JP4666932B2 - Method for producing carbohydrate-carotenoid pigment fat solution and / or solid solution - Google Patents

Description

The present invention relates to a method for producing a saccharide-carotenoid pigment fat solution and / or solid solution, and more specifically, a method for producing a fat solution by dissolving and / or uniformly dispersing a carotenoid pigment that is not dissolved and / or uniformly dispersed in water. Further, the present invention relates to a method for producing a solid solution which is not dissolved and / or uniformly dispersed in water but is in an easily usable form.
In the present invention, a carotenoid pigment in the form of a solution is expressed as a fat solution, and this includes a state in which the pigment is uniformly and stably present in the liquid even in a suspension. . In addition, a carotenoid pigment that is uniformly mixed with other materials and separated as a solid from the liquid is expressed as a solid solution. The fat solution and the solid solution are collectively referred to as both solutions, and the term “sugar wrap” is used as a general concept in the sense that the pigment is encapsulated with carbohydrates.

Carotenoid pigments are also called carotenoids, carotenoids, and carotenoid pigments, and are yellow, red, and purple water-insoluble pigments produced by green plants, molds, yeasts, mushrooms, bacteria, and the like. Many of these pigments have a tetraterpenoid structure with 40 carbon atoms, and are based on lycopene (a carotene or carotene: a generic name for carotenoid hydrocarbons) that are common in tomato fruits. The dyes are known. In addition to chloroplast β-carotene, lutein, violaxanthin, etc., spiroloxanthine and spheroidene are also contained in photosynthetic microorganisms, and animals contain red astaxanthin contained in shrimp and crab shells by binding to proteins. It is.
Yellow to red carotenoid pigments widely present in animals and plants such as carrots, pumpkins, egg yolks and butter are taken from animals or plants and converted into physiologically active substances such as vitamin A and used. In addition, it has been used as a dye and food coloring for a long time. However, its structural formula is a polyene structure in which every other double bond is repeated, and it is susceptible to air oxidation and photooxidation, and easily decomposes and fades.

  Therefore, development of a method for making the material easy to use by increasing its stability and solubility in water has been sought, and several methods have been developed. One of them is “a red coloring method for marine products” (for example, see Patent Document 1). In this method, a carotenoid pigment is dispersed using one or more of an emulsifier, a thickening stabilizer and an emulsion stabilizing effect, and then refined, or an oil-soluble carotenoid pigment is refined. Thereafter, the reddish colorant obtained by dispersing the emulsifier, the thickening stabilizer, and one or more food materials having an emulsion stabilizing effect is used as a raw material, and the aquatic product is colored red.

  In addition, “stable inclusion compound of astaxanthin and γ-cyclodextrin and method for producing the same, and liquid, food and drink, feed, pharmaceutical and cosmetic use” (for example, see Patent Document 2), “stable astaxanthin-cyclodextrin There are also clathrate compounds and methods for producing the same, and solutions, foods, drinks, feeds, pharmaceuticals and cosmetics containing the clathrate compounds (see, for example, Patent Document 3). This is a method for stabilizing and expanding the use surface by forming a clathrate using an abbreviation.

Japanese Unexamined Patent Publication No. 7-135929 JP 2002-348275 A JP 2002-348276 A

However, these methods are complicated and require many processes and time for production, and emulsifiers, thickening stabilizers, CDs and the like are somewhat expensive as food materials and disadvantageous for practical use. Therefore, if a method for improving the water insolubility of carotenoid pigments by using cheaper and safer raw materials and making them into fat solutions or solid solutions is found, the use is expected to expand more than ever. Is done.
Accordingly, an object of the present invention is to provide a method for producing a carbohydrate-carotenoid pigment fat solution and a carbohydrate-carotenoid pigment solid solution.

