JP7340411B2 - Manufacturing method of pigment preparation - Google Patents

Description

The present invention relates to a method for producing a pigment preparation, and more particularly to a method for producing a pigment preparation whose main component is a yellow pigment component made from gardenia, saffron, or the like.

Examples of yellow food pigments include gardenia yellow pigment, safflower yellow pigment, marigold pigment, riboflavin, and β-carotene. Gardenia yellow pigment is mainly composed of crocin contained in the fruits of gardenias belonging to the Rubiaceae family, and crocetin obtained by hydrolyzing sugars from crocin using acids, alkalis, enzymes, etc. Crocin is also found in the stigma, which is the tip of the pistil of saffron, a member of the Iridaceae family. Crocetin, along with crocin, is widely used as a yellow pigment for coloring foods such as sweets, bread, Chinese noodles, desserts, processed seafood products, and pickles. Comparing the color tone of crocetin and crocin, crocetin exhibits a brighter and more vivid lemon yellow color than crocin, so it can be said that it is highly useful when used in food.

However, since crocetin is poorly water-soluble, it could not be easily used in aqueous foods such as drinks, even though it is superior in color tone to crocin. In addition, when the pH of crocetin becomes lower than 6, it becomes slightly brownish and causes aggregation and precipitation.

Conventionally, several methods have been proposed for producing pigment preparations that allow crocetin to be used as a coloring agent for aqueous foods. For example, a method for producing a crocetin preparation (Patent Document 1) characterized in that when a dispersion of crocetin is prepared in an aqueous solution containing saccharides, the particle size of the dispersion is adjusted to a median diameter of less than 0.5 μm (Patent Document 1). ), a method for producing a powdered crocetin preparation characterized by dispersing crocetin in an aqueous solution containing saccharides to have an average particle size of 0.5 to 5 μm, and drying the resulting dispersion (Patent Document 2).

In addition, as a method for dissolving crocetin in water without using an emulsifier, the carotenoid pigment crocetin is first dissolved by adjusting the pH to alkaline, then cyclodextrin is mixed into the solution, and the pH is neutralized to solubilize crocetin. However, a solubilization method (Patent Document 3) has been proposed in which a stable liquid preparation is prepared by adding a thickener as necessary to give it viscosity, and it also provides resistance to light and various drugs. For this purpose, crocetin dissolved in sodium hydroxide is added to α-cyclodextrin made into a paste by adding a small amount of water, stirred vigorously, and then centrifuged to obtain α-cyclodextrin-clathrated crocetin (patented method). Reference 4) has been proposed.

However, these technologies mentioned above are not intended to be added to acidic beverages, which are more likely to cause precipitation, and even if they can be used for aqueous foods in the neutral range, flocculation and precipitation may occur in the acidic range. This was not satisfactory in that it could occur.

JP2012-29585A Japanese Patent Application Publication No. 2006-335859 Japanese Patent Application Publication No. 7-23736 Japanese Patent Application Publication No. 6-248193

Therefore, the present inventor conducted extensive research to solve the above problem, and found that under alkaline conditions, acidic coloring was achieved using a pigment preparation obtained by mixing polyglycerin fatty acid ester, gum arabic, and crocetin. It has been found that when a beverage is colored, aggregation and precipitation can be suppressed while maintaining the original yellow color of crocetin. After further various studies, the present invention was completed.

The present invention provides a method for producing a pigment preparation that suppresses the occurrence of aggregation and precipitation even when crocetin is used under acidic conditions, for example for coloring acidic drinks, and can be colored in a yellow tone. The purpose is to

More preferably, in the present invention, crocetin is mixed with polyglycerin fatty acid ester as an emulsifier and a thickening polysaccharide derived from a sap such as gum arabic under alkaline conditions, and the pigment solution is further adjusted to be neutral. An object of the present invention is to provide a method for producing a pigment preparation that can be colored in a yellow tone while suppressing the occurrence of aggregation and precipitation even when used under acidic conditions, for example, for coloring acidic beverages. shall be.

In order to solve the above problems, the present invention as set forth in claim 1 includes the steps of: preparing a dye liquid containing crocetin, polyglycerin fatty acid ester, and polysaccharide thickener and having an alkaline pH; Provided is a method for producing a pigment preparation, further comprising a step of adjusting the dye to neutrality.

