JP2007289064A - Powdery carotinoid agent - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a powdery carotinoid agent transparently dissolving in water, and excellent in storage stability. <P>SOLUTION: The powdery carotinoid agent is obtained by subjecting a dispersion solution containing water and sucrose fatty acid ester having ≥90 mass% of monoester to vacuum freeze dry, wherein the content of the sucrose fatty acid ester having ≥90 mass% of the content of the monoester accounts for 22.5-50 mass% in 100 mass% of the agent. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a powdered carotenoid preparation that dissolves almost transparently in water.

  A carotenoid is a pigment having a hue of yellow, orange to red, and many carotenoids such as β-carotene, pepper, and marigold pigments are widely used for coloring foods. At that time, for coloring of water-based foods such as soft drinks, since almost all carotenoids including β-carotene are insoluble in water, liquid or powder preparations in which carotenoids are water-soluble are usually used. However, although a conventional formulation is dispersed or dissolved in water, the solution becomes turbid, and therefore cannot be used for coloring beverages that require high transparency such as near water.

In order to solve this problem, when the composition of food carotenoid pigment and polyglycerin fatty acid ester is finely divided and the absorbance at the maximum absorption wavelength in the visible region is 1, the transmittance at 660 nm is 99% or more. A carotenoid pigment solubilized liquid preparation for foods (see Patent Document 1), and when dissolved in water at a concentration of 0.2% by weight, the absorbance at 680 nm measured by a spectrophotometer is 0.02 or less. An edible oily material-containing powder material that is transparently soluble in water and has the following composition: (a) 1 to 30% by weight of edible oily material, (b) polyglycerin fatty acid ester and / or shochu Edible property that dissolves transparently in water obtained by drying an aqueous mixture comprising 1 to 20% by weight of sugar fatty acid ester, (c) 5 to 60% by weight of excipient, and (d) 30 to 80% by weight of water. Sex material containing powder material (see Patent Document 2), have been proposed.
When liquid and powder preparations are compared, powder preparations are easier to use from the viewpoint of workability such as automatic weighing. However, since the powder preparation undergoes a drying process at the time of manufacture, its performance is likely to change, and the fact is that a powder preparation with stable quality has not yet been obtained.

JP-A-10-120933 JP 2003-55688 A

  An object of the present invention is to provide a powdered carotenoid preparation which is almost transparently soluble in water and excellent in storage stability.

As a result of intensive studies on the above problems, the inventors of the present invention vacuum-freeze-dried a dispersion containing carotenoids, saccharides, monoesters having a sucrose fatty acid ester content of 90% by mass or more and water. As a result, it was found that a powdered carotenoid preparation having the characteristics shown in the above-mentioned problems was obtained, and the present invention was made based on this finding.
That is, the present invention
(1) A preparation obtained by vacuum lyophilization of a dispersion containing sucrose fatty acid ester having a carotenoid, saccharide, monoester content of 90% by mass or more and water, and in 100% by mass of the preparation, A powdered carotenoid preparation, wherein the content of sucrose fatty acid ester having a monoester content of 90% by mass or more is 22.5 to 50% by mass,
(2) The powdered carotenoid preparation according to 1 above, wherein the saccharide is lactose,
It is made up of.

The powdered carotenoid preparation of the present invention dissolves almost transparently in water.
The powdered carotenoid preparation of the present invention is excellent in long-term storage stability.

  Examples of the carotenoid used in the present invention include those obtained by extraction and purification from animals and plants, those obtained by fermentation or synthesis, and any of them can be preferably used. Specific examples of the carotenoid used in the present invention include, for example, β-carotene, α-carotene, γ-carotene, β-apo-8'-carotenal, β-apo-10'-carotenal, β-apo-8'- Carotenic acid, citranaxanthin, lycopene, zeaxanthin, cryptoxanthine, echinone, 3-hydroxy-β-carotene, fucoxanthin, lutein, astaxanthin, canthaxanthin, capsanthin, capsorbin, bixin, crocetin and the hydroxyl or carboxyl group of these groups Examples include esters of contained compounds. Examples of natural carotenoids containing the above carotenoids include annatto pigment, imo carotene, shrimp pigment, krill pigment, orange pigment, crab pigment, Dunaliella carotene, red pepper pigment (also known as paprika pigment), corn pigment, tomato pigment, carrot carotene. , Palm oil carotene, Phaffia pigment, Beninoki powder, Hematococcus alga pigment, Marigold pigment and the like. The carotenoids may be used alone or in any combination of two or more.

