JP2002226729A - Manufacturing method of coloring matter solution - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a manufacturing method of a coloring matter solution derived from nature reducing the odor of coloring matter solution derived from nature and especially restraining the generation of returning odor when the coloring matter solution is stored for a long time. SOLUTION: In this method of manufacturing a coloring matter solution, an extract solution obtained by extracting a coloring matter (e.g. an anthocyanin-based coloring matter) from a natural matter is heated in contact with an oxidizing gas such as ozone, oxygen, or others, then it is treated to deodorize.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a dye solution containing an anthocyanin-based dye such as a red radish dye or a red cabbage dye, which is used as a colorant in the food industry or the like. For more information,
The present invention relates to a method for producing a dye solution containing a dye derived from a natural product, which suppresses generation of odor again during storage of the dye solution, that is, suppressed return odor.

[0002]

2. Description of the Related Art In the food industry, a large number of pigments are used. However, as consumers' safety consciousness increases, attention has been paid to pigments derived from natural products. The conditions required for dyes used for food are, of course, safe, stable to acids and alkalis, excellent in heat resistance, excellent in light fastness, and resistant to oxidation. Be stable,
Good hue, good color development, tasteless and odorless. In recent years, pigments derived from cruciferous plants such as red radish and red turnip are red to red-purple anthocyanin pigments, and are known as having excellent heat resistance, light resistance, excellent color tone, and good color development, and attracted attention. I have. However, many of the pigments derived from natural products have high safety and are useful for coloring foods, cosmetics, and the like. However, since they have odors derived from their raw materials, the range of use is often limited. In particular, in a pigment solution containing anthocyanin-based pigments derived from cruciferous plants such as red radish pigments, odors derived from raw materials due to sulfur compounds and the like are attached, and unless they are removed to the extent that humans can not sense, It is considered difficult to apply widely in foods, etc.
Reduction of this odor has been required.

[0003] In order to solve this, various purification techniques have been developed. For example, a method for producing an anthocyanin-based dye, in which a dye solution as described in JP-A-59-223756 is purified using a cationic or adsorptive resin, and then further subjected to ultrafiltration membrane treatment for purification. JP-A-4-154871, JP-A-7-157679
There is generally known a method for purifying an anthocyanin-based dye in which a dye solution is treated with an anion-exchange resin, as described in Japanese Patent Application Laid-Open No. H10-163, etc. However, although the dye solution obtained by these methods has very little odor immediately after the production, if the dye solution after this deodorization treatment is stored for a long time, it is difficult to completely suppress the return odor generated during storage. there were.

[0004]

DISCLOSURE OF THE INVENTION The present invention reduces the odor associated with a dye solution derived from a natural product, and in particular, the odor regenerated when the dye solution after purification treatment is stored for a long time.
That is, an object of the present invention is to provide a method for producing a dye solution derived from a natural product in which the generation of return odor is effectively suppressed.

[0005]

Means for Solving the Problems The present inventors have studied a red radish, a red turnip containing a dye derived from a natural product, in particular, an anthocyanin dye which is a red dye exhibiting a red to reddish purple color.
About the return odor which is a problem after the purification of the dye solution extracted from the natural product such as red cabbage, the diligent study was carried out on the method of producing the dye solution for suppressing the return odor. As a result, the return odor of the dye solution is generated by the oxidization of the impurities in the solution over time, and it is found that oxygen is greatly involved in the oxidation. Further, the impurities are converted into a gas having an oxidizing power such as oxygen and ozone. It has been found that the cause of the return odor can be efficiently eliminated by positively oxidizing with a gas containing. In other words, a dye extraction solution from a natural product is oxidized by heating with ozone and / or an oxygen-containing gas under a heating condition prior to the purification process, and then deodorized, whereby almost no return odor is generated even when stored for a long period of time. It has been found that a dye solution that does not need to be produced can be produced, and the present invention has been completed. This is quite surprising compared to the conventional perception that, in general, excessive heating in the extraction / purification process of anthocyanin-based dyes causes reduction in dye yield and deterioration in color tone of the dye solution, which should be avoided as much as possible. That is.

That is, the gist of the present invention is to provide a method for producing a dye solution, which comprises heating an extraction solution obtained by extracting a dye from a natural product in contact with an oxidizing gas and then deodorizing the solution. Exist.