In order to solve the above-mentioned problems, the present inventors diligently studied a method for producing a fat solution and a solid solution using starch as a raw material, and as a result of studying a method for dissolving and / or uniformly dispersing a pigment with starch, It has been found that sugar-dye solutions can be prepared with most starches other than corn starch. However, when the starch concentration is high, it is difficult to use because it is gelled and difficult to become powder. Therefore, a sugar material that is easy to be powdered was sought. As a result, it was found that the low hydrolyzate of starch has the ability to form a fat solution, and that it is difficult to form a fat solution with the high hydrolyzate of starch, and the starch was partially hydrolyzed with an enzyme. A method for directly preparing a saccharide-dye solution was established by using a partially hydrolyzed saccharide or by allowing starch hydrolase to act on a mixture of starch and pigment.
Furthermore, when the lipid solution formation of a pigment | dye is inadequate only with starch and amylolytic enzyme, solubility will improve if a pigment | dye is melt | dissolved and / or uniformly disperse | distributed in a 5-25% ethanol solution. What was prepared in this way can be dried as needed, and can be set as a saccharide-dye mixture powder and a saccharide-dye mixture powder.
Conversely, if the saccharide-pigment precipitates in a uniformly mixed state, it becomes a solid solution and can be an easy-to-use material. For this purpose, it is appropriate to use high amylose corn starch as the starch. If a dye is added in the form of a dissolved and / or uniformly suspended sugar solution and shaken or mixed by heating, the solid solution is obtained. can get. Furthermore, in the case of ordinary starch, a solid solution is formed when the enzyme action is performed under conditions stronger than the fat solution forming conditions. However, the present inventors have found that no solid solution is formed under strong reaction conditions and that the formation of a solid solution is facilitated by the addition of an ionic component, and the present invention has been reached based on these findings.

The present invention according to claim 1 is used to dissolve and / or uniformly disperse astaxanthin , which is a carotenoid pigment, to obtain a fat solution; potato starch, corn starch, waxy corn starch, wheat starch, tapioca starch A partially decomposed saccharide satisfying any one of the following conditions (a) to (c) of sago starch, glutinous rice starch and one or more types of starch among glutinous rice starch; It is a method for producing a carbohydrate-carotenoid pigment fat solution characterized by preparing a mixture containing a carbohydrate and water.
(A) Acid partially degraded carbohydrate having a Dextrose Equivalent value of 15 to 40.
(B) Low partial hydrolysis reaction using cyclodextrin synthase under conditions of enzyme concentration 0.4 to 1.0 THU / g starch, reaction pH 5.0 to 6.5, reaction temperature 35 to 65 ° C., reaction time 2 to 24 hours Partially decomposed carbohydrates obtained by
(C) Using α-amylase, an enzyme concentration of 3.35 to 6.7 U / g starch (a paste refining power measurement Amano method), reaction pH 5.0 to 6.5, reaction temperature 35 to 65 ° C., reaction time 2 to 24 hours Partially decomposed saccharide obtained by performing a low partial hydrolysis reaction under conditions.
The present invention described in claim 2 uses a carotenoid pigment dissolved and / or uniformly dispersed in a 5 to 25% ethanol solution as the carotenoid pigment, according to claim 1. This is a method for producing a fat solution.

According to a third aspect of the invention, claim 1 or 2 carbohydrate prepared by any of the methods described - a carotenoid-based pigments butter solution, dried to give carbohydrate - carotenoid-based dye mixture dried product Or its powder.
The present invention according to claim 4 is the dried product or the powder thereof according to claim 3 , wherein the drying treatment is spray drying or freeze drying.
The present invention according to claim 5 is a solution in which the carbohydrate-carotenoid pigment fat solution prepared by the method according to claim 1 or 2 is dissolved and / or a uniform dispersion; sodium chloride and organic acid are added to caustic soda. A method for producing a carbohydrate-carotenoid pigment solid solution, which comprises adding at least one substance selected from salts, amino acids, and proteins produced by neutralization in step (b).
The present invention according to claim 6 is the method for producing a solid solution according to claim 5 , wherein the organic acid is acetic acid or citric acid, the amino acid is glycine or sodium glutamate, and the protein is milk casein. .