  Examples of the saccharide used in the present invention include monosaccharides such as glucose, fructose, and galactose, disaccharides such as sucrose, lactose, and maltose, fructooligosaccharides, galactooligosaccharides, maltotriose, maltotetraose, maltopentaose, Examples include oligosaccharides such as maltohexaose and cyclodextrin, dextrin, starch degradation products such as powdered starch syrup, sugar alcohols such as sorbitol, mannitol, maltitol, powdered reduced starch syrup, powdered reduced palatinose, polysaccharides such as gum arabic, etc. Preferably, it is lactose.

  The sucrose fatty acid ester used in the present invention is an esterification product of sucrose and a fatty acid, and the constituent fatty acid is not particularly limited as long as it is a fatty acid originating from edible animal and vegetable oils and fats. 6 to 24 linear saturated fatty acids (for example, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, etc.) and unsaturated fatty acids (for example, , Palmitooleic acid, oleic acid, elaidic acid, linoleic acid, γ-linolenic acid, α-linolenic acid, arachidonic acid, ricinoleic acid, condensed ricinoleic acid and the like, preferably a saturated fatty acid having 16 to 18 carbon atoms. It is. Industrially, it is preferable to use a fatty acid mixture containing about 90% by mass or more of one or more saturated fatty acids selected from saturated fatty acids having 16 to 18 carbon atoms.

  The content of the monoester in the sucrose fatty acid ester is preferably about 90% by mass or more, particularly preferably about 95% by mass or more. The outline of the production method is as follows. That is, a mixture containing sucrose monofatty acid ester, sucrose difatty acid ester, sucrose trifatty acid ester and the like is obtained by esterification reaction of sucrose and fatty acid. Next, the mixture is purified by a method known per se, such as column chromatography, liquid-liquid extraction, or Shosei, to obtain a sucrose fatty acid ester containing about 90% by mass or more of a monoester. As a commercial item, DK ester SS (made by Daiichi Kogyo Seiyaku Co., Ltd.) is mentioned, for example.

  The content of monoester in the sucrose fatty acid ester was determined by conducting an organic GPC analysis using THF as an eluent and preparing a standard curve of sucrose monostearate purified by normal phase column chromatography. From this, it can be obtained by the absolute calibration curve method.

  The water used in the present invention is not particularly limited as long as it is drinkable. For example, distilled water, ion exchange resin treated water, reverse osmosis membrane (RO) treated water, ultrafiltration membrane (UF) treated water, etc. Purified water, tap water, and natural water such as groundwater or brine

  There is no particular limitation on the method for producing a dispersion containing sucrose fatty acid ester having 90% by mass or more of carotenoid, saccharide, and monoester content in the present invention, and water can be used by a method known per se. Below, the manufacturing method of a preferable dispersion liquid is illustrated. For example, in a normal stirring / mixing tank equipped with a stirrer, a heating jacket, a baffle plate and the like, sucrose fatty acid ester having a content of water, saccharides and monoesters of 90% by mass or more is added, and about 60 to 95 C., preferably about 80-90.degree. C. and dissolved to form an aqueous phase. As a stirrer to be equipped, a high-speed rotary dispersing / emulsifying machine such as TK homomixer (made by Tokushu Kika Kogyo Co., Ltd.) or Claremix (made by M Technique Co., Ltd.) is preferably used. While stirring the aqueous phase, a carotenoid kept at about 100 ° C. or less, preferably about 80 to 90 ° C., or an oil phase comprising a carotenoid-containing oil and fat is slowly added and homogenized to obtain a dispersion. Examples of the homogenization conditions include a rotation speed of about 4000 to 20000 rpm and a stirring time of about 10 to 60 minutes.

  The obtained dispersion liquid may be further homogenized using a high-pressure homogenizer. Examples of the high-pressure homogenizer include an APV gorin homogenizer (manufactured by APV), a microfluidizer (manufactured by Microfluidics), an optimizer (manufactured by Sugino Machine), and a nanomizer (manufactured by Daiwa Steel). It is done. The operating conditions of these homogenizers vary depending on the specifications of the apparatus and are not constant, but can be exemplified by 1 to 3 times at about 5 to 30 MPa, for example. Instead of the high-pressure homogenizer, a homogenizer such as an ultrasonic emulsifier may be used.