In order to solve the above problem, the present invention as set forth in claim 2 provides a method for producing a pigment preparation as set forth in claim 1, in which a mixed solution of water and polyglycerin fatty acid ester is used, the mixed solution having an alkaline pH. and a step of adding crocetin and polysaccharide thickener to the alkaline-adjusted mixed solution to prepare a dye solution.

According to the method for producing a pigment preparation according to the present invention, it has high solubility in water, suppresses aggregation and precipitation even when coloring acidic drinks, and moreover, can be colored with the yellow tone inherent to crocetin. There is an effect that it can be done.

FIG. 1 is a flowchart showing one embodiment of the method for producing a pigment preparation according to the present invention.

Hereinafter, the method for producing a pigment preparation according to the present invention will be described in detail based on preferred examples.

First, crocetin can be obtained by hydrolyzing crocin, which is the main component of gardenia yellow pigment, but it can also be prepared by enzymatically treating crocin. In the present invention, any crocetin may be used regardless of the method for producing crocetin, and is not limited to the production method. Furthermore, the crocetin used in the present invention may be a mixture with crocin.

1. [Adjustment of mixed liquid]
The method for producing a pigment preparation according to the present invention is, for example, adjusted according to the following steps. First, a mixed solution of water with an alkaline pH and polyglycerin fatty acid ester as an emulsifier is prepared (step S1). As the usable polyglycerin fatty acid ester, for example, one or more of decaglycerin stearate, decaglycerin myristate, and decaglycerin oleate can be used. Further, as the polyglycerin fatty acid ester, it is preferable to use a polyglycerin fatty acid ester having a degree of glycerin polymerization of 10 and a degree of esterification of 1.

Water and polyglycerin fatty acid ester are mixed by adding polyglycerin fatty acid ester to water, but the mixture may be adjusted at room temperature (20 to 30°C), or while heating the water as necessary. A mixed solution may be prepared by adding polyglycerol fatty acid ester or by adding polyglycerol fatty acid ester to warm water that has been heated in advance. The heating temperature is 40 to 95°C, preferably 60 to 90°C, and the concentration of polyglycerol fatty acid ester is 0.5 to 30.0% by mass, more preferably 1.0 to 15.0%. Further, when preparing the mixed liquid, it is preferable to carry out the preparation while stirring. The stirring conditions are not particularly limited, but for example, the stirring time is about 10 minutes (for example, 5 to 800 rpm) using Three-One Motor TYPE-600G (manufactured by Shinto Kagaku Co., Ltd.) as a stirrer at about 600 rpm (for example, 400 to 800 rpm). 15 minutes).

Further, when preparing the mixed liquid, one or more types of viscosity modifiers such as D-sorbitol, reduced starch syrup, and glycerin may be added to adjust the viscosity. A viscosity modifier such as D-sorbitol is preferably added in a state dissolved in water.

Next, an alkaline agent is added to the mixed solution to adjust the pH to alkaline. This is because crocetin is poorly water-soluble and is difficult to dissolve in water as it is, so making the pH alkaline makes it easier to dissolve. The alkaline agent added to the mixture is not particularly limited, but examples include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, L-potassium hydrogen tartrate, DL-potassium hydrogen tartrate, sodium hydrogen carbonate, and pyrophosphoric acid. One or more of sodium dihydrogen, dipotassium hydrogen phosphate, potassium dihydrogen phosphate, disodium hydrogen phosphate, sodium dihydrogen phosphate, etc. can be used, and sodium hydroxide is preferably used. can. The pH to be adjusted is, for example, pH 9.0 to 14.0, preferably pH 10.0 to 12.0. Note that this pH adjustment is also carried out while stirring; for example, the above three-one motor TYPE-600G (manufactured by Shinto Kagaku Co., Ltd.) is used for stirring at about 600 rpm (for example, 400 to 800 rpm) for about 5 minutes ( For example, 3 to 10 minutes).

Here, the preparation of the mixed liquid is not limited to the above procedure, and the emulsifier may be mixed after adding the alkaline agent to water. In this case, the pH of the mixed solution, heating of water, stirring conditions, etc. are the same as the above procedure.

