JP2021104971A - Astaxanthin-containing particles - Google Patents

Abstract

To provide astaxanthin-containing particles in which the deterioration of astaxanthin due to long-term storage is suppressed.SOLUTION: There is provided an astaxanthin-containing particles that contains the following components (A), (B) and (C): (A) agar and/or gelatin; (B) astaxanthin; and (C) a tocopherol composition having a total content of d-γ-tocopherol and d-δ-tocopherol in total tocopherol of 90 mass% or more; the astaxanthin-containing particles having a continuous phase containing component (A) and a dispersed phase containing components (B) and (C) dispersed in the continuous phase.SELECTED DRAWING: Figure 1

Description

The present invention relates to astaxanthin-containing particles.

Carotenoids are oil-soluble pigment components that have long-chain conjugated double bonds and exhibit yellow to red or the like, and have been conventionally used as colorants for foods and the like. In addition, various physiological activities such as provitamin A activity that can be converted to vitamin A in the living body, antioxidant action, anticancer / antitumor action, etc. are recognized, and it has been attracting attention as an active ingredient of pharmaceuticals and health foods. ing.

When carotenoids are used in pharmaceuticals, health foods, etc., it is generally practiced to granulate them, mix them with other active ingredients, excipients, etc. in powder form, and tablet them into tablets. There is. As a method for atomizing carotenoids, for example, carotenoids are dispersed in an aqueous solution containing a hydrophilic polymer gelling agent (gelatin, agar, etc.) having a thermoreversible sol-gel transition property as a main component to produce the carotenoids. An example is a method of drying after graining. The particles obtained by this method are easily tableted because the hydrophilic polymer gel in the continuous phase forms a film that protects the carotenoids in the dispersed phase and appropriate strength is imparted.

Examples of the carotenoid-containing particles include carotenoid-containing particles (Patent Document 1) and β-cryptoxanthin, which have a structure in which carotenoids are dispersed in an agar gel containing cyclodextrin and / or a vegetable protein. A multi-core type microcapsule (Patent Document 2) or the like containing a paprika pigment composition having an amount of 1.0% or more as a core substance and the film-forming substance being a hydrophilic polymer gelling agent has been proposed.

However, for astaxanthin, which is a kind of carotenoid, in producing similar particles, even if L-ascorbic acid palmitic acid ester is used as an antioxidant in order to suppress the deterioration of astaxanthin due to oxidation during storage, it takes a long time. The effect was not sufficient in the preservation of. Therefore, for astaxanthin-containing particles, a method capable of sufficiently suppressing the deterioration of astaxanthin during long-term storage has been required.

International Publication No. 2017/170528 Japanese Unexamined Patent Publication No. 2013-0344446

An object of the present invention is to provide astaxanthin-containing particles in which deterioration of astaxanthin due to long-term storage is suppressed.

As a result of diligent studies on the above problems, the present inventor has found that the above problems can be solved by using extracted tocopherol having a specific composition, and based on this finding, the present invention has been made. ..

That is, the present invention
The following components (A), (B) and (C):
(A) Agar and / or gelatin,
(B) Astaxanthin,
(C) Astaxanthin-containing particles containing a tocopherol composition having a total content of d-γ-tocopherol and d-δ-tocopherol in total tocopherol of 90% by mass or more, and continuously containing the component (A). It is composed of astaxanthin-containing particles having a phase and a dispersed phase containing the components (B) and (C) dispersed in the continuous phase.

The astaxanthin-containing particles of the present invention are those in which deterioration of astaxanthin due to long-term storage is sufficiently suppressed.

FIG. 1 is a schematic view showing the structure of astaxanthin-containing particles of the present invention.

[Ingredient (A)]
The astaxanthin-containing particles of the present invention contain agar and / or gelatin as the component (A).

The agar is not particularly limited, but one extracted from red algae such as Amakusa, Gracilaria, Gelidiaceae, and Gelidiaceae is preferable. The shape of the agar may be any of powdered agar, flake agar, stick agar, thread agar and the like, but powdered agar is preferably used because of its high solubility and ease of handling.