  The dispersion obtained by the above treatment accurately weighed 0.050 g of the dispersion, dissolved in purified water at 20 ± 5 ° C. to make exactly 100 mL, used as a test solution, and water as a control solution at a wavelength of 660 nm. When the transmittance (T%) is measured, the transmittance value is preferably 99.0% or more.

  In the present invention, in 100% by mass of the dispersion, about 1 to 15% by mass, preferably about 4 to 10% by mass of fats and oils containing carotenoid or carotenoid, and about 1 to 30% by mass, preferably about 5% of saccharides. It is preferable to adjust the sucrose fatty acid ester having a content of ˜15% by mass and a monoester body of 90% by mass or more to about 1 to 15% by mass, preferably about 5 to 10% by mass, and the remainder to be water. .

  In the present invention, the dispersion contains, for example, a polyglycerin fatty acid ester, a sucrose fatty acid ester having a monoester content of less than 90% by mass, and a polyoxyethylene sorbitan fatty acid as long as the objects and effects of the present invention are not impaired. Food emulsifiers such as esters, and for example extracted tocopherol, ascorbyl palmitate, L-ascorbic acid and its salts, catechins, enzyme-treated rutin, sunflower seed extract, grape seed extract and enzyme-degraded apple extract An antioxidant may be added.

  The dispersion is then dried by vacuum freeze drying and powdered. There is no restriction | limiting in particular in the apparatus used for vacuum freeze-drying, A itself well-known apparatus can be used. The method of vacuum lyophilization may be in accordance with a method known per se. For example, the dispersion is frozen at −20 ° C. or lower, preferably −30 to −40 ° C., and the obtained frozen product is about 613 Pa or lower, preferably about 107 It is preferable to dry for about 10 to 72 hours while heating at about 30 to 60 ° C. under a vacuum of about ˜13 Pa. A powdered carotenoid preparation can be obtained by pulverizing the dried product obtained, and preferably sieving. The dry weight loss of the obtained powdered carotenoid preparation is usually about 5% by mass or less, preferably about 1 to 3% by mass.

  An example of a preferred embodiment of the powdered carotenoid preparation of the present invention is about 9 to 35% by weight of fats and oils containing carotenoid or carotenoid, preferably about 20 to 30% by weight and about 5% of saccharides in 100% by weight of the preparation. -60% by mass, preferably about 30-50% by mass, monoester content of 90% by mass or more sucrose fatty acid ester about 22.5-50% by mass, preferably about 25-45% by mass It is a powder.

  The color value of the powdered carotenoid preparation of the present invention is preferably about 50 to 200, more preferably about 100 to 150. The color value is measured in accordance with “17. Color value measurement method” described in “7th edition Food Additives Official Document” (Japan Food Additives Association, 1999). The test solution used for the measurement accurately measures the amount of the powdered carotenoid preparation of the present invention based on the estimated color value, dissolves by adding 1 mL of 65 ± 5 ° C. purified water, and adds acetone to accurately 100 mL. And filtered, and if necessary, it is further diluted accurately with acetone.

  The powdered carotenoid preparation of the present invention is characterized by being almost transparently soluble in water. Specifically, 0.010 g of the powdered carotenoid preparation of the present invention is accurately weighed, dissolved by adding 10 mL of 65 ± 5 ° C. purified water, cooled to room temperature, and purified by adding 20 ± 5 ° C. purified water. When the transmittance (T%) at a wavelength of 660 nm was measured using 100 mL as a test solution and water as a control solution, the transmittance value was 98.0% or more.

  Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited thereto.

