JP5600513B2 - Method for producing crocetin preparation - Google Patents

Description

  The present invention relates to a method for producing a crocetin preparation.

  Crocetin is obtained by hydrolyzing crocin extracted from dried fruits of gardenia (coconut) fruits and saffron stigmas using alkalis and enzymes. Crocin is water-soluble, and in Japan, it is used as a main pigment component of gardenia yellow pigment for coloring a wide range of foods, but crocetin is insoluble in water. Therefore, although crocetin is superior in color to crocin, its use has been limited.

  Under such circumstances, with the aim of providing a method for producing a crocetin preparation that is well dispersed in water and suitable as a colorant for aqueous foods, crocetin is dispersed in an aqueous solution containing saccharides and the average particles thereof are dispersed. A method for producing a powdery crocetin preparation characterized in that the diameter is 0.5 to 5 μm and the obtained dispersion is dried has been proposed (see Patent Document 1).

  However, when a transparent food or drink (for example, a plastic bottle drink) is colored using the above preparation, a precipitate derived from the preparation may be generated to such an extent that it can be easily confirmed with the naked eye. It wasn't possible.

JP 2006-335859 A

  This invention makes it a subject to provide the manufacturing method of the crocetin formulation which can suppress the precipitation which arises when a drink is colored.

  As a result of intensive studies to solve the above-mentioned problems, the present inventor, when preparing a preparation containing crocetin, uses a high-pressure homogenizer such as a microfluidizer to keep the particle diameter of the preparation constant. By adjusting within the range, it found out that the precipitation of the drink colored using the obtained formulation was suppressed, and came to make this invention based on this knowledge.

That is, the present invention
[1]. Following formula

で表されるクロセチンを、糖類を含有する水溶液中に分散して分散液を調製する際に、該分散液の粒子径をメジアン径で０．５μｍ未満とすることを特徴とするクロセチン製剤の製造方法、
［２］．前記調整は、高圧式均質化処理機を用いて行うことを特徴とする［１］に記載のクロセチン製剤の製造方法、
を提供するものである。

The preparation of a crocetin preparation characterized in that when preparing a dispersion by dispersing crocetin represented by the formula in an aqueous solution containing saccharides, the particle diameter of the dispersion is less than 0.5 μm in median size Method,
[2]. The method for producing a crocetin preparation according to [1], wherein the adjustment is performed using a high-pressure homogenizer.
Is to provide.

  The beverage colored using the crocetin preparation obtained by the production method of the present invention is one in which precipitation is suppressed.

  Crocetin used in the present invention has the formula

で表される化合物である。このクロセチンは、通常、カロテノイド系の黄色色素であるクロシン（クロセチンのジゲンチオビオースエステル）を加水分解することにより得られる。クロシンは、アカネ科クチナシ（Ｇａｒｄｅｎｉａ ａｕｇｕｓｔａ ＭＥＲＲＩＬ ｖａｒ．ｇｒａｎｄｉｆｌｏｒａ ＨＯＲＴ．，Ｇａｒｄｅｎｉａ ｊａｓｍｉｎｏｉｄｅｓ ＥＬＬＩＳ）の果実、サフランの柱頭の乾燥物などに含まれるが、クロシンを得るための工業的原料としてはクチナシの果実が好ましく用いられる。

It is a compound represented by these. This crocetin is usually obtained by hydrolyzing crocin (a digentiobiose ester of crocetin), which is a carotenoid yellow pigment. Crocin is included in the fruits of Rubiaceae gardenia (Gardenia augusta MERRIL var.grandiflora HORT., Gardenia jasminoides ELLIS), dried saffron stigma, etc. Used.

  In the present invention, there is no limitation on the method for extracting crocin from the above plant base, for example, extraction from pulverized dry fruit of gardenia using water, alcohol (eg, methanol, ethanol, etc.), or a mixture thereof. A known method, such as, is used. For example, in the case of using a water / alcohol mixed solution, the extraction condition is preferably room temperature (about 0 to 30 ° C.) to 50 ° C. for about 1 to 18 hours, more preferably about 30 to 40 ° C. for about 2 to 4 hours. The extraction operation is usually repeated several times.