The jelly strength of agar is not particularly limited, but for example, 250 to 750 g / cm ² is preferably used. The jelly strength is a value measured by the Nichikansui method. That is, it refers to the maximum load (g) that can withstand fracture of a gel prepared by preparing an aqueous agar solution having a concentration of 1.5% by mass and allowing it to stand at 20 ° C. for 15 hours to solidify the gel for ^{20 seconds per 1 cm 2 of its surface.}

Examples of agar include Ultra Agar RB (trade name; powdered agar; jelly strength: 280 to 320 g / cm ² ; manufactured by Ina Food Industry Co., Ltd.) and Ina Agar UP-37 (trade name; powdered agar; jelly strength: 670- 730 g / cm ² ; manufactured by Ina Food Industry Co., Ltd.) and the like are commercially manufactured and sold, and these can be used in the present invention.

As the gelatin, one usually produced by heat-extracting crude collagen obtained by treating the skin, bones, tendons of cows, pigs, chickens, etc. with acid or alkali with water is used. Further, fish gelatin made from the skin and bone of fish such as tuna, salmon and tilapia can also be used.

The gelatin jelly strength may be in the range of 0 to 285 g, preferably a jelly strength of 85 g or more, and more preferably a jelly strength of 100 to 280 g. The jelly strength is measured according to the jelly strength test specified in "Gelatin and gelatin" of Japanese Industrial Standards (JIS) K6503-1996.

As the gelatin, for example, gelatin BP-250 (trade name; jelly strength: 240 to 280 g; manufactured by Nippi Co., Ltd.) and the like are commercially manufactured and sold, and this can be used in the present invention.

[Component (B)]
The astaxanthin-containing particles of the present invention contain astaxanthin as the component (B). The astaxanthin may be derived from a natural product or chemically synthesized as long as it is obtained according to a conventional method. Examples of astaxanthin derived from natural products include those extracted from red yeast fafia, green alga Hematococcus, marine bacteria, krill, etc. Among them, green algae are industrially available in large quantities and stably. It is preferably extracted from Hematococcus.

Astaxanthin is generally distributed in the form of astaxanthin-containing fats and oils in which astaxanthin is dissolved or dispersed in fats and oils for the purpose of preventing oxidation and adjusting the viscosity. The astaxanthin used in the present invention may be in the form of such astaxanthin-containing fats and oils.

Astaxanthin includes astaxanthin oil 50F (trade name; fat and oil containing 5% by mass of astaxanthin; manufactured by Fuji Chemical Industry Co., Ltd.), AstaZine haematococcus algae pigment oil 20% (trade name; fat and oil containing 20% by mass of astaxanthin; BGG). (Manufactured by the company) and the like are commercially manufactured and sold, and these can be used in the present invention.

[Component (C)]
The astaxanthin-containing particles of the present invention have the total content of d-γ-tocopherol and d-δ-tocopherol in the total tocopherol as the component (C) (hereinafter, also referred to as “d-γ, δ-tocopherol amount”). Contains 90% by mass or more, preferably 95% by mass or more, more preferably 97% by mass or more of the tocopherol composition.

Here, the total tocopherol refers to a family of four types of tocopherols, d-α-tocopherol, d-β-tocopherol, d-γ-tocopherol and d-δ-tocopherol.

The tocopherol composition is not particularly limited as long as it contains d-γ-tocopherol and / or d-δ-tocopherol so that the amount of d-γ, δ-tocopherol is within the above range. Specifically, it is preferable to use extracted tocopherol.

Extracted tocopherol is a mixture of tocopherols recovered from deodorized distillates (for example, deodorized scum, deodorized sludge, hot well oil, etc.) produced as a by-product in the process of refining vegetable oil, and is d-α-tocopherol, d. It contains tocopherol homologues such as -β-tocopherol, d-γ-tocopherol and d-δ-tocopherol. Extracted tocopherols are obtained by separating and refining from deodorized distillates such as canola oil, sesame oil, rice oil, safflower oil, soybean oil, corn oil, rapeseed oil, palm oil, sunflower oil, cottonseed oil, and peanut oil. Examples thereof include a mixture containing a homologous form of the above-mentioned tocopherol.

Since the composition of each homologous in the extracted tocopherol is affected by the type, variety, production area, etc. of the plant, in the present invention, the amount of d-γ, δ-tocopherol is 90% by mass by a purification step such as molecular distillation. The above-enhanced extracted tocopherol is preferably used.

Some extracted tocopherols are distributed in a form containing fats and oils in addition to total tocopherols for concentration adjustment, viscosity adjustment, and the like. The extracted tocopherol used in the present invention may have such a form.