In a preferred embodiment of the present invention, the gas having an oxidizing power is ozone and / or an oxygen-containing gas;
The supply amount of the ozone and / or oxygen-containing gas to be brought into contact with the dye extraction solution is not less than 0.01 [gas volume / dye extraction solution volume / minute] with respect to the dye extraction solution; Heating time is 2 hours or more; pH of the pigment extraction solution at the time of heat treatment is 3 or less; pigment derived from a natural product is a pigment derived from cruciferous plants, and is an anthocyanin pigment. That the deodorizing treatment is a treatment of contacting the heated dye extraction solution with an adsorbent; and that the adsorbent is a synthetic resin adsorbent.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The extraction solution obtained by extracting a pigment derived from a natural product that can be used in the present invention is arbitrary, and examples thereof include a carotenoid-based yellow and an anthocyanin-based pigment solution. The method of the present invention is particularly effective for anthocyanin-based dye solutions containing sulfides as main odor components. Specific examples of natural dye raw materials for obtaining an anthocyanin dye solution include red radish, red turnip, and red cabbage belonging to the Brassicaceae family. As red radish, Brassicaceae radish (Raphanus sativus)
L.) and Chinese red radish (such as red heart red radish) and Iwakuni red, and the red turnip is Brassicaceae Brassica (Brass
ica Rapa L.). In addition, as a member belonging to the Brassicaceae family, red cabbage, also known as purple sweet orchid, may be mentioned, and purple sweet potato may also be mentioned.

The extraction of the dye from the raw material of the natural dye can be performed by a known method. Anthocyanin-based dye solution, for example, the plant is cut into a size capable of extracting the dye, an appropriate amount of water and a pH adjuster are added, and immersed at room temperature,
It is obtained by extracting the pigment component contained in the plant by stirring if necessary, and filtering the extract. in this case,
It is desirable to extract while maintaining the pH of the aqueous solution on the acidic side. The pH of the liquid used for the extraction is usually preferably 4 or less, and more preferably about 1 to 4. Examples of the acid used for adjusting the pH include organic acids such as citric acid, tartaric acid, malic acid, and acetic acid, and inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid. The extraction temperature depends on the extraction time, but if the temperature is too high, the natural pigment may be deteriorated. Therefore, the extraction temperature is usually 10 ° C to 40 ° C, preferably 15 ° C.
Performed at ３０30 ° C. The amount of water used for extraction is arbitrary, but for example, in the case of extraction from red radish or red turnip, about 1 to about 10 times the weight of these is preferable because of easy handling. At the time of extraction, alcohol may be added to water for use. The alcohol concentration at this time is optional, but is preferably about 1 to 50% by weight. The dye extraction solution thus obtained has a unique odor from the raw material.

Next, the extraction solution is heated while being brought into contact with an oxidizing gas such as ozone or an oxygen-containing gas. The temperature of the heat treatment may be at least the extraction temperature in the dye extraction, and is usually at least 50 ° C. The heating time is optional, but is preferably 2 hours or more.
During the treatment, not only the oxidation of impurities but also the deterioration of the dye itself may occur at the same time. Therefore, it is necessary to set conditions within a range where the dye does not extremely deteriorate. It is preferable to perform heat treatment for about 20 hours. In addition, by setting the pH of the dye extraction solution at the time of the treatment to 3 or less, the cause of the odor can be more efficiently removed and the stability of the dye can be enhanced. This is preferable because the loss, that is, the degree of decrease in absorbance at the maximum absorption wavelength of the dye extraction solution can be reduced. The pH of the dye extraction solution may be adjusted to 3 or less at the start of the extraction process, or immediately after the extraction process and immediately before the heating process. It is. Examples of a method for adjusting the pH include a method of adding an appropriate amount of an organic acid such as citric acid, tartaric acid, malic acid, or acetic acid, or an inorganic acid such as hydrochloric acid, sulfuric acid, or phosphoric acid.

Regarding the contact between the extraction solution and the ozone or oxygen-containing gas during the heat treatment, the gas may be passed through the solution, or the gas in the gas phase may be immersed in the solution by stirring. However, it is more effective to combine aeration and agitation. As for the gas supply, a batch method in which a certain amount of gas is previously charged into the processing tank may be considered, but it is more efficient to supply the gas continuously. In that case, the supply rate of the gas was set at 0.1 to the dye extraction solution under the conditions of the heat treatment.
01 [gas volume / dye extraction solution volume / min] (hereinafter vvm
It is described. ) Or more, especially 0.1 to 10
A feed rate of vvm is preferred. The pressure of the supplied gas is not particularly limited, but is preferably 0.001 to 0.5 MPa (gauge pressure) for operation. The composition of the gas having an oxidizing power to be supplied is arbitrary, but is not particularly limited as long as it contains ozone and / or oxygen. In actual production, air or oxygen-enriched air or ozone-enriched air is used. Most convenient to use.