  In the present invention, it is preferable to further perform adsorption resin treatment or membrane separation treatment on the extract from gardenia to remove iridoid glycosides such as geniposide and increase the concentration of crocin.

  The hydrolysis of crocin may be carried out according to a conventional method, and is usually carried out by the action of acid, alkali or an appropriate hydrolase. Here, examples of the acid include hydrochloric acid, sulfuric acid, and phosphoric acid, and examples of the alkali include sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate. Examples of hydrolases include β-glucosidase.

Industrially, the hydrolysis of crocin is preferably hydrolysis with alkali.
The hydrolysis may be performed with stirring and / or heating. Preferably, it is heated to about 20 to 70 ° C., preferably about 40 to 60 ° C. with stirring, and is performed for about 1 to 24 hours, preferably about 3 to 5 hours. In this way, hydrolysis can be accelerated by hydrolysis.

  When the hydrolysis of crocin is an alkali hydrolysis, usually, after completion of the hydrolysis, an appropriate amount of an aqueous solution of an inorganic acid such as hydrochloric acid, sulfuric acid or phosphoric acid, or an organic acid such as citric acid is added to the reaction solution to improve the liquidity. The pH is adjusted to about 4.0 or less, preferably about pH 1.0 to 3.0, or the reaction solution is added to an aqueous solution of an inorganic acid such as hydrochloric acid, sulfuric acid or phosphoric acid, or an organic acid such as citric acid. The crocetin is precipitated by adjusting the property to about pH 4.0 or less, preferably about pH 1.0 to 3.0. Thereafter, the crocetin can be recovered as a paste-like solid by centrifuging the mixed liquid in which crocetin is precipitated or filtering through a filter paper or a filter cloth.

  When crocin is hydrolyzed with acid, crocetin is usually precipitated simultaneously with the hydrolysis, so that the reaction solution is obtained as a suspension. After completion of the reaction, crocetin can be recovered as a pasty solid by centrifuging the obtained suspension or filtering through a filter paper or filter cloth.

  The crocetin obtained in this way (paste-like solid) usually has acid, neutralized salt, and impurities derived from the raw material attached to the surface of the solid, so that it is washed for the purpose of removing the impurities. Processing is performed. The treatment may be performed using a known method, for example, washing the pasty solid with a sufficient amount of water. Next, the water remaining in the solid material may be removed by drying using a shelf-type ventilation dryer or a vacuum dryer, preferably at a temperature not exceeding about 50 ° C. in an atmosphere of nitrogen gas.

  As the crocetin according to the present invention, those obtained by washing the paste-like solid with water or those obtained by drying the water after washing with water are preferably used, but purified crocetin obtained by purifying these crocetins may also be used. Here, there is no restriction | limiting in the method of refine | purifying crocetin, For example, methods known per se, such as column chromatography and recrystallization, are used.

  The saccharides used in the present invention are not particularly limited. For example, monosaccharides such as glucose, fructose, and galactose, disaccharides such as maltose, lactose, and sucrose, starches, modified starches, polysaccharides such as amylose, amylopectin, dextrin, and cyclodextrin , Oligosaccharides such as fructooligosaccharides, galactooligosaccharides, maltotriose, maltotetraose, maltooligosaccharides such as maltopentaose and maltohexaose, gum arabic, carrageenan, caraya gum, agar, xanthan gum, guar gum, tamarind seed gum, tragacanth gum, Examples thereof include polysaccharides such as pectin and locust bean gum, sugar alcohols such as sorbitol, mannitol, maltitol or reduced starch syrup, preferably polysaccharides.

  As a method for producing a crocetin preparation according to the present invention, when preparing a dispersion by dispersing crocetin in an aqueous solution containing saccharides, the particle diameter (median diameter) of the dispersion is set to less than about 0.5 μm. Although it will not specifically limit if it is a thing, For example, it can manufacture by the following method 1 or 2.