  According to the present invention, a carotenoid pigment can be dissolved and / or uniformly dispersed using a starch that is a saccharide to form a fat solution. Furthermore, since it becomes difficult to form a powder when the starch concentration is high, a low hydrolyzate of starch is used as an easy-to-powder material, and a fat solution is formed with or without ethanol. Can be dried and powdered. On the other hand, when a high hydrolyzate of starch is used, a solid solution is formed with or without the addition of ethanol. In this case, the solid solution formation efficiency can be increased by adding an ionic substance. The material prepared in this way is easy to use and the carotenoid pigment is stabilized, so that it can be used for a wider range of applications.

In the present invention, carotenoid (also referred to as carotenoid) is used as a pigment, and examples of food materials include commercially available anato pigments. This pigment is a pigment extracted from the seeds of the genus Beninoki, which is mainly composed of bixin and norbixin, and is acidic yellow and neutral and red. There are commercially available “Orange Color 100” and “Orange Color 75 WS” (both trade names), which are mainly capsanthins obtained from red pepper fruits, orange to red. Presents.
In addition, as gardenia yellow, there are commercially available “Kirishin L Conch”, “Kirishin LY”, “Kirishin A-15P”, “Kirishin K-400 (G)” (all trade names), etc. Water-soluble crocin and crocetin obtained from the above. These dyes have a beautiful yellow color, but are relatively weak to light and acid. This dye is water-soluble because its molecular end is an ester with a carboxylic acid or saccharide, but it also dissolves well in ethanol solution and has fat solubility. The method of the present invention can be applied to these carotenoid pigments, and its application range is extremely wide.

Various types of starch can be applied to the present invention. Generally, starch containing a large amount of amylopectin is preferable for forming a fat solution, and starch containing a large amount of amylose is preferable for forming a solid solution. Since starch normally contains about 20 to 30% amylose and 80 to 70% amylopectin, if the conditions of the starch to be used are set appropriately, either a fat solution or a solid solution can be prepared. However, in the case of solid solution formation, amylose 50% and 70% of high amylose corn starch can be applied, but it is difficult to apply it to a product that has been heat-treated and processed into indigestible.
As the starch hydrolyzate, there are various commercially available dextrins. Generally, those produced by the enzymatic hydrolysis method are not suitably used for forming any solution. On the other hand, the product produced by the acid hydrolysis method can be used for the formation of a fat solution and further for the formation of a solid solution if DE is appropriately selected. The reason for this is considered that the enzyme decomposition method is a saccharide molecule that has a more uniform molecular size and is easily dissolved. On the other hand, in the acid decomposition method, saccharide molecules are heterogeneous and large and small molecules are mixed, and it is considered that large molecules are involved in the formation of fat and solid solutions. Even if this large molecule carbohydrate contains a small molecule (except CD), there is no significant change in the formation of both solutions.
In the case of other sugars such as monosaccharides such as glucose and fructose, oligosaccharides such as maltose and trehalose, sugar alcohols such as erythritol and sorbitol alone or a mixture thereof, the carotenoid pigment is slightly dissolved. However, it is not suitable for the production of food materials. However, there is a possibility that it can be applied to medicines, cosmetics and the like with a small amount of addition.