Examples of the extracted tocopherol include Emix D (trade name; d-γ, δ-tocopherol amount: 99.3% by mass; manufactured by Mitsubishi Chemical Foods Co., Ltd.), RIKEN E Oil CP-3 Plus L (trade name; d-). γ, δ-tocopherol amount: 98.5% by mass; manufactured by RIKEN Vitamin), RIKEN E Oil Super 80 (trade name; d-γ, δ-tocopherol amount: 98% by mass; manufactured by RIKEN Vitamin), etc. are commercially available. It is manufactured and sold in Japan, and these can be used in the present invention.

The content of each homologous substance in the extracted tocopherol is determined by the quantitative method (liquid chromatography) described in "d-α-tocopherol" of "9th Edition Food Additives Official Standard" (Japan Food Additives Association). It is measured according to the quantitative method).

[Structure of astaxanthin-containing particles]
The astaxanthin-containing particles of the present invention have a continuous phase containing the component (A) and a dispersed phase containing the components (B) and (C) dispersed in the continuous phase.

[Method for producing astaxanthin-containing particles]
The method for producing astaxanthin-containing particles of the present invention is particularly limited as long as it is a method for obtaining particles having a structure in which the dispersed phases containing the components (B) and (C) are dispersed in a continuous phase containing the component (A), for example. However, specifically, a dispersion liquid is prepared by dispersing the dispersion phase containing the components (B) and (C) in the aqueous phase containing the component (A), and the dispersion liquid is made into droplets. There is a method of cooling and solidifying. More specifically, it can be produced, for example, by carrying out the following steps (1) to (5).

Step (1): Ingredient (A) is added to warmed water, stirred and dissolved, and this is used as an aqueous phase.
Step (2): The components (B) and (C) are stirred and mixed, and this is used as a dispersed phase.
Step (3): While keeping the temperature of the aqueous phase prepared in (1) constant, the dispersed phase prepared in (2) was added thereto and stirred to uniformly disperse the dispersed phase in the aqueous phase. Obtain a dispersion.
Step (4): The dispersion liquid prepared in (3) is made into droplets by a method known per se, such as a dropping method, a spraying method, and a dispersion method, and cooled to obtain frozen fine particles.
Step (5): Collect the fine particles produced in (4), and use a shelf-type ventilation dryer, fluidized bed dryer, vacuum freeze dryer, vibration vacuum dryer, etc. to collect the desired moisture content. Dry to obtain particles having a structure in which the dispersed phase containing the components (B) and (C) is dispersed in the continuous phase containing the component (A).

The temperature of water in the step (1) and the temperature of the aqueous phase in the step (3) are preferably 70 to 90 ° C. when the component (A) is agar, and when the component (A) is gelatin, the temperature is preferably 70 to 90 ° C. It is preferably 45 to 75 ° C.

When the component (A) is agar, the dispersion prepared in the step (3) has a content of the component (A) of 10 to 60 parts by mass and a content of the component (B) of 5 to 50 parts by mass. , The content of the component (C) is preferably 0.05 to 5 parts by mass, and the content of water is preferably 100 to 400 parts by mass. Further, when the component (A) is gelatin, the content of the component (A) is 20 to 70 parts by mass, the content of the component (B) is 5 to 60 parts by mass, and the component (C) is blended. The content of gelatin is preferably 0.05 to 10 parts by mass, and the content of water is preferably 100 to 300 parts by mass.

The ratio (mass ratio) of the aqueous phase to the dispersed phase in the dispersion prepared in the step (3) is 80/20 to 99/1, preferably 80/20 to 99/1 in the aqueous phase / dispersed phase when the component (A) is agar. It is 90/10 to 97/3. When the dispersion liquid is prepared in such a ratio, the ratio of the continuous phase to the dispersed phase in the astaxanthin-containing particles after drying in the step (5) is about 50/50 to 96/4 in the continuous phase / dispersed phase. Is preferable.

The ratio (mass ratio) of the aqueous phase to the dispersed phase in the dispersion prepared in the step (3) is 85/15 to 99/1 in the aqueous phase / dispersed phase when the component (A) is gelatin. It is preferably 90/10 to 97/3. When the dispersion liquid is prepared in such a ratio, the ratio of the continuous phase to the dispersed phase in the astaxanthin-containing particles after drying in the step (5) is about 40/60 to 96/4 in the continuous phase / dispersed phase. Is preferable.