[Method 1]
A suspension obtained by suspending water-washed crocetin (a paste-like solid) in water contains gum arabic heated to room temperature (about 0 to 30 ° C.) to 100 ° C., preferably about 45 to 65 ° C. In addition to the aqueous solution to be processed, this is processed using a high-pressure homogenizer to obtain the crocetin formulation according to the present invention.

[Method 2]
A suspension obtained by suspending water-washed crocetin (a pasty solid) in water is processed using a high-pressure homogenizer. The obtained treatment liquid is added to an aqueous solution containing gum arabic heated to room temperature (about 0 to 30 ° C.) to 100 ° C., preferably about 45 to 65 ° C., and a stirrer, a heating jacket, a baffle plate, etc. The mixture is stirred using a normal stirring / mixing tank provided to obtain a crocetin preparation according to the present invention.

  Examples of the high-pressure homogenizer include Claremix W Motion (M Technique), APV Gorin homogenizer (APV), Microfluidizer (Mizuho Kogyo), Ultimateizer (Sugino Machine) or Nanomizer (manufactured by Yamato Steel Co., Ltd.) The operating conditions by the homogenizer vary depending on the specifications of the apparatus and are not uniform. However, for example, it is preferable to set one pass (single-time treatment) or multiple passes (multiple-time treatment) at about 5 to 80 MPa.

  As the agitator, for example, a high-speed rotating dispersion / emulsifier such as TK homomixer (made by Tokushu Kika Kogyo Co., Ltd.) or Claremix (made by M Technique Co., Ltd.) is preferably used. As the operating conditions of the dispersing / emulsifying machine, for example, in a small laboratory machine, a rotation speed of about 2000 to 20000 rpm and a stirring time of about 5 to 60 minutes can be exemplified.

  The particle diameter (median diameter) of crocetin in the dispersion obtained by the above treatment is preferably less than about 0.5 μm, more preferably less than about 0.4 μm, and less than about 0.3 μm. Further preferred. When the particle diameter exceeds 0.5 μm, it is not preferable because precipitation of food and drink colored using the obtained preparation is not sufficiently suppressed. On the other hand, if the particle diameter is too small, the particles are aggregated and the dispersed state cannot be maintained, which is not preferable. Therefore, the lower limit is usually about 0.06 μm.

  In 100% by mass of the crocetin preparation according to the present invention, about 0.05 to 6% by mass of crocetin, preferably about 0.5 to 5% by mass, and about 0.05 to 60% by mass of saccharide, preferably about 1 to 30%. It is preferable to adjust the mass% so that the balance is water. The ratio of crocetin and saccharide is preferably adjusted to be about 1: 1 to 1:10, preferably about 1: 2 to 1: 6.

  The crocetin preparation produced by the above methods 1 and 2 has a water-dispersible form in which crocetin is dispersed in an aqueous solution. These water-dispersible crocetin preparations are dried by a method known per se, A powdery crocetin preparation may be used.

  Examples of the drying method include spray drying, drum drying, belt drying, vacuum drying, vacuum freeze drying, and the like, preferably vacuum freeze drying or spray drying.

  There is no restriction | limiting in particular as an 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, a water-dispersible crocetin preparation (preferably a mixture of the preparation and an appropriate amount of excipients such as water and dextrin) is -20 ° C. or less, about It is preferable to freeze at −30 to −40 ° C. and dry the obtained frozen product for about 10 to 72 hours while heating at about 30 to 60 ° C. under a vacuum of about 10 to 100 Pa. The obtained freeze-dried product is pulverized by a method known per se and preferably sieved to obtain a powdery crocetin preparation. The loss on drying of the resulting powdery crocetin preparation is usually about 5% by mass or less, preferably about 1 to 3% by mass.