2. [Adjustment of dye solution]
Next, crocetin and polysaccharide thickener are added to and dissolved in the mixed solution adjusted to be alkaline to prepare a dye solution (step S2). The dye solution may be prepared by adding crocetin to the mixed solution and dissolving it, and then adding the thickening polysaccharide, or by adding the thickening polysaccharide to the mixed solution and dissolving it, and then adding crocetin. Of course, crocetin and polysaccharide thickener can be added to the mixture at the same time. As the thickening polysaccharide, for example, thickening polysaccharides derived from tree sap such as gum arabic, gum gati, gum karaya, and gum tragacanth can be suitably used, and one or two kinds of thickening polysaccharides derived from these sap can be used. or more can be used. Among these, gum arabic or gum gati is preferable from the viewpoint of viscosity characteristics, and at least one type of gum arabic or gum gati is preferably used.

The method for dissolving crocetin and polysaccharide thickener in the mixed solution is not particularly limited, but for example, dissolving crocetin and polysaccharide thickener in the mixed solution at 600 rpm (for example, 400 to 800 rpm) for a stirring time of about 15 minutes (eg, 10 to 20 minutes).

Furthermore, when preparing the dye solution, a quality preservation agent such as ethanol may be added for preservative purposes.

[Adjustment of dye solution using other procedures]
In addition to the procedure described above, the dye solution can also be adjusted by the following procedure. First, a dye solution containing crocetin in a mixture of water and polyglycerol fatty acid ester as an emulsifier is prepared. The mixing conditions for the dye liquid (temperature, rotation speed of the stirring device, etc.) are also the same as above. Further, as described above, a viscosity modifier such as D-sorbitol may be added if necessary. Then, a polysaccharide thickener is added to this dye solution, and the pH is further adjusted to alkaline. The mixing conditions (rotation speed of the stirring device, etc.) are also the same as in the above case. Further, as described above, a quality preserving agent such as ethanol may be added as necessary. Note that since crocin is converted into crocetin when the pH is alkaline, the crocetin added when preparing the dye solution may contain crocin, or crocin may be added instead of crocetin.

Next, the pH of the agitated and mixed dye solution is adjusted to neutral (step S3). The reason for adjusting the pH to neutral is to maintain the bright yellow color tone of crocetin. Examples of pH adjusting agents (acid agents) for the dye solution used to adjust the pH of the dye solution to neutral include adipic acid, citric acid, trisodium citrate, glucono delta-lactone, gluconic acid, and succinic acid. , L-tartaric acid, DL-tartaric acid, acetic acid, lactic acid, fumaric acid, DL-malic acid, and other organic acids; and hydrochloric acid, sulfuric acid, oxalic acid, phosphoric acid, and other inorganic acids. Preferably, citric acid can be used. The pH to be adjusted is from 6.0 to 8.0, preferably from 6.2 to 7.2. Note that "neutral" herein refers to a pH range of 6.0 to 8.0, "acidic" refers to a pH range below 6.0, and alkaline refers to a pH range above 8.0. The pH adjuster (acid agent) is stirred and mixed slowly for about 30 minutes (for example, 15 to 45 minutes) so that the pH does not fluctuate rapidly. Note that the pH adjuster (acid agent) can also be added in multiple portions.

The pH of the dye solution is adjusted to neutrality by stirring and mixing using a high-speed stirrer. By stirring and mixing using a high-speed stirrer, the effect of suppressing precipitation can be further enhanced. As the high-speed stirrer, for example, a high-speed rotary dispersion/emulsifier such as Homomixer MARK II (manufactured by Primix Co., Ltd.), TK Homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), or Clearmix (manufactured by M Techniques Co., Ltd.) can be used. Examples of stirring and mixing conditions include a rotation speed of 4,000 to 12,000 rpm, preferably about 5,000 rpm, and a stirring time of 15 to 45 minutes, preferably about 30 minutes. Further, for example, in the case of a small machine for laboratory use, the rotation speed may be 2000 to 20000 rpm, and the stirring time may be about 5 to 60 minutes. Note that the present invention is not limited to the above-mentioned devices as long as they are capable of similar operations.

The pigment preparation obtained by the production method of the present invention as described above can be used as a yellow coloring agent in a wide range of food and drink products, but is particularly suitable for acidic drinks filled in transparent containers such as PET bottles (PET containers). It can be suitably used for coloring.

Next, some examples will be shown below regarding the method for producing a pigment preparation according to the present invention. However, the present invention is not limited to these specific examples. In the following experimental examples, unless otherwise specified, "parts" means "parts by mass" and "%" means "% by mass."