In the present invention, as the enzyme agent, a starch dextrinase such as cyclodextrin synthase (hereinafter sometimes abbreviated as CGTase), α-amylase, glucoamylase, pullulanase, etc. is used. The main function of the enzyme agent is starch. The internal chain of the molecule is cleaved to an appropriate size, and the standard is that the starch starts to liquefy and begins to become a non-viscous sugar solution.
Thus, the type of enzyme is not limited to a specific one, and any enzyme may be used as long as it can cleave starch molecules with a slight viscosity remaining. In particular, in CGTase, enzymes derived from microorganisms such as macerans, stealthermophilus, and avensis are known, but are not limited thereto. Similarly, various α-amylases can be used. As a commercially available enzyme, there is “Contizyme” (Bacillus macerans enzyme) manufactured by Amano Enzyme Co., Ltd., which is 600 THU / mL (Tilden-Hudson method EBTilden and CSHudson: J. Bacteriol., 43, 527 (1942)) or more It is a solution having the activity of As other α-amylase, there is “Amylase AD [Amano] 1” manufactured by Amano Enzyme, and 10,000 U / g powder (pH 6.0, measured by the Amano method for measuring paste refinement power) per dry starch. 0.1 to 0.3% is the standard usage. In addition, since there are commercially available enzymes such as glucoamylase and pullulanase, these can be used, but the effect is inferior to that of CGTase and α-amylase, and in particular, the effect of pullulanase is inferior.

Enzyme reaction standard conditions for fat solution formation are as follows: CGTase 0.1-0.25 μL (0.4-1.0 THU / g starch), reaction temperature 35-65 ° C. (preferably 45 ° C.), reaction time 2 It is a shaking reaction at a reaction pH of 5.0 to 6.5 (preferably 5.0 to 6.0) for -24 hours (preferably 12 hours). The amount of enzyme used in normal CD production is 10 THU / g starch, 24 hours.
On the other hand, α-amylase was added in an amount of 0.1 mg to 0.05 mg of enzyme powder with respect to 150 mg of corn starch, a reaction temperature of 35 to 65 ° C. (preferably 45 ° C.), a reaction time of 2 to 24 hours (preferably 12 hours), and a reaction. This is a shaking reaction of pH 5.0 to 6.5 (preferably 5.0 to 6.0). When the amount of the enzyme is calculated, it becomes 3.35 to 6.7 U / g starch (a paste refining power measurement Amano method). Since 0.1% per dry starch is the normal amount used, the amount added per gram starch is 1 mg, which corresponds to 10 U / g. Therefore, the enzyme amount in the present invention is about the normal amount used. That is a half to a third. In addition, since a fat solution and a solid solution may be formed depending on conditions even outside this range, an enzyme amount suitable for the conditions should be selected.

  By the way, about the type of starch and the formation of both solutions, 10ml of corn starch, waxy corn starch, high amylose corn starch, roadster (processed starch processed from high amylose corn starch), potato starch, wheat starch, glutinous rice starch or glutinous rice starch Weigh each 150 mg into a pressure-resistant vial, add 1 mL of an ethanol solution containing 25 mg of dye and 4 mL of 0.2 M acetate buffer (pH 5.0), dissolve by heating in a hot water bath, and allow to cool to 45 ° C. Thereafter, 50 μL of an enzyme solution containing 0.1 THU / 50 μL of CGTase was added to the same buffer, and a shaking reaction was performed at 45 ° C. for 12 hours. The results are shown in Table 1. The color after 12 hours in the table indicates the color of the supernatant / precipitation color when there is a supernatant, and the color changes from orange to red when the color of the precipitate changes by shaking. . Further, + in the CGTase column indicates that the enzyme is added,-indicates no addition, ◎ in the fat solution / solid solution formation column indicates that the fat solution formation is good, ○ indicates that the fat solution is formed, □ indicates that the solid solution is formed, Δ indicates that the solid solution is not formed, X indicates that neither a fat solution nor a solid solution is formed.

As is clear from Table 1, it was difficult to form both solutions by the reaction of CGTase in waxy corn starch and glutinous rice starch. In addition, when starch is added and a fat solution is formed, there is no change in color tone even after 12 hours of this treatment, indicating that it has been stabilized. In the control experimental group (1) where no starch was added, the color faded to orange.
In addition, also in other starches, when an enzyme reaction is strengthened, the formation degree of both solutions will fall. In addition, glucoamylase shows the same tendency as α-amylase, but the formation effect is poor. When pullulanase is added and reacted, both solutions are not formed regardless of the strength of the reaction.