  There is no restriction | limiting in particular as an apparatus used for spray-drying, Well-known apparatuses, such as a spray-type spray-drying apparatus or a rotary disk-type spray-drying apparatus, can be used. In addition, as operation conditions for spray drying, for example, the dispersion is supplied to a pressure nozzle type spray drying apparatus, hot air inlet temperature is about 120 to 170 ° C, preferably about 140 to 150 ° C, exhaust temperature is about 70 to 140 ° C, Preferably, the powdered crocetin preparation can be obtained by spray-drying under conditions of about 85 to 90 ° C. and collecting the dried product with a cyclone. The powdery crocetin preparation obtained has an average particle size of about 20 to 200 μm, preferably about 60 to 100 μm. Further, the loss on drying is preferably about 10% by mass or less, and more preferably about 7% by mass or less.

  An example of a preferred embodiment of the powdered crocetin formulation according to the present invention is about 0.1 to 10% by mass of crocetin, preferably about 0.2 to 4% by mass and about 90 to 90% of saccharide in 100% by mass of the formulation. It is a powder containing 99.9% by weight, preferably about 96-99.8% by weight. The color value is preferably about 50 to 1000, and more preferably about 100 to 400.

  In the present invention, a food emulsifier such as glycerin fatty acid ester, sucrose fatty acid ester, sorbitan fatty acid ester, propylene glycol fatty acid ester and lecithin is added to the crocetin preparation within a range not inhibiting the purpose and effect of the present invention. May be. Here, the glycerin fatty acid ester includes, in addition to an ester of glycerin and a fatty acid, glycerin acetic acid ester, glycerin acetic acid fatty acid ester, glycerin lactic acid fatty acid ester, glycerin citrate fatty acid ester, glycerin succinic acid fatty acid ester, glycerin diacetyl tartaric acid fatty acid ester, Examples include polyglycerin fatty acid ester and polyglycerin condensed ricinoleic acid ester. The lecithin is not particularly limited as long as it is obtained from oil seeds or animal raw materials and contains phospholipid as a main component. For example, oil is removed from liquid lecithin containing oil such as soybean lecithin and egg yolk lecithin. Examples thereof include dry powdered lecithin, fractionated lecithin obtained by separating and purifying liquid lecithin, and enzymatically decomposed lecithin obtained by treating lecithin with an enzyme and enzyme-treated lecithin.

  The crocetin preparation obtained by the production method of the present invention can be used as a coloring agent for a wide range of foods and drinks, but is particularly suitable for coloring beverages filled in transparent containers such as PET bottles (PET containers). be able to.

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

[Preparation of crocetin]
60 L of an ethanol / water mixture (50:50) was added to 30 kg of the pulverized dried fruit of gardenia and stirred at room temperature for 3 hours, followed by suction filtration. After filtration, 60 L of an ethanol / water mixture (50:50) was added to the extraction residue, and the mixture was stirred at room temperature for 30 minutes and then suction filtered twice to obtain about 175 L of extract as a filtrate. The extract was concentrated using a rotary evaporator under the conditions of about 60 ° C. and about 4 kPa to obtain about 10.5 kg of a concentrate 1 (color value = about 570).

  Purified water is added to the obtained concentrate 1 to make 100 L, the resulting solution is suction filtered, and the filtrate is packed in a column packed with 50 L of Amberlite XAD-7 (manufactured by Organo) at a flow rate of SV = 0.5. The liquid was passed. Subsequently, 400 L of purified water was passed through the column at a flow rate SV = 0.5, and the discharged liquid was discarded. Next, 50 L of an ethanol / water mixture (70:30) was passed at a flow rate SV = 0.5 to desorb and elute the dye. The obtained eluate was concentrated using an evaporator under the conditions of about 60 ° C. and about 4 kPa to obtain about 3.5 kg of concentrate 2 (color value = about 1600) containing crocin.

  The obtained concentrate 2 and 600 g of 40% by mass aqueous sodium hydroxide solution were mixed and subjected to a hydrolysis reaction at 60 ° C. for about 3.5 hours with stirring. After completion of the reaction, the reaction solution was acidified by adding it to 15 L of 4% by mass phosphoric acid aqueous solution, and then allowed to stand at room temperature for about 3 hours. Next, the precipitated precipitate was collected by centrifugation (10,000 × g, 10 minutes), further washed with 5 L of water, and centrifuged twice to repeat the operation of crocetin composition (a pasty solid) ( (Color value = about 2000) About 2750 g was obtained. The crocetin content in the crocetin composition was about 5.5% by mass.

