sterilized by heating at 21 ° C. for 15 minutes. After cooling, 50 g of the solution was collected, 200 ml of a 2% aqueous solution of metaphosphoric acid and 200 ml of n-hexane were added, and the mixture was shaken and extracted at room temperature. Was collected and filtered through a 0.45 μm membrane filter to obtain a test solution, and an HPL equipped with an amide-bonded reverse-phase column (Amide 80, manufactured by Tosoh Corporation) was used.
C was used to measure the amount of L-ascorbic acid. The elution solvent was acetonitrile / 2.5 mM potassium phosphate solution (50 mM).
/ 50), and the detection was measured by the absorbance at 254 nm. Thereafter, both were stored at 40 ° C. for 3 weeks, and the same measurement was carried out every week, and the emulsified state was observed.

As a result, as shown in Table 3, W of Example 3
The / O dispersion composition showed excellent stabilization even with little attenuation of L-ascorbic acid even under unstable emulsification conditions of the W / O / W type.

[0029]

[Table 3]

Application Example 1 3 parts by weight of the L / ascorbic acid W / O dispersion composition of Example 3 was added to 100 parts by weight of a commercially available plain yogurt and mixed by stirring to prepare 1200 mg / g vitamin C-enriched yogurt. . L-ascorbic acid 1.2 as a control
A part of the yogurt was prepared by adding 100 parts by weight of the same plain yogurt and dissolved, and the flavor, the product form and the residual ratio of L-ascorbic acid were compared. It was remarkably remarkable, and the milk protein was dissolved by the decrease in pH, and the state became out of the form of yogurt,
In the case where the W / O dispersion composition of Example 3 was added, the original flavor was hardly impaired.

When the residual ratio of L-ascorbic acid was analyzed in accordance with the measuring method of Test Example 3, the residual ratio of the control product was 45.0%, whereas the residual ratio of W / O of Example 3 was 45.0%.
The residual ratio in the case where the dispersion composition was added was 94.3%, and the effect of the present invention in an aqueous acidic food was sufficiently confirmed.

Application Example 2 3 parts by weight of the L / ascorbic acid W / O dispersion composition of Example 1 was added to 100 parts by weight of a commercially available cake premix, mixed by stirring, and baked at 160 ° C. for 30 minutes to form a pound cake. Was prepared. As a control, 1.2 parts by weight of L-ascorbic acid was added to and dissolved in 100 parts by weight of the same cake premix to prepare a pound cake.
When the product form and the residual ratio of L-ascorbic acid were compared, the acidity of L-ascorbic acid was remarkably remarkable in the control product, and the foaming property of the cake was reduced to a low bulk state. In the case where the W / O dispersion composition of Example 3 was added, the original flavor and foamability were hardly impaired.

When the residual ratio of L-ascorbic acid was analyzed in accordance with the measuring method of Test Example 3, the residual ratio of the control product was 30.0%, whereas the W / O ratio of Example 3 was
The residual ratio in the case where the dispersion composition was added was 87.3%, and the effect of the present invention in the heating step could be sufficiently confirmed.

[0034]

It is needless to say that effective supply of vitamins is necessary for maintaining health. However, since water-soluble vitamins have their own degradability and peculiar flavor, they are conventionally used in sugar-coated tablets, tablet tablets and drinks. Pharmaceutical supply forms such as have been generalized. In recent years, many types of foods such as soft drinks and biscuits have been found in foods.However, in foods that require a severe heat history such as sterilization and baking, the natural physiological activity of vitamins is significantly impaired. It is in the present situation. In the aqueous solution of the water-soluble vitamin composition of the present invention, preferably milk drink, soft drink, fruit juice drink,
Emulsification when dispersed in taste drinks such as tea drinks and coffee drinks, dairy products such as yogurt, ice cream and whipped cream, water-based foods such as desserts such as pudding and jelly, or water-based cosmetics such as cosmetic milky lotions and lotions Water-soluble vitamins included by phase inversion do not elute,
It is characterized by constituting a stable W / O / W emulsion system. The W / O / W emulsification system referred to herein has a double emulsification structure in which ultrafine crystal particles of a water-soluble vitamin are stably dispersed in oil droplets of a neutral lipid dispersed in water. The present invention provides water-soluble vitamins essential to human beings in a form that can be adapted to various food processing, and is applicable to all water-soluble vitamins without being limited to specific vitamins.

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Claims (4)

[Claims] 1. A vitamin composition comprising a water-soluble vitamin, a glycerin fatty acid ester and a neutral lipid. 2. The vitamin composition according to claim 1, wherein the water-soluble vitamin is a solid having an average particle size of 1 μm or less. 3. The vitamin composition according to claim 2, wherein the glycerin fatty acid ester has an HLB of 4 or less. 4. The vitamin composition according to claim 1, wherein the melting point of the neutral lipid is 45 ° C. or lower.