Next, the heat-treated dye solution is subjected to a deodorizing treatment. Regarding deodorization, steam distillation, molecular distillation, extraction with organic solvents and supercritical fluids, membrane filtration,
Any generally known deodorizing method such as an adsorption method can be applied. Among them, a method in which a solution containing a dye component or the like is passed through a column filled with a synthetic resin adsorbent is preferable. In the case of this method, in particular, a dye extract containing a dye component and an odor component is passed through a synthetic resin adsorbent column, and first, both the odor component and the dye component are adsorbed to the resin, and the resin is first broken through and discharged. It is preferable to start the recovery from the passing solution containing the coloring component and then recover the coloring solution between the passing solution containing the odor component that breaks out later.

The synthetic resin adsorbent used is a non-polar porous adsorbent resin, for example, a network-like molecular structure such as a styrene-divinylbenzene cross-linked copolymer resin or a (meth) acrylate cross-linked copolymer resin. Are preferred. In a styrene-divinylbenzene cross-linked copolymer resin, for example, a specific surface area of about 300 to about 700
Resins of about m ² / g are preferable, and as the porous synthetic resin corresponding thereto, HP resins such as Diaion HP-20 and Diaion HP-50 (“Diaion”: registered trademark, manufactured by Mitsubishi Chemical Corporation), SP resins (manufactured by Mitsubishi Chemical Corporation) such as Diaion SP-206 and Diaion SP-825;
XAD-4 (manufactured by Rohm and Haas) and the like. Examples of the methacrylic acid ester resin include XAD-7 and XAD-8 (manufactured by Rohm and Haas).

Following the passage of the dye aqueous solution containing the odor component and the dye component through the column, a water solvent (desorption water) not containing these components may be passed. The pH of the aqueous solvent used for the passage is preferably 7 or less, more preferably about 1 to 4. As the acid used for adjusting the pH, those used for adjusting the pH of the dye solution described above are used. The passage speed of the liquid is not particularly limited, but if the flow rate per unit volume is large, even if the throughput per unit can be secured, the deodorization may be insufficient, so there is a limit.On the other hand, the lower the speed, the lower the odor component. Is improved, but the throughput per unit time decreases. Therefore, the liquid passing speed is usually SV = 0.
1-10, especially 0.5-5 are preferred.

The flow rate until the breakthrough of the dye component starts is about four times the bed volume (BV) (4 BV).
The start of dye collection is usually 1 to 10 BV, preferably 2 to 10 BV.
It may be performed after the passage of 6 BV. In addition, while the dye component is adsorbed on the resin, the passing liquid is transparent, and when the dye component starts to break through, it changes to red.Therefore, it is necessary to check the absorbance of the passing liquid to determine the recovery start point. preferable. The end point of the collection may be determined by previously confirming the breakthrough point of the odor component with the bed volume as described above, or it can be sufficiently determined even if a person smells the odor. The determination can also be made by analyzing the sulfides in the gas phase sample used. By deodorizing treatment with this resin,
A dye solution having almost no odor and extremely low return odor is obtained.

The dye solution obtained by the present invention can be used for various applications as it is, but is usually concentrated, distributed, stored and used. Concentration is carried out by a usual method. For example, a concentrated solution of the dye having a color value of 200 to 2000 is obtained by distilling off the solvent used at a temperature of about 20 to 90 ° C. under atmospheric or reduced pressure conditions. be able to. The dye solution thus obtained has excellent color tone, does not regenerate odor for a long period of time, and can be widely used as a coloring agent for foods, beverages, cosmetics, etc. even if stored for a long period of time. Depending on the application, use as is or emulsification,
It can be used in powdered form. Emulsification is usually performed by adding an emulsifier such as gum arabic, polyglycerin fatty acid ester, sucrose fatty acid ester, polyhydric alcohol, etc.
The emulsification can be performed by a homomixer, a colloid mill, a high-pressure homogenizer, or the like. Further, powdering can be usually performed by adding an excipient such as lactose, dextrin, or gum arabic, and using drying means such as vacuum drying and spray drying.