  The color value was measured by the following [Color value measuring method].

[Color value measurement method]
1) A sample is accurately weighed so that the absorbance to be measured is in the range of 0.3 to 0.7, and dissolved in dimethyl sulfoxide to make exactly 100 ml.
2) Weigh exactly 5 ml, and add Kolthoff buffer solution (50 mM Na2B4O7 · 10H2O-50 mM Na2CO3, pH 10.0) to make 50 ml.
3) Weigh exactly 5 ml of the solution, and add Kolthoff buffer (pH 10.0) to make 50 ml.
4) Weigh exactly 5 ml, add Kolthoff buffer (pH 10.0) to make 50 ml, and use this solution as the test solution.
5) Using a Kolthoff buffer solution (pH 10.0) as a control, measure the absorbance A at the maximum absorption portion near 420 nm with a liquid layer length of 1 cm, and obtain the color value by the following formula.

[Example 1]
685.0 g of the previously prepared crocetin composition (color value = about 2000) was suspended in 436.0 g of purified water to obtain 1121.0 g of crocetin suspension. Next, 187.5 g of gum arabic (trade name: San Arabic, manufactured by Sanei Pharmaceutical Co., Ltd.) and 779.0 g of purified water were added to a 3000 mL beaker, heated to 40 ° C. and dissolved, and then the crocetin suspension was added. Added and mixed uniformly. The obtained mixed solution was passed through an 83 mesh sieve, and then subjected to a 2-pass treatment at 50 MPa using a microfluidizer (manufactured by Mizuho Kogyo Co., Ltd .; equipped with L-210Z chamber). ) 3100 g was obtained. The average particle size of crocetin in the obtained preparation was about 0.34 μm.

[Measurement method of particle size]
For the measurement of the particle diameter, a laser diffraction / dispersion particle size distribution analyzer (model: LA-920; manufactured by Horiba, Ltd.) was used, and the particle diameter was calculated from the volume frequency as the median diameter. The particle diameter of crocetin was measured using water as a medium.

[Example 2]
1222 g of the previously prepared crocetin composition (color value = about 2000) was suspended in 778 g of purified water to obtain 2000 g of crocetin suspension. The suspension was passed through an 83 mesh sieve, and then subjected to 1 pass treatment at 50 MPa using a microfluidizer (manufactured by Mizuho Kogyo Co., Ltd .; L-210Z chamber mounted) to obtain 1900 g of treatment liquid A. Next, 93.75 g of gum arabic (trade name: San Arabic, manufactured by Sanei Pharmaceutical Co., Ltd.) and 389.5 g of purified water were added to a 1000 mL volume meter, and the mixture was heated to 40 ° C. for dissolution, and then treated liquid A560. 5 g was added and mixed uniformly. The obtained mixed solution was passed through an 83 mesh sieve, and stirred at 12 000 rpm for 12 minutes using Claremix (manufactured by MTechnic Co., Ltd.) while being kept at 40 ° C., and a water dispersible crocetin preparation (Example product) 2) 1040 g was obtained. The particle size of crocetin in the obtained preparation was about 0.26 μm.

[Example 3]
223.8 g of a water dispersible crocetin preparation prepared in the same manner as in Example 1, 372.5 g of dextrin, and 1403.7 g of purified water were mixed. After filling the obtained mixed liquid in a metal tray having a length of 298 mm, a width of 435 mm, and a height of 25 mm and pre-freezing at −35 ° C. for 24 hours using a freeze dryer (model: DC500; manufactured by Yamato Scientific Co., Ltd.) The sample was freeze-dried for about 27 to 28 hours at a shelf temperature of 50 ° C. under a vacuum of 13 Pa. The resulting lyophilized product was pulverized using a pin mill having a 0.5 mm screen to obtain 380 g of a powdery crocetin powder formulation (Example Product 3). The loss on drying of the obtained preparation was 2.5% by mass.