As crocetin, Nichino Color YK-40 (manufactured by Nichino Kagaku Kogyo Co., Ltd., color value 440) was used.

In addition, the following polyglycerin fatty acid esters were used.
[Example 1]: Decaglycerin stearate (NIKKOL Decaglyn 1-SVEX: manufactured by Nippon Surfactant Industries Co., Ltd.)

[Examples 2 and 3]: Decaglycerin myristate ester (NIKKOL Decaglyn 1-MVEX PN: manufactured by Nippon Surfactant Industries Co., Ltd.)

Further, in Examples 1 and 2, gum arabic (Arabic Call SS: manufactured by Sanei Yakuhin Trading Co., Ltd.), which is a thickening polysaccharide derived from tree sap, was used as the thickening polysaccharide. Furthermore, in Example 3, gati gum (Gaticol SS, manufactured by Sanei Pharmaceutical Trading Co., Ltd.), which is a polysaccharide thickener derived from tree sap, was used as the polysaccharide thickener. On the other hand, as Comparative Example 1, a sample was produced using only gum arabic without using polyglycerin fatty acid ester. In Examples 1 to 3 and Comparative Example 1, ethanol and D-sorbitol solutions were used, respectively. In addition, the respective compounding ratios are as shown in Table 1. Then, for Examples 1 to 3 and Comparative Example 1, mixed liquids were prepared according to the procedure shown in the above embodiment.

Specifically, water, polyglycerol fatty acid ester, and D-sorbitol solution were mixed, heated to 70°C, and stirred for 10 minutes at 600 rpm using a three-one motor TYPE-600G (hereinafter referred to as the "stirrer"). Mixing was done. Next, sodium hydroxide was added as an aqueous solution so that the pH of the mixture became 12.0, and the mixture was stirred for 5 minutes.

Next, crocetin (Nichino Color YK-40) was added to this mixed solution, and stirred and mixed for 5 minutes at 600 rpm using a stirrer, and then gum arabic (Arabic Call SS) or gati gum (Gati Call SS) was added. The mixture was stirred and mixed for 10 minutes at 600 rpm using a stirrer, and then ethanol was added and mixed for 5 minutes using a stirrer. Then, while stirring at 5000 rpm using a high-speed stirrer (Homomixer MARK II: manufactured by Primix Co., Ltd.) so that the pH of this dye solution becomes 6.8, citric acid is slowly added to the aqueous solution to avoid sudden pH changes. The pigment preparations of Examples 1 to 3 and Comparative Example 1 were prepared by stirring and mixing for 30 minutes. On the other hand, as Comparative Example 2, Nichino Color YK-40 was used as it was as a pigment preparation without using polyglycerol fatty acid ester, sap-derived thickening polysaccharide, etc.

[Evaluation method]
Acid resistance tests were conducted on Examples 1 to 3 and Comparative Examples 1 and 2 above. The acid resistance test was conducted using an acidic drink-like solution with pH 3.5 and Brix 16 (sodium ascorbate: 0.05% by mass, citric acid (crystals): 0.07% by mass, fructose glucose liquid sugar: 21% by mass, purified water: remainder). (Total amount: 100% by mass)), add 0.5% by mass of each of the pigment preparations shown in Examples 1 to 3 and Comparative Example 1 above and mix, and after heating to 60 ° C., dispense each into a PET container. It was used as a test product. For Comparative Example 2, samples were prepared in which crocetin was added at the same concentration as in Examples 1 to 3 and Comparative Example 1, and similarly used as test products. Then, each test product was stored in a refrigerator for 3 days, and the occurrence of precipitation/aggregation and color tone were evaluated. The evaluation criteria for the presence or absence of flocculation and precipitates are "○: No precipitates and aggregates are observed," and "×: Precipitates and aggregates are observed." The evaluation criteria for color tone evaluation is " ○: yellow", "x: orange or colorless". The results are shown in Table 1.

As shown in Table 1, the dye preparations of Examples 1 to 3 showed no precipitation or aggregation even under acidic conditions of pH 3.5, and the color tone was clear yellow. On the other hand, in Comparative Example 1, although the color tone was yellow, aggregation and precipitation were observed. In addition, in Comparative Example 2, aggregation and precipitation occurred immediately after addition to the acidic drink-like solution, and the color became almost colorless.