When used in the above forms, if necessary, organic acids such as lactic acid, citric acid, malic acid, tartaric acid, or chlorogenic acid, rutin, tea flavonoids, tannin, etc., for the purpose of improving the stability of the pigment. It is also possible to add an antioxidant such as an antioxidant. The various forms of the pigments obtained in this manner include foods and drinks, luxury goods, feedstuffs,
It can be widely used in various fields such as health, pharmaceuticals, cosmetics, etc. For example, in the food and drink field, drop, candy, chocolate, ice cream, sorbet, jelly, soft drink, milk drink, candy, processed meat,
Natural coloring for sauces, pickles, etc .; Natural coloring for luxury items; Natural coloring for health and pharmaceutical products such as tablets, liquid oral medicines, compresses, etc .; or coloring of soaps, detergents, shampoos It is useful as a natural coloring agent for cosmetics. The amount added to the food or drink as described above depends on the type of product to be obtained, required consumer preference, and the like, but is usually about 0.005 to about 10% by weight based on the product. , Preferably about 0.0
A range of 1 to about 0.1% by weight can be exemplified.

[0018]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the scope of the invention. In the following, "%"
Represents "% by weight". The color value of the dye solution is shown by measuring the absorbance of the anthocyanin dye at the maximum absorption wavelength of 512 nm.

Example 1 1 kg of red radish was cut into an appropriate size, 5 liters of an aqueous solution of 1% citric acid was charged in an extractor, extracted at room temperature for about 8 hours, and repeated three times. The extract was separated and collected, and the collected liquid was concentrated by removing the water content by evaporation using a heating vacuum evaporator. A part of the obtained concentrated solution was filtered through a glass filter having an average pore diameter of 1.6 μm, and then subjected to a test described below as a red radish dye stock solution. Also,
The pH of the dye stock solution was 2.6. The absorbance of the red radish dye stock solution with respect to light having a wavelength of 512 nm (hereinafter, abbreviated as A512 value) was 610. A process in which 600 mL of the above red radish dye stock solution is put into a 1 L separable flask, air is passed at a ventilation speed of 1 vvm, and the mixture is heated to 80 ° C. using a water bath while stirring at 1000 rpm using a disk turbine blade. 8
Time went. Thereafter, the liquid was cooled to about room temperature to obtain 580 mL of a heat treatment liquid for the dye. The A512 value of the treatment liquid was 550.

400 mL of the heat-treated solution was placed in a glass column (diameter 12.5 mmφ) filled with 20 cm ³ of synthetic adsorption resin Diaion HP20 (manufactured by Mitsubishi Chemical Corporation).
3 at a flow rate of 3 to remove the red radish dye deodorizing solution 39
0 mL was obtained. The A512 value of the deodorized liquid was 450. The deodorized solution was analyzed for sulfides in the headspace GC, and the odor was evaluated by a sensory test. Table 1 shows the results. Further, the deodorized solution was placed in a closed container and stored in a refrigerator (about 4 ° C.) for 2 months. Thereafter, sulfides were analyzed in headspace GC, and at the same time, odor was evaluated by a sensory test. Table 1 shows the results.

Example 2 600 mL of the red radish dye stock solution obtained in Example 1 was mixed with 1 L
, And air mixed with 100 ppm ozone was aerated at a ventilation speed of 0.5 vvm, and heated to 80 ° C. using a water bath while stirring at 1000 rpm using a disk turbine blade. 4
Time went. Thereafter, the liquid was cooled to about room temperature to obtain 580 mL of a heat treatment liquid for the dye. The A512 value of the treatment liquid was 530. 400 mL of the heat-treated liquid was added to a synthetic adsorption resin Diaion HP20 (manufactured by Mitsubishi Chemical Corporation) 20 cm ³
Into a glass column (diameter 12.5 mmφ) filled with
= 3 and passed through a red radish dye deodorizing solution 3
90 mL was obtained. The A512 value of the treatment liquid was 420. The dye treatment liquid was analyzed for sulfides by headspace GC, and at the same time, the odor was evaluated by a sensory test. Table 1 shows the results. Further, the treatment liquid was placed in a closed container and stored in a refrigerator (about 4 ° C.) for two months. Thereafter, sulfides were analyzed by head space GC, and at the same time, odor was evaluated by a sensory test. Table 1 shows the results.