  Next, the influence of CD on the solution of carotenoid pigment (astaxanthin) was examined. The results are shown in Table 2. All solutions contain 1 mL of ethanol solution containing 25 mg of dye and 4 mL of 0.2 M acetate buffer (pH 5.0), the amount of CD is 150 mg, + in the table is added,-is not added Show. The mixture was shaken at 45 ° C. for 12 hours. The color after 12 hours in the table indicates the color of the supernatant / precipitation color when the supernatant is present, and expresses from orange to red when the color of the precipitate changes by shaking. .

  As shown in Table 2, in the control experiment using α, β, and γ-CD, all inhibited the formation of lipid solution, and the strength was in the order of γ> β> α, and in particular, γ-CD The inhibition by is great. In addition, in β-CD, slight precipitation occurs due to inclusion body formation. Therefore, it is inferred that formation of both solutions becomes difficult by hydrolysis with CGTase and CD formation.

Furthermore, the lipid solution and the solid solution forming ability according to the type of starch were examined and roughly classified into three systems as follows.
Series 1: Starch that has the ability to form a fat solution by itself and forms a solid solution by the action of CGTase.
System 2: Starch that has the ability to form a fat solution by itself, does not form a solid solution by the action of CGTase, and inhibits the formation of a fat solution.
Series 3: Starch that has the ability to form a solid solution by itself and forms a solid solution even by CGTase action.
Starch belonging to system 1 is a starch composed of a combination of amylopectin and amylose, and starch belonging to system 2 is a starch containing only amylopectin. Moreover, the starch which belongs to 3 type | system | groups corresponds to the starch which has amylose as a main component.

If fat solution formation is desired, non-degraded starch (except high amylose starch) and / or low-hydrolysis starch may be used. If the formation of fat solution is insufficient, hydrolyzing enzyme and waxy starch may be combined. It is effective to add ethanol as a supplement.
On the other hand, for the formation of the solid solution, it is effective to use high amylose starch and / or highly hydrolyzed starch, or to add ionic materials such as sodium chloride, sodium acetate and amino acids to non-degraded starch or low-hydrolyzed starch. is there. In addition, wheat starch and glutinous rice starch have low solid solution forming ability by CGTase.

Next, hydrolysis conditions were examined. Low partial hydrolysis conditions: For CGTase, enzyme concentration of 0.4 to 1.0 THU / g starch, reaction pH of 5.0 to 6.5, reaction temperature of 35 to 65 ° C., reaction time of 2 to 24 hours are suitable. In addition, α-amylase has an enzyme concentration of 3.35 to 6.7 U / g starch (a paste scouring power measurement Amano method), a reaction pH of 5.0 to 6.5, a reaction temperature of 35 to 65 ° C., and a reaction time of about 2 to 24 hours. Is appropriate.
High partial hydrolysis conditions: For CGTase, an enzyme concentration of 1.0 to 10 THU / g starch, reaction pH 5.0 to 6.5, reaction temperature 35 to 65 ° C., reaction time 12 to 24 hours are appropriate, and α-amylase Then, the enzyme concentration is 6.7 to 20 U / g starch (a paste refinement force measuring Amano method), reaction pH is 5.0 to 6.5, reaction temperature is 35 to 65 ° C., and reaction time is about 12 to 24 hours. However, depending on the conditions, it is expected that a fat solution and a solid solution can be formed even outside this range. It may be possible to use materials that have been made resistant to digestion by removing low molecular weight components from acid hydrolyzed starch or making various bonds by acid / high temperature treatment.

  In addition, when ethanol is used in dissolving and / or uniformly dispersing a carotenoid pigment using a carbohydrate to form a fat solution, the amount of ethanol added is usually preferably 5% to 25%, Although about 20% is suitable, it is not necessary to add it as long as a fat solution is formed even if ethanol is not present depending on the type of sugar used.