Next, using decaglycerin myristate ester (NIKKOL Decaglyn 1-MVEX PN, manufactured by Nippon Surfactant Industries, Ltd.), which gave good results in the above test, the preferred pH range of the pigment preparation was investigated. That is, 7.0% by mass of decaglycerin myristate, 15.0% by mass of gum arabic (arabic call SS) as a thickening polysaccharide derived from sap, 3.0% by mass of D-sorbitol solution, and 10% by mass of ethanol. 0% by mass and adjusted according to the same procedure as Examples 1 to 3, and the final pH of the pigment preparation was adjusted to pH 7.2 (Example 4), pH 6.2 (Example 5), and pH 5.2 (Example 5), respectively. Comparative Example 5).

Similarly, in order to investigate the addition amount of decaglycerin myristate ester (NIKKOL Decaglyn 1-MVEX PN), which is an emulsifier, 7.0% by mass (Example 6) and 9.0% by mass (Example 7), respectively. , 11.0% by mass (Example 8). Note that the amount of water was adjusted for the difference so that the final content was 100% by mass. Note that in Example 8, no D-sorbitol solution was added.

On the other hand, as Comparative Example 3, a dye preparation was prepared in which the pH of the mixed solution was neither adjusted to alkaline nor neutral (no addition of sodium hydroxide and citric acid (crystals)), and Comparative Example 4. After adjusting the mixed solution to alkaline, a pigment preparation was prepared without adjusting the pH to neutral (without adding citric acid (crystals)). In Examples 4 to 8 and Comparative Examples 3 to 5, dye preparations were also prepared according to the same procedure as in Examples 1 to 3 above. The blending ratios of Examples 4 to 8 and Comparative Examples 3 to 5 are shown in Table 2.

Acid resistance tests were also conducted for Examples 4 to 8 and Comparative Examples 3 to 5. The acid resistance test was conducted using an acidic drink-like solution of pH 3.5 and Brix 16 (sodium ascorbate: 0.05% by mass, citric acid (crystals): 0.07% by mass, as in Examples 1 to 3 above). Fructose glucose liquid sugar: 21% by mass, purified water: remaining amount (total amount: 100% by mass)), add 0.5% by mass of each of the pigment preparations shown in Examples 4 to 8 and Comparative Examples 3 to 5 above. The mixture was mixed, further heated to 60°C, and then dispensed into PET containers to prepare test products. The evaluation criteria for the occurrence of agglomeration and precipitation and the evaluation criteria for color tone are also the same as above. The results are shown in Table 2.

As shown in Table 2, the pigment preparations of Examples 4 and 5, in which the pigment liquid was adjusted to neutrality (pH 6.2 to 7.2), showed no precipitation or aggregation even under acidic conditions of pH 3.5. Moreover, the color tone was a beautiful yellow. In addition, if the amount of the emulsifier decaglycerin myristate ester added is within the range of Examples 6 to 7 (7 to 11% by mass), no precipitation or aggregation will be observed even under acidic conditions of pH 3.5. The result was that the color tone was a beautiful yellow. On the other hand, in Comparative Example 5, in which the dye liquid was adjusted to be acidic (pH 5.2), no aggregation or precipitation was observed, but the color tone became orange when mixed into the acidic drink-like solution. Furthermore, although no aggregation or precipitation was observed in Comparative Examples 3 and 4, the color tone during mixing was orange and did not have the beautiful yellow color that crocetin has.

As is clear from the above results, according to the method for producing a pigment preparation according to the present invention, the occurrence of aggregation and precipitation is suppressed even when used in acidic beverages, and it is possible to color with a beautiful yellow tone. This effect is recognized.

It goes without saying that the present invention is not limited to the embodiments or examples described above, and that various modifications can be made without departing from or changing the technical idea of the present invention.

Claims (2)

A step of adjusting a dye solution containing crocetin, polyglycerin fatty acid ester, and polysaccharide thickener and having an alkaline pH;
further adjusting the dye liquid to neutrality;
1. A method for producing a pigment preparation, comprising: A step of adjusting a mixed solution of water and polyglycerin fatty acid ester, the mixed solution having an alkaline pH;
Adding crocetin and polysaccharide thickener to the alkaline-adjusted mixture to prepare a pigment solution;
The method for producing a pigment preparation according to claim 1, characterized in that it is comprised of:

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