Example 3 Phosphoric acid was added to the red radish dye stock solution obtained in Example 1 so that the concentration became 1%, and the pH became 1.8. The stock solution 60
0 mL is placed in a 1 L separable flask, and air is
A process of heating to 80 ° C. using a water bath was performed for 8 hours while aeration was performed at a ventilation speed of vvm and stirring was performed at 1000 rpm using a disk turbine blade. Thereafter, the liquid was cooled to about room temperature to obtain 580 mL of a heat treatment liquid of the dye. The A512 value of the treatment liquid was 570. 400 mL of the heat-treated liquid was added to the synthetic adsorption resin Diaion HP2
0 (manufactured by Mitsubishi Chemical Corporation) at a flow rate of SV = 3 through a glass column (diameter 12.5 mmφ) packed with 20 cm ³ ,
390 mL of a deodorized solution of red radish dye was obtained. The A512 value of the deodorized liquid was 465. The deodorized solution was analyzed for sulfides by headspace GC, and at the same time, the odor was evaluated by a sensory test. Table 1 shows the results. Further, the treatment liquid was placed in a closed container and stored in a refrigerator (about 4 ° C.) for two months. Thereafter, sulfides were analyzed by head space GC, and at the same time, odor was evaluated by a sensory test. Table 1 shows the results.

Comparative Example 1 400 mL of the red radish dye stock solution obtained in Example 1 was synthesized with a synthetic adsorption resin Diaion HP20 (manufactured by Mitsubishi Chemical Corporation) 20c.
It was passed through a glass column (diameter 12.5 mmφ) filled with m ³ at a flow rate of SV = 3 to obtain 390 mL of a deodorized solution of red radish dye. The A512 value of the treatment liquid was 490. The dye treatment liquid was analyzed for sulfides by headspace GC, and at the same time, the odor was evaluated by a sensory test. Table 1 shows the results. Further, the processing solution is placed in a closed container and stored in a refrigerator (about 4 ° C.) for two months.
Thereafter, the sulfides were analyzed in the headspace GC, and at the same time, the odor was evaluated by a sensory test. Table 1 shows the results.

[0024]

[Table 1]

Description of sensory evaluation +++++: The off-flavor is extremely strong. ++: Offensive odor is quite strong. ++: Offensive odor is slightly strong. +: Slight smell is felt. -: No off-flavor. As is clear from the results in Table 1, in the dye solution treated with the present invention, the numerical value indicating the odor hardly increased even after 2 months, and no return odor was generated. It can be seen that in the stock solution, the odor remains at the same level, and in the comparative example, the numerical value increases and the return odor is generated.

[0026]

As described above, according to the method of the present invention, it is possible to produce a natural dye solution with very little return odor, and the method of the present invention is industrially extremely useful.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Akihiko Toyosawa 1-1 Kurosaki Castle Stone, Yawatanishi-ku, Kitakyushu-shi, Fukuoka Mitsubishi Chemical Corporation Kurosaki Works (72) Inventor Shuichi Abe 1 Kurosaki Castle Stone, Yawata-Nishi-ku, Kitakyushu City, Fukuoka Prefecture 1 Mitsubishi Chemical Corporation Kurosaki Office (72) Inventor Makoto Ishikawa 1-1 Kurosaki Castle Stone, Yawatanishi-ku, Kitakyushu-shi, Fukuoka F-term in Mitsubishi Chemical Corporation Kurosaki Office 4B018 MA02 MF04 MF10

Claims (10)

[Claims] 1. An extraction solution obtained by extracting a pigment from a natural product,
A method for producing a dye solution, comprising heating under contact with an oxidizing gas, followed by deodorizing treatment. 2. The method according to claim 1, wherein the oxidizing gas is ozone and / or oxygen-containing gas. 3. The supply amount of ozone and / or oxygen-containing gas to be brought into contact with the dye extraction solution is 0.01 [gas volume / dye extraction solution volume / minute] or more based on the dye extraction solution. The production method according to claim 1 or 2, wherein: 4. The method according to claim 1, wherein the heating temperature is 50 ° C. or higher. 5. The method according to claim 1, wherein the heating time is 2 hours or more. 6. The method according to claim 1, wherein the pH of the dye extraction solution during the heat treatment is 3 or less. 7. The method according to claim 1, wherein the pigment derived from a natural product is a pigment derived from a cruciferous plant. 8. The production method according to claim 1, wherein the pigment derived from a natural product is an anthocyanin pigment. 9. The production method according to claim 1, wherein the deodorizing treatment is a treatment in which the heated dye extraction solution is contacted with an adsorbent. 10. The method according to claim 9, wherein the adsorbent is a synthetic resin adsorbent.