Next, conditions for forming the desired fat solution using dextrin were examined using commercially available starch hydrolyzate products. All solutions contain 25 mg of the dye astaxanthin and 5 mL of distilled water. The amount of dextrin used is 150 mg, + in the table indicates addition, and-indicates no addition. The mixture was shaken at 45 ° C. for 12 hours. An example of the result is shown in Table 3. In the table, ◯ indicates that a fat solution is formed, Δ indicates that the fat solution is not formed, and × indicates that a fat solution is not formed.
As a result of the investigation, a fat solution was formed when a product of DE 15 to 40 was used as an acid partial decomposition product, but formation of a fat solution was difficult with other dextrins. As is apparent from the results in Table 3, the acid-decomposed dextrin may be a dextrin that forms a fat solution even if the DE is 15 or less. In addition to this, there is a possibility of application to branched dextrin, highly branched cyclic dextrin, etc., pullulan, dextran, and other carbohydrates having different binding modes. It is also conceivable to add monosaccharides, oligosaccharides, sugar alcohols and the like as solubilizing agents.

  When about 0.2M sodium chloride is added to the fat solution thus prepared, a red precipitate is formed. If this is left or centrifuged, flakes can be obtained. When starch hydrolase such as CGTase is reacted under conditions stronger than the conditions for forming a fat solution, a solid solution is obtained. In addition to salt, amino acids such as glycine and sodium glutamate, and proteins such as milk casein also form a solid solution, so that it can be seen that the addition of an ionic substance is effective in forming a solid solution. In addition, it is expected that the same effect will be obtained by the peptide. Furthermore, a solid solution is easily formed even with a salt formed by neutralizing an organic acid such as acetic acid or citric acid with caustic soda.

  If the fat solution is dried, a powder is obtained. Since this powder dissolves into a red solution, it can be used for the production of various foods. There is no particular limitation on the drying method, and an economical method should be selected, but spray drying is convenient. If it is only concentrated, heating concentration using a utility can or the like can also be used.

  In addition to the above, starch containing a large amount of amylose can also be used for the preparation of the solid solution. The desired solid solution can be obtained simply by adding a dye to this type of starch, stirring and dissolving with heating, and allowing to stand at room temperature. Moreover, if it is an alkaline and stable pigment | dye, a high amylose corn starch can be solubilized with an alkali, and after adding a pigment | dye to this, it can also neutralize and make it a solid solution. In the case of this standard, the solubility is inferior, making it difficult to use it in liquid food. In addition, in the case of a dye having poor alkalinity, it should be neutralized as soon as possible.

The fat solution and solid solution obtained by the present invention are also effective in stabilizing the pigment. For example, the gardenia yellow pigment is effectively inhibited from fading by using a sugar wrap. As described above, the carotenoid-based saccharide wrap has a wide range of applications, mainly foods, and can be used in the fields of cosmetics, pharmaceuticals, and the like.
In addition, in the method of this invention, starch processed products (for example, chemically modified starch etc.) other than dextrin, a soluble fiber, etc. may be utilized. A carbohydrate can be precipitated with ethanol, and a fat-soluble component can be mixed in the precipitate and dissolved in water to form a fat solution, or kneaded and mixed to form a solid solution.

By the way, about various commercially available edible pigment | dyes, it experimented using potato starch, and it was investigated whether a fat solution and a solid solution could be formed. That is, the presence or absence of the formation of fat solution and solid solution by high partial hydrolysis reaction with potato starch and CGTase (conditions: CGTase concentration 10 THU / g starch, reaction pH 5.0, reaction temperature 45 ° C., reaction time 12 hours) was examined. The results are shown below. There were three types of solid solutions that were difficult to form.
Commercial food dyes that form fat solutions with potato starch and form solid solutions by high partial hydrolysis
KC yellow KL-15, KC yellow CP-15, KC yellow CP-35, KC yellow GC,
KC yellow GE-2, KC orange PP, KC orange PE-3C, KC orange PE-DK,
KC orange PE-S, Paprika base No.30, KC orange YE-3, KC orange YE-2,
KC orange BE-03, KC orange TO-10, Anato yellow, Anato yellow No.2,
Orange S, Orange S conc, Anato yellow K, Paprika CWS, Paprika CKD25Y,
Paprika CKD30Y, Paprika CKD30, Haematococcus WS-10, Haematococcus KD-10,
β-carotene WS, β-carotene KD30, Palm carotene KD30
Formation of fat solution with potato starch, commercial food coloring that does not form solid solution by high partial hydrolysis (however, solid solution is formed by adding salt)
Gardenia 120, Annatto color 100, Gardenia yellow AYNo.5D

  Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.