A high-speed rotary dispersion / emulsifier such as TK Homomixer (manufactured by Primix Corporation) or Clairemix (manufactured by M-Technique Co., Ltd.) is used for stirring the steps (1) and (3). As the stirring conditions, it is preferable that the rotation speed is 3000 to 12000 rpm and the stirring time is 5 to 60 minutes.

From the viewpoint of productivity, the fine particle formation in the step (4) is preferably carried out by spraying droplets into a column filled with liquid nitrogen by a spraying method. For spraying, for example, a pressurized spray nozzle, a rotary spray nozzle, a rotary disk, or the like is used, and a rotary spray nozzle is preferable. When a rotary spray nozzle is used, a preferred rotation speed of 200 to 2000 rpm can be exemplified. The cooling temperature is preferably -196 to −15 ° C., more preferably −120 to −20 ° C.

The drying in the step (5) is preferably performed using a fluidized bed dryer because it can be dried in a short time. In this case, in order to suppress adhesion between the particles after drying, the particles are made into fine particles in advance before drying. On the other hand, it is preferable to add a desiccant such as calcium stearate and glycerin fatty acid ester and mix them. The amount of the lubricant added is usually 1 to 6% by mass with respect to 100% by mass of the fine particles. Drying is carried out until the water content is usually 10% by mass or less, preferably 5% by mass or less. After drying, the astaxanthin-containing particles obtained may be mixed by adding a fluidizing agent such as fine silicon dioxide in order to prevent the particles from adhering to each other or solidifying due to static electricity or the like. The amount of the fluidizing agent added is usually 0.1 to 4% by mass with respect to 100% by mass of the astaxanthin-containing particles.

The average particle size of the astaxanthin-containing particles obtained through each of the above steps is preferably 100 to 1000 μm, more preferably 100 to 400 μm. Examples of the method for measuring the average particle size include a laser diffraction method, a wet image analysis method, a centrifugal sedimentation method, an electrical detection band method, and a sieving method. Examples of the average particle size measuring device include a laser diffraction type particle size distribution measuring device, a laser diffraction type particle size distribution measuring device, a spray particle size distribution measuring device, an image analysis type particle size distribution measuring device, and a sonic vibration type sieving measuring device. , Centrifugal sedimentation type particle size distribution measuring device, high precision particle size distribution measuring device, precision particle size distribution measuring device and the like.

[Other ingredients]
The astaxanthin-containing particles of the present invention may contain any component other than the above-mentioned components (A), (B) and (C) as long as the object of the present invention is not impaired. Examples of such components include excipients, antioxidants, emulsifiers, pH regulators, sweeteners, flavors and the like. These components may be added to either the aqueous phase or the dispersed phase depending on their properties.

Examples of excipients include celluloses such as crystalline cellulose, sugars such as lactose and purified sucrose, sugar alcohols such as D-sorbitol, D-mannitol, erythritol and trehalose, corn starch, potato starch, partially pregelatinized starch and the like. Examples thereof include starches, calcium phosphate, anhydrous calcium hydrogen phosphate, aluminum silicate, magnesium aluminometasilicate and other inorganic substances. As the antioxidant, for example, vitamin Es [excluding those used as component (C)). ], Ascorbic acids (eg, L-ascorbic acid palmitic acid ester, etc.), catechin, rosemary extract, sunflower extract, enzyme-treated rutin, ferulic acid, quercetin and the like. Examples of the emulsifier include glycerin fatty acid ester, sorbitan fatty acid ester, sucrose fatty acid ester, polyoxyethylene sorbitan fatty acid ester, lecithin and the like. Examples of the pH adjuster include sodium hydroxide, sodium hydrogencarbonate and the like. Examples of the sweetener include acesulfame potassium, aspartame, neotame and the like. Examples of fragrances include citrus essential oils such as orange, lemon, lime and grapefruit, flower essential oils, peppermint oil, sparemint oil, vegetable essential oils such as spice oil, cola nut extract, coffee extract, crocodile extract and cocoa extract. Oily extracts such as kuto, tea extract, spice extract and their oleoledins, synthetic fragrance compounds (eg L-menthol, etc.), oily blended fragrance compositions and any mixture thereof, oily dressing Examples thereof include powdered fragrances dried together with fragrances and excipients.