[Example 1]
1) 80.2 g of purified water was placed in a 300 mL tall beaker and heated to 80 ° C.
2) 5.4 g of lactose (USP grade; manufactured by Friesland Foods Domo), sucrose fatty acid ester (trade name: DK) while stirring at low speed with Claremix (model: CLM-1.5S; manufactured by M Technique) (Ester SS; manufactured by Daiichi Kogyo Seiyaku Co., Ltd., monoester content: 98% by mass) 9.0 g was added and dissolved to obtain an aqueous phase.
3) 5.04 g of marigold pigment (trade name: Lutein 400; manufactured by Riken Vitamin Co., color value: 5600) and 0.36 g of extracted tocopherol (trade name: RIKEN E Oil Super 80; manufactured by Riken Vitamin Co., Ltd.) It heated and melt | dissolved to about 80 degreeC, and was set as the oil phase.
4) The oil phase of 3) was gradually added to the aqueous phase of 2), and then homogenized at 10,000 rpm for 30 minutes to obtain a dispersion.
5) About 20 g of the dispersion of 4) was put in a 30 mL beaker and kept in a -35 ° C freezer for 16 hours to freeze the dispersion.
6) The beaker of 5) was placed in a 120 mL dry flask and attached to a freeze dryer (model: DC800; manufactured by Yamato Scientific Co., Ltd.), and freeze-dried for about 48 hours under a vacuum degree of about 100 Pa.
7) The obtained dried product was pulverized in a mortar to obtain about 4 g of a powdered carotenoid preparation (Formulation 1). The loss on drying of the obtained powder was about 2.8% by mass.

[Example 2]
In Example 1 2), lactose (USP grade; manufactured by Friesland Foods Domo) 5.4 g, sucrose fatty acid ester (trade name: DK Ester SS; manufactured by Daiichi Kogyo Seiyaku Co., Ltd., monoester content 98% by mass) 9 Example 1 except that 9.4 g of lactose and 5.0 g of sucrose fatty acid ester (trade name: DK Ester SS; manufactured by Daiichi Kogyo Seiyaku Co., Ltd., monoester content 98% by mass) were used instead of 0.0 g. And about 4 g of a powdered carotenoid preparation (Formulation 2) was obtained. The loss on drying of the obtained powder was about 3.2% by mass.

[Example 3]
In Example 1 2), lactose (USP grade; manufactured by Friesland Foods Domo) 5.4 g, sucrose fatty acid ester (trade name: DK Ester SS; manufactured by Daiichi Kogyo Seiyaku Co., Ltd., monoester content 98% by mass) 9 In place of 0.0 g, the above lactose 9.0 g, sucrose fatty acid ester (trade name: DK Ester SS; manufactured by Daiichi Kogyo Seiyaku Co., Ltd., monoester content 98% by mass) and sucrose fatty acid ester (trade name) : Ryoto sugar ester P-1570; manufactured by Mitsubishi Chemical Foods Co., Ltd., monoester content 70% by mass) 0.9 g was used, and the same procedure as in Example 1 was carried out, and about 4 g of powdered carotenoid preparation (Formulation 3) Got. The loss on drying of the obtained powder was about 2.6% by mass.

[Comparative Example 1]
In Example 1 2), lactose (USP grade; manufactured by Friesland Foods Domo) 5.4 g, sucrose fatty acid ester (trade name: DK Ester SS; manufactured by Daiichi Kogyo Seiyaku Co., Ltd., monoester content 98% by mass) 9 Example 1 except that 14.0 g of the above lactose and 2.0 g of sucrose fatty acid ester (trade name: DK Ester SS; manufactured by Daiichi Kogyo Seiyaku Co., Ltd., monoester content 98% by mass) were used instead of 0.0 g. And about 4 g of a powdered carotenoid preparation (Formulation 4) was obtained. The loss on drying of the obtained powder was about 3.1% by mass.

[Comparative Example 2]
In Example 1 2), lactose (USP grade; manufactured by Friesland Foods Domo) 5.4 g, sucrose fatty acid ester (trade name: DK Ester SS; manufactured by Daiichi Kogyo Seiyaku Co., Ltd., monoester content 98% by mass) 9 Example 1 except that instead of 0.0 g, the above lactose 10.4 g and 4.0 g of sucrose fatty acid ester (trade name: DK Ester SS; manufactured by Daiichi Kogyo Seiyaku Co., Ltd., monoester content 98 mass%) were used. And about 4 g of a powdered carotenoid preparation (Formulation 5) was obtained. The loss on drying of the obtained powder was about 2.6% by mass.