Example 1
Potato starch is used as the starch, 150 mg is placed in a 10 mL vial, 4 mL of 0.2 M acetic acid buffer (pH 5.0) and 1 mL of the dye astaxanthin in ethanol (containing 25 mg / mL of the dye) are added and dissolved in a boiling water bath. As a result, a red solution was prepared (formation of fat solution). As a result of observing this by shaking at 45 ° C. for 12 hours, the dye was uniformly dissolved and dispersed, and the formation of a fat solution was maintained. On the other hand, when the same treatment was carried out without adding potato starch, the dye faded and turned orange. This indicates that the dye is stabilized by the formation of the fat solution. Although a carotenoid pigment may be directly coated on starch such as potato starch, this method is difficult to mix uniformly and it is difficult to obtain a dry powder.

Example 2
When it implemented like Example 1 except having used corn starch as starch, a fat solution was formed. In addition, the solubility of starch was inferior, and a slight precipitate was formed.

Example 3
A stable fat solution was formed in the same manner as in Example 1 except that waxy corn starch was used as the starch.

Example 4
Use potato starch as the starch, add 150 mg to a 10 mL vial, add 4 mL of 0.2 M acetate buffer (pH 5.0) and 1 mL of the dye astaxanthin in ethanol (containing 25 mg / mL of the dye), and dissolve in a boiling water bath. Then, after cooling to about 50 ° C., 50 μL of an enzyme solution containing 0.3 THU of CGTase was added and a shaking reaction was performed for 12 hours. After the reaction, the mixture was treated in an autoclave at 120 ° C. for 10 minutes and then allowed to cool to room temperature, whereby a fat solution could be prepared. In addition, instead of CGTase, α-amylase was reacted under the conditions of 1 U / g starch (gel paste sizing force measurement Amano method), reaction pH 5.0, reaction temperature 45 ° C., reaction time 12 hours to prepare a fat solution. We were able to.

Example 5
Using brown rice starch, 150 mg was placed in a 10 mL vial, 5 mL of water and 25 mg of the pigment astaxanthin were added, and dissolved in a boiling water bath. As a result, a fat solution could be prepared.

Example 6
A fat solution could be prepared by shaking and mixing 150 mg of a commercial dextrin of DE 19 ± 1, 25 mg of the dye astaxanthin and 5 mL of distilled water in a boiling water bath. The pigment oil layer was slightly floating.

Example 7
When 4 mL of distilled water and 1 mL of ethanol were used instead of 5 mL of distilled water in Example 6, a fat solution having no pigment oil layer floating could be prepared.

Example 8
The fat solution obtained in Example 1 was lyophilized by a conventional method to obtain a red powder.

Example 9
2 liters of the fat solution obtained in Example 7 was spray-dried by a conventional method to obtain a red powder.

Example 10
Using high amylose corn starch as starch, place 150 mg in a 10 mL vial, add 4 mL of water and 1 mL of an ethanol solution of the dye astaxanthin (containing 25 mg / mL of the dye), dissolve, mix in a boiling water bath, and release. A solid solution was prepared by cooling.