Further, the astaxanthin-containing particles of the present invention are cyclodextrin as disclosed in Japanese Patent No. 6470471 in order to suppress the exudation of astaxanthin from the particles when the component (A) is agar during tableting or storage. It may contain dextrin and / or vegetable protein. The cyclodextrin and / or vegetable protein is preferably added to the aqueous phase.

The astaxanthin-containing particles of the present invention can be preferably used by blending them in foods, health foods, pharmaceuticals and the like. Further, the astaxanthin-containing particles of the present invention may be used as they are as pharmaceuticals, foods, health foods and the like.

When the astaxanthin-containing particles of the present invention are used in combination with a pharmaceutical product, the form of the pharmaceutical product is not particularly limited, and a pharmaceutical additive, a food additive, a food material, etc. are appropriately blended together with the astaxanthin-containing particles of the present invention. According to the law, it can be produced as a preparation in the form of, for example, powder, granules, tablets, hard capsules and the like.

When the astaxanthin-containing particles of the present invention are used in a food or health food, the form of the food or health food is not particularly limited, and for example, baked confectionery, chocolate, chewing gum, candy, confectionery such as gummy, yogurt. , Ice cream, desserts such as pudding, tablet confectionery / tablets manufactured by tableting together with powders such as excipients, and infant formulas and the like.

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited thereto.

[Preparation of astaxanthin-containing agar particles]
(1) Raw materials 1) Water 2) Agar (Product name: Ultra agar RB; Powdered agar; Ina Food Industry Co., Ltd.)
3) Pea protein (trade name: Protein GP; manufactured by Daiichi Kaseisha)
4) β-Cyclodextrin (trade name: Dixipal β-100; manufactured by Shiomizu Port Refinery Co., Ltd.)
5) Granulated sugar (trade name: granulated sugar GN; manufactured by Mitsui Sugar Co., Ltd.)
6) L-ascorbic acid palmitic acid ester (trade name: Grindox ascorbic palmitate; manufactured by Danisco)
7) Sodium hydroxide (trade name: Toso Pearl; manufactured by Tosoh Co., Ltd.)
8) Astaxanthin (trade name: AstaZine Haematococcus algae pigment oil 20%; oil and fat containing 20% by mass of astaxanthin; manufactured by BGG)
9) Extracted tocopherol 1 (trade name: RIKEN E Oil Super 80; manufactured by RIKEN Vitamin Co., Ltd.)
10) Extracted tocopherol 2 (trade name: RIKEN E Oil 800; manufactured by RIKEN Vitamin Co., Ltd.)
11) Extracted tocopherol 3 (trade name: RIKEN E Oil 705; manufactured by RIKEN Vitamin Co., Ltd.)
12) Extracted tocopherol 4 (trade name: RIKEN E Oil 900α; manufactured by RIKEN Vitamin Co., Ltd.)
13) Calcium stearate (trade name: calcium stearate; manufactured by San Ace)
14) Fine silicon dioxide (trade name: Carplex FPS-500; manufactured by Evonik Industries, Ltd.)

Table 1 shows the total tocopherol content, the composition of each homologue in the total tocopherols, and the d-γ, δ-tocopherol amounts of the extracted tocopherols 1 to 4 among the above raw materials.

(2) Formulation of Astaxanthin-Containing Agar Particles Table 2 shows the composition of astaxanthin-containing agar particles 1 to 5 prepared using the above raw materials. Of these, astaxanthin-containing agar particles 1 are examples according to the present invention, astaxanthin-containing agar particles 2 to 5 are comparative examples, and astaxanthin-containing agar particles 5 are controls produced without using extracted tocopherols. This is an example.

In Table 2, among the raw materials of astaxanthin-containing agar particles, the description of calcium stearate and fine silicon dioxide that do not form a continuous phase or a dispersed phase of the particles is omitted.