[Comparative Example 3]
In Example 1 2), lactose (USP grade; manufactured by Friesland Foods Domo) 5.4 g, sucrose fatty acid ester (trade name: DK Ester SS; manufactured by Daiichi Kogyo Seiyaku Co., Ltd., monoester content 98% by mass) 9 In place of 0.0 g, 9.4 g of the above lactose, 2.0 g of sucrose fatty acid ester (trade name: DK Ester SS; manufactured by Daiichi Kogyo Seiyaku Co., Ltd., monoester content 98% by mass) and sucrose fatty acid ester (trade name) : Ryoto Sugar Ester P-1570; manufactured by Mitsubishi Chemical Foods Co., Ltd., monoester content 70% by mass) The same procedure as in Example 1 was carried out except that 3.0 g was used, and about 4 g of powdered carotenoid preparation (Formulation 6) Got. The loss on drying of the obtained powder was about 3.3% by mass.

[Comparative Example 4]
1) 1604 g of purified water was put into a 3 L stainless steel beaker and heated to 80 ° C.
2) Lactose (USP grade; manufactured by Friesland Foods Domo) 180 g, sucrose fatty acid ester (trade name: DK Ester SS) while stirring at low speed with CLEARMIX (model: CLM-1.5S; manufactured by M Technique) ; 90 g of monoester body content manufactured by Daiichi Kogyo Seiyaku Co., Ltd. and 18 g of sucrose fatty acid ester (trade name: Ryoto Sugar Ester P-1570; manufactured by Mitsubishi Chemical Foods Co., Ltd., 70 mass% monoester body content) In addition, it was dissolved into an aqueous phase.
3) Marigold pigment (trade name: Lutein 400; manufactured by Riken Vitamin Co., Ltd., color value: 5600) 100.8 g and extracted tocopherol (trade name: Riken E Oil Super 80; manufactured by Riken Vitamin Co., Ltd.) 7.2 g It heated to about 80 degreeC and melt | dissolved, and it was set as the oil phase.
4) The oil phase of 3) was gradually added to the aqueous phase of 2), and then homogenized at 10,000 rpm for 30 minutes to obtain a dispersion.
5) The dispersion liquid of 4) is spray-dried under the conditions of a hot air inlet temperature of 180 ° C. and an exhaust temperature of 90 ° C. in a pressure nozzle type spray drying apparatus (model: L-8i; manufactured by Okawara Chemical Co., Ltd.) The dried product was collected with a cyclone to obtain about 330 g of a powdered carotenoid preparation (Formulation 7). The loss on drying of the obtained powder was about 3.6% by mass.

  Table 1 summarizes the formulation of the powdered carotenoid preparations (formulations 1 to 7) prepared in Examples 1 to 3 and Comparative Examples 1 to 4.

[Test Example 1]
Accurately measure 0.010 g of the powdered carotenoid preparations (formulations 1 to 7) prepared in Examples 1 to 3 and Comparative Examples 1 to 4, dissolve in 10 mL of purified water at 65 ± 5 ° C., and then cool to room temperature. The sample was dissolved in purified water at 20 ± 5 ° C. to make exactly 100 mL, and the transmittance (T%) at a wavelength of 660 nm was measured using water as a control solution. The results are shown in Table 2.

[Test Example 2]
1 g of each of the powdered carotenoid preparations (formulations 1 to 3) prepared in Examples 1 to 3 was put in an aluminum bag and heat-sealed, and stored in a 40 ° C. incubator for 4 months. After completion of the test, 0.010 g of each preparation was accurately weighed, dissolved by adding 10 mL of purified water at 65 ± 5 ° C, cooled to room temperature, dissolved in purified water at 20 ± 5 ° C to make exactly 100 mL Was used as a test solution, and the transmittance (T%) at a wavelength of 660 nm was measured using water as a control solution. The results are shown in Table 3.

The powdered carotenoid preparation of the present invention can be used as a coloring agent for a wide range of foods, but can be preferably used for coloring beverages that require high transparency, such as near water. The amount of the powdered carotenoid preparation of the present invention added to the beverage is not constant because it varies depending on the type of carotenoid and the hue of the beverage, but is usually in the range of about 0.001 to 0.02% by mass in 100% by mass of the beverage.

Claims (2)

A preparation obtained by freeze-drying a dispersion containing a sucrose fatty acid ester containing 90% by mass or more of a carotenoid, a saccharide, and a monoester, and water, and the monoester in 100% by mass of the preparation A powdered carotenoid preparation characterized in that the content of sucrose fatty acid ester having a content of 90% by mass or more is 22.5 to 50% by mass. 2. The powdered carotenoid preparation according to claim 1, wherein the saccharide is lactose.