[Example 4]
223.8 g of a water dispersible crocetin preparation prepared in the same manner as in Example 2, 372.5 g of dextrin, and 1403.7 g of purified water were mixed. After filling the obtained mixed liquid in a metal tray having a length of 298 mm, a width of 435 mm, and a height of 25 mm and pre-freezing at −35 ° C. for 24 hours using a freeze dryer (model: DC500; manufactured by Yamato Scientific Co., Ltd.) The sample was freeze-dried for about 27 to 28 hours at a shelf temperature of 50 ° C. under a vacuum of 13 Pa. The obtained freeze-dried product was pulverized using a pin mill having a 0.5 mm screen to obtain 380 g of a powdery crocetin powder formulation (Example product 4). The loss on drying of the obtained preparation was 2.5% by mass.

[Comparative Example 1]
342.5 g of the previously prepared crocetin composition (color value = approximately 2000) was suspended in 217.0 g of purified water to obtain 560.5 g of crocetin suspension. Next, 93.75 g of gum arabic (trade name: San-Arabic; manufactured by Sanei Pharmaceutical Co., Ltd.) and 389.5 g of purified water were added to a 1000 mL volume meter, dissolved by heating to 40 ° C., and then the crocetin suspension 560.5 g of liquid was added and mixed uniformly. The obtained mixed solution was passed through an 83 mesh sieve, and then stirred at 12 000 rpm for 12 minutes using Claremix (manufactured by M Technique Co., Ltd.) while being kept at 40 ° C., and a water dispersible crocetin preparation (comparative example product) 1) 1040 g was obtained. The particle size of crocetin in the obtained preparation was about 0.77 μm.

[Comparative Example 2]
223.8 g of a water dispersible crocetin preparation prepared in the same manner as in Comparative Example 1, 372.5 g of dextrin and 1403.7 g of purified water were mixed. After filling the obtained mixed liquid in a metal tray having a length of 298 mm, a width of 435 mm, and a height of 25 mm and pre-freezing at −35 ° C. for 24 hours using a freeze dryer (model: DC500; manufactured by Yamato Scientific Co., Ltd.) The sample was freeze-dried for about 27 to 28 hours at a shelf temperature of 50 ° C. under a vacuum of 13 Pa. The obtained freeze-dried product was pulverized using a pin mill having a 0.5 mm screen to obtain 380 g of a powdery crocetin powder formulation (Comparative Example product 2). The loss on drying of the obtained preparation was 2.5% by mass.

[Test example]
Crocetin preparations obtained in the above Examples and Comparative Examples (Examples 1 to 4 and Comparative Examples 1 and 2) 1.1 g, fructose glucose liquid sugar (trade name: Hyfract M; manufactured by Nippon Cornstarch), citric acid (Anhydrous) (Wako Pure Chemical Industries, Ltd.) 0.15 g, sodium citrate (anhydrous) (Wako Pure Chemical Industries, Ltd.) 0.06 g and purified water 84.69 g were mixed to prepare a simulated beverage. After filling the simulated beverage with 50 g in a 50 mL capacity plastic bottle (PET container), it was allowed to stand overnight, and the bottom of the PET bottle was visually observed to evaluate the degree of precipitation that occurred. The results are symbolized according to the following criteria and shown in Table 1.
○: A very small amount of precipitation is observed Δ: A small amount of precipitation is recognized ×: A large amount of precipitation is observed

  As is clear from the results in Table 1, the beverage colored using the crocetin preparations (Example products 1 to 4) obtained by the production method of the present invention had clearly suppressed precipitation.

Claims (1)

formula

When preparing a dispersion by dispersing crocetin represented by the formula in an aqueous solution containing gum arabic , the particle diameter of crocetin in the dispersion is less than 0.4 μm in median size. A method for producing a crocetin preparation.