(3) Method for preparing astaxanthin-containing agar particles Agar, pea protein, β-cyclodextrin, granu sugar, L-ascorbic acid palmitic acid ester, and sodium hydroxide were preliminarily heated to 85 ° C. according to the blending amounts shown in Table 2. In addition to 300 g of warmed tap water, the mixture was uniformly mixed and dissolved at 4000 rpm with a TK homomixer (manufactured by Primix Corporation) to prepare an aqueous phase.
While maintaining this aqueous phase at 85 ° C., a dispersed phase obtained by uniformly mixing astaxanthin and extracted tocopherol preheated to 70 ° C. according to the blending amount shown in Table 2 was added to the aqueous phase (however, astaxanthin). In the case of the agar particles 5 contained, since the extracted tocopherol is not used, only astaxanthin is added to the aqueous phase as it is), and the mixture is stirred with a TK homomixer at 10000 rpm for 10 minutes to obtain a dispersion liquid in which the dispersed phase is dispersed in the aqueous phase. rice field.
Next, the dispersion liquid was sent to a spray cooling device (prototype) in which the lower part of the tower was cooled with liquid nitrogen, and the rotary spray nozzle was rotated at a rotation speed of 1200 rpm to spray in a spherical shape. The sprayed composition was cooled and dropped to the bottom of the tower and collected as frozen particles.
After adding 4 g of calcium stearate to each 320 g of the collected particles and mixing them, a fluidized bed dryer (model: LAB-1; manufactured by Paulec) was used at 20 ° C. for 30 minutes, 30 ° C. for 1 hour, and 60 ° C. It was dried in the order of 30 minutes. After drying, 0.2 g of fine silicon dioxide was added to the obtained dried product and mixed, and this was sieved with a No. 36 sieve (opening 425 μm) to obtain 78 g of each astaxanthin-containing agar particles 1 to 5 as a passing product. rice field. The obtained astaxanthin-containing agar particles had an average particle size of about 250 μm and a water content of about 2.5% by mass determined by a sieving method.

[Storage stability test of astaxanthin-containing agar particles]
10 g of each of astaxanthin-containing agar particles 1 to 5 was taken in a glass petri dish (diameter 80 mm × depth 15 mm; manufactured by AS ONE), and stored in an incubator (incubator) at a temperature of 60 ° C. for 60 days under an open lid.
The evaluation was carried out by measuring the astaxanthin content of the astaxanthin-containing agar particles before and after storage, determining the residual rate (mass%) of astaxanthin based on the following formula, and visually confirming the color tone. The results are shown in Table 3.
Residual rate (mass%) = A / B x 100
A: Astaxanthin content after storage B: Astaxanthin content before storage

A and B in the above formula were measured by the following "method for measuring astaxanthin content".

[Astaxanthin content measurement method]
100 mg of the sample was precisely weighed in a 100 mL brown volumetric flask, 10 mL of ultrapure water was added, and the mixture was heated and dissolved at 90 ° C. for 20 minutes. Then, using a desktop ultrasonic cleaner (model: M5800HJ; manufactured by Yamato Kagaku Co., Ltd.), heating and ultrasonic treatment were performed at 60 ° C. for 10 minutes to completely dissolve the mixture.
The obtained solution was cooled to room temperature, 60 mL of acetone (special grade reagent; manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) was added, and the mixture was mixed and dissolved with a shaker for 30 minutes. Then, the volumetric flask was adjusted to 100 mL with the same acetone. Then, the solution was transferred to a centrifuge tube, and astaxanthin was extracted with a centrifuge (3000 rpm, 10 minutes).
5 mL of the upper layer (acetone layer) containing the extracted astaxanthin was collected in a 50 mL brown volumetric flask, diluted and dissolved in the same acetone, and the volumetric flask was increased to 50 mL to prepare a sample for measurement.
The absorbance of the measurement sample was measured using a spectrophotometer (model: U-5100; manufactured by Hitachi High-Tech Science Co., Ltd.), and the extinction coefficient of astaxanthin in acetone at the maximum absorption wavelength (478 nm) (E ^1% _{1 cm} = The astaxanthin content (% by mass) was calculated based on 220) and the following equation.
Astaxanthin content (% by mass) = (A x B) / (220 x C) x 100
A: Absorbance at maximum absorption wavelength (478 nm) B: Dilution factor (100 x 10)
C: Sample collection amount (100 mg)