Example 11
Use potato starch as the starch, add 150 mg to a 10 mL vial, add 4 mL of 0.2 M acetic acid buffer (pH 5.0) and 1 mL of an ethanol solution of the dye astaxanthin (containing 25 mg / mL of the dye) in a boiling water bath. Dissolved. Then, after allowing to cool to about 50 ° C., add CGTase concentration 1.5 THU or α-amylase concentration 3 U / g starch (a paste refining power measurement Amano method), pH 5.0, temperature 45 ° C., 12 hours. The reaction was performed under conditions. Then, after processing for 10 minutes at 120 degreeC with an autoclave, it stood to cool and obtained the solid solution.

Example 12
To the fat solution prepared in Example 4, 1 mL of 1M citric acid solution adjusted to pH 5.0 with caustic soda was added to prepare a solid solution. A solid solution was similarly formed when sodium chloride or glycine was added to 0.5 M concentration instead of citric acid and when 3% of milk casein was added.

Example 13
Using high amylose corn starch as starch, put 150 mg in a 10 mL vial, add 4 mL of 0.1 N sodium hydroxide and dissolve, add 1 mL of ethanol solution of dye astaxanthin (containing 25 mg / mL of dye), and mix. A solid solution was prepared by neutralization with 1N hydrochloric acid.
Similarly, for cellulose and chitin, 150 mg of each fine powder was stirred with 1N sodium hydroxide overnight at room temperature, the solubilized portion was centrifuged, and 1 mL of an ethanol solution of pigment astaxanthin (containing 25 mg / mL of pigment) was added and mixed uniformly. And then neutralized with 5N hydrochloric acid to prepare a saccharide-carotenoid pigment solid solution. In addition, alkali treatment does not completely solubilize, it becomes colloidal, but even in this state, after adding carotenoid pigment and mixing uniformly, neutralize with 5N hydrochloric acid to prepare a saccharide-carotenoid pigment solid solution it can.

According to the present invention, the fat solution and / or solid solution can be formed by improving the physical properties of the water-insoluble carotenoid pigment. Therefore, the said pigment | dye can be utilized simply and effectively as a dye, a food coloring agent, etc.

Claims (6)

To dissolve and / or uniformly disperse astaxanthin , which is a carotenoid pigment, to obtain a fat solution; A partially decomposed saccharide satisfying any one of the following conditions (a) to (c) of one or more starches of: a mixture containing the carotenoid pigment, the saccharide and water A method for producing a carbohydrate-carotenoid pigment fat solution characterized by comprising:
(A) Acid partially degraded carbohydrate having a Dextrose Equivalent value of 15 to 40.
(B) Low partial hydrolysis reaction using cyclodextrin synthase under conditions of enzyme concentration 0.4 to 1.0 THU / g starch, reaction pH 5.0 to 6.5, reaction temperature 35 to 65 ° C., reaction time 2 to 24 hours Partially decomposed carbohydrates obtained by
(C) Using α-amylase, an enzyme concentration of 3.35 to 6.7 U / g starch (a paste refining power measurement Amano method), reaction pH 5.0 to 6.5, reaction temperature 35 to 65 ° C., reaction time 2 to 24 hours Partially decomposed saccharide obtained by performing a low partial hydrolysis reaction under conditions.   The method for producing a carbohydrate-carotenoid pigment fat solution according to claim 1, wherein a carotenoid pigment dissolved and / or uniformly dispersed in a 5 to 25% ethanol solution is used as the carotenoid pigment. A dried carbohydrate-carotenoid pigment mixture or a powder thereof obtained by drying the carbohydrate-carotenoid pigment fat solution prepared by the method according to claim 1 or 2 . The dried product or powder thereof according to claim 3 , wherein the drying treatment is spray drying or freeze drying. A salt and amino acid produced by neutralizing sodium chloride and an organic acid with caustic soda in a solution and / or uniform dispersion of a carbohydrate-carotenoid pigment solution prepared by the method according to claim 1 or 2 And a method for producing a carbohydrate-carotenoid pigment solid solution, comprising adding at least one substance in protein. The method for producing a solid solution according to claim 5 , wherein the organic acid is acetic acid or citric acid, the amino acid is glycine or sodium glutamate, and the protein is milk casein.