As is clear from the results in Table 3, the astaxanthin-containing agar particles 1 according to the examples of the present invention are obtained by adding extracted tocopherol 1, which is a tocopherol composition having a d-γ, δ-tocopherol amount of 90% by mass or more. However, there was no change in color tone even under the harsh storage conditions of "60 ° C. for 60 days", and the residual rate was significantly improved as compared with the astaxanthin-containing agar particles 5 of the control example to which no extracted tocopherol was added. It had been. On the other hand, the astaxanthin-containing agar particles 2 to 4 of the comparative example were obtained by adding extracted tocopherols 2 to 4, which are tocopherol compositions having a d-γ, δ-tocopherol amount of less than 90% by mass. Fading was observed, and their residual rates were similar to or surprisingly inferior to those of the astaxanthin-containing agar particles 5 of the control example. From the above, it is effective to suppress the deterioration of astaxanthin in the long-term storage of astaxanthin-containing agar particles only in the extracted tocopherols in which the amount of d-γ, δ-tocopherol in the total tocopherol is 90% by mass or more. I found out.

[Preparation of astaxanthin-containing gelatin particles]
(1) Raw materials 1) Water 2) Gelatin (trade name: gelatin BP-250; powdered gelatin; jelly strength: 240 to 280 g; manufactured by Nippi)
3) Granulated sugar (trade name: granulated sugar GN; manufactured by Mitsui Sugar Co., Ltd.)
4) L-ascorbic acid palmitic acid ester (trade name: Grindox ascorbic palmitate; manufactured by Danisco)
5) Astaxanthin (trade name: AstaZine Haematococcus algae pigment oil 10%; oil and fat containing 10% by mass of astaxanthin; manufactured by BGG)
6) Extracted tocopherol 1 (trade name: RIKEN E Oil Super 80; manufactured by RIKEN Vitamin Co., Ltd.)
7) Extracted tocopherol 2 (trade name: RIKEN E Oil 800; manufactured by RIKEN Vitamin Co., Ltd.)
8) Extracted tocopherol 3 (trade name: RIKEN E Oil 705; manufactured by RIKEN Vitamin Co., Ltd.)
9) Extracted tocopherol 4 (trade name: RIKEN E Oil 900α; manufactured by RIKEN Vitamin Co., Ltd.)
10) Calcium stearate (trade name: calcium stearate; manufactured by San Ace)
11) Fine silicon dioxide (trade name: Carplex FPS-500; manufactured by Evonik Industries)

(2) Formulation of Astaxanthin-Containing Gelatin Particles Table 4 shows the composition of astaxanthin-containing gelatin particles 1 to 5 prepared using the above raw materials. Of these, astaxanthin-containing gelatin particles 1 are examples according to the present invention, astaxanthin-containing gelatin particles 2 to 5 are comparative examples, and astaxanthin-containing gelatin particles 5 are controls produced without using extracted tocopherols. This is an example.

In Table 4, among the raw materials of astaxanthin-containing gelatin particles, the description of calcium stearate and fine silicon dioxide that do not form a continuous phase or a dispersed phase of the particles is omitted.

(3) Method for preparing astaxanthin-containing gelatin particles According to the blending amounts shown in Table 4, gelatin, granusaccharide, and L-ascorbic acid palmitic acid ester were added to 220 g of tap water preheated to 60 ° C. and TK. It was uniformly mixed and dissolved at 4000 rpm with a homomixer (manufactured by Primix Corporation), and this was used as an aqueous phase.
While maintaining this aqueous phase at 60 ° C., a dispersed phase obtained by uniformly mixing astaxanthin and extracted tocopherol preheated to 70 ° C. according to the blending amount shown in Table 4 was added to the aqueous phase (however, astaxanthin). In the case of the contained gelatin particles 5, since the extracted tocopherol is not used, only astaxanthin is added to the aqueous phase as it is), and the mixture is stirred with a TK homomixer at 10000 rpm for 10 minutes to obtain a dispersion in which the dispersed phase is dispersed in the aqueous phase. rice field.
Next, the dispersion liquid was sent to a spray cooling device (prototype) in which the lower part of the tower was cooled with liquid nitrogen, and the rotary spray nozzle was rotated at a rotation speed of 1200 rpm to spray in a spherical shape. The sprayed composition was cooled and dropped to the bottom of the tower and collected as frozen particles.
After adding 2 g of calcium stearate to each 300 g of the collected particles and mixing them, a fluidized bed dryer (model: LAB-1; manufactured by Paulec) was used at 20 ° C. for 30 minutes, 30 ° C. for 1 hour, and 60 ° C. It was dried in the order of 30 minutes. After drying, 0.2 g of fine silicon dioxide was added to the obtained dried product and mixed, and this was sieved with a No. 36 sieve (opening 425 μm) to obtain 85 g of each astaxanthin-containing gelatin particles 1 to 5 as a passing product. rice field. The obtained astaxanthin-containing gelatin particles had an average particle size of about 250 μm and a water content of about 2.5% by mass determined by a sieving method.

[Storage stability test of astaxanthin-containing gelatin particles]
10 g of each of astaxanthin-containing gelatin particles 1 to 5 was taken in a glass petri dish (diameter 80 mm × depth 15 mm; manufactured by AS ONE), and stored in an incubator (incubator) at a temperature of 60 ° C. for 60 days under an open lid.
The evaluation was carried out by measuring the astaxanthin content of the astaxanthin-containing gelatin particles before and after storage, determining the residual ratio (mass%) of astaxanthin based on the following formula, and visually confirming the color tone. The results are shown in Table 5.
Residual rate (mass%) = A / B x 100
A: Astaxanthin content after storage B: Astaxanthin content before storage

A and B in the above formula were measured by the following "method for measuring astaxanthin content".

[Astaxanthin content measurement method]
100 mg of the sample was precisely weighed in a 100 mL brown volumetric flask, 10 mL of ultrapure water was added, and the mixture was heated and dissolved at 90 ° C. for 20 minutes. Then, using a desktop ultrasonic cleaner (model: M5800HJ; manufactured by Yamato Kagaku Co., Ltd.), heating and ultrasonic treatment were performed at 60 ° C. for 60 minutes to completely dissolve the mixture.
The obtained solution was cooled to room temperature, 60 mL of acetone (special grade reagent; manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) was added, and the mixture was mixed and dissolved with a shaker for 30 minutes. Then, the volumetric flask was adjusted to 100 mL with the same acetone. Then, the solution was transferred to a centrifuge tube, and astaxanthin was extracted with a centrifuge (3000 rpm, 10 minutes).
5 mL of the upper layer (acetone layer) containing the extracted astaxanthin was collected in a 50 mL brown volumetric flask, diluted and dissolved in the same acetone, and the volumetric flask was increased to 50 mL to prepare a sample for measurement.
The absorbance of the measurement sample was measured using a spectrophotometer (model: U-5100; manufactured by Hitachi High-Tech Science Co., Ltd.), and the extinction coefficient of astaxanthin in acetone at the maximum absorption wavelength (478 nm) (E ^1% _{1 cm} = The astaxanthin content (% by mass) was calculated based on 220) and the following equation.
Astaxanthin content (% by mass) = (A x B) / (220 x C) x 100
A: Absorbance at maximum absorption wavelength (478 nm) B: Dilution factor (100 x 10)
C: Sample collection amount (100 mg)

As is clear from the results in Table 5, the astaxanthin-containing gelatin particles 1 according to the examples of the present invention are obtained by adding extracted tocopherol 1 which is a tocopherol composition having a d-γ, δ-tocopherol amount of 90% by mass or more. However, there was no change in color tone even under the harsh storage conditions of "60 ° C. for 60 days", and the residual rate was significantly improved as compared with the astaxanthin-containing gelatin particles 5 of the control example to which no extracted tocopherol was added. It had been. On the other hand, the astaxanthin-containing gelatin particles 2 to 4 of the comparative example were obtained by adding extracted tocopherols 2 to 4, which are tocopherol compositions having a d-γ, δ-tocopherol amount of less than 90% by mass. Fading was observed, and their residual rates were similar to or surprisingly inferior to the astaxanthin-containing gelatin particles 5 of the control example. From the above, it is effective to suppress the deterioration of astaxanthin in the long-term storage of astaxanthin-containing gelatin particles only in the extracted tocopherols in which the amount of d-γ, δ-tocopherol in the total tocopherol is 90% by mass or more. I found out.

1 continuous phase 2 dispersed phase

Claims (1)

The following components (A), (B) and (C):
(A) Agar and / or gelatin,
(B) Astaxanthin,
(C) Astaxanthin-containing particles containing a tocopherol composition having a total content of d-γ-tocopherol and d-δ-tocopherol in total tocopherol of 90% by mass or more, and continuously containing the component (A). Astaxanthin-containing particles having a phase and a dispersed phase containing the components (B) and (C) dispersed in the continuous phase.

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