JP5103296B2 - Method for producing purified ginger oleoresin - Google Patents

Description

  The present invention relates to a method for producing a purified product of ginger oleoresin.

  Ginger is used as a spice and seasoning due to its pungent taste and aroma, and in addition to its pungent effect, it also has a digestion promoting action, a laxative action, an antitussive action, a blood circulation promoting action, a gastrointestinal action, an antipyretic action, an antibacterial action, etc. Since it exhibits various pharmacological actions, it is also widely used as a crude drug.

  Ginger oleoresin (oleo-resin) is a resinous and viscous substance extracted from ginger with an organic solvent and concentrated. This includes active ingredients such as gingeron, gingerol, and shogaol, but there are also various unnecessary ingredients such as resins, pigments, polysaccharides and proteins extracted together during extraction. Under the influence of this unnecessary component, ginger oleoresin is dark brown in appearance and has a problem that the amount of use and application are limited because it is gum-like and has high viscosity. In addition, it has a strong irritating odor peculiar to ginger. For this reason, it is necessary to remove irritation from these viscous components and coloring components.

By the way, as a purification method of oleoresin, for example, crude chili oleoresin is washed with water or a mixed solution of water and lower fatty acid alcohol to remove unnecessary components and further purified (see Patent Document 1), crude marigold oleores A method of purifying gin to marigold oleoresin having a high lutein content by supercritical extraction treatment and then ketone precipitation treatment (see Patent Document 2) is known.
Moreover, although activated carbon is generally known as an industrial material used for decolorization (see Non-Patent Document 1), activated carbon is generally very effective for decolorization of a solution having a high water content as a mother solvent, When the mother solvent is a solution having a low water content, in other words, a solution having a high organic solvent concentration, it is said that the adsorption effect on most organic compounds is inferior (see Non-Patent Document 2). Specifically, when the organic compound to be separated and refined is oil-soluble and the impurity to be removed is oil-soluble, it is not suitable as a means for separation and purification.

Therefore, in the purification of oleoresin, the ingredients to be extracted are different because the raw materials to be extracted are different, and if the active ingredient to be purified has the same oil solubility as the ingredient to be removed, it is industrially simple. In some cases, it is difficult to purify, and some of these active ingredients volatilize, decompose, and adsorb during the purification process, so it is necessary to study the most suitable purification method for each oleoresin. is there.
And about the ginger oleoresin, the refinement method which can remove a coloring component, an adhesion component, etc. effectively has not been found until now.

JP-A-8-168356 JP 2004-131696 A Hideki Tachimoto, supervised by Ikuo Abe, “Applied technology of activated carbon”, Techno System Co., Ltd., p65, 2000. J. et al. W. Hustler, “Activated carbon: A guide to effective application”, Yoshitomo Eguchi, Takashi Oda, Kyoritsu Shuppan, p16-17, 1976.

  The present invention relates to providing a method for purifying ginger oleoresin with reduced viscosity and coloring components and improved irritation.

Although the present inventors tried removal of a coloring component and an adhesive component from ginger oleoresin with a water / alcohol mixed solution with reference to Patent Document 1, it was not possible to sufficiently remove the coloring component and the adhesive component, and the inventors wanted The effect was not obtained.
Further, from Non-Patent Document 2, ginger oleoresin produced by solvent extraction is basically an oil-soluble substance, and the contained shogaol, coloring components, resins causing odor and stimulating odor components are also oil-soluble. Because it is a substance, when ginger oleoresin is treated with activated carbon, it is necessary to use a solvent with a low water content as a mother solvent in order to uniformly disperse and dissolve, and in that case, the target active ingredient Shogaol Although the recovery rate was high, it was thought that the pigments and resins that were impurities to be removed at the same time could not be removed without being adsorbed, and the expected effect could not be obtained.
As a result of various investigations on the purification method of ginger oleoresin, the present inventors surprisingly dispersed ginger oleoresin in a high concentration organic solvent solution, and the dispersion was activated carbon having a pore size distribution of 15 to 40 mm. The purified product of ginger oleoresin, which minimizes the loss of active ingredients such as gingerol, and reduces unnecessary ingredients such as viscous ingredients and coloring ingredients, while improving irritation It was found that can be obtained.

  That is, the present invention is a method for producing a purified ginger oleoresin, characterized in that diginger oleoresin is dispersed in a 60 to 100% by mass organic solvent solution and contacted with activated carbon having a pore size distribution of 15 to 40 mm. A method is provided.

  The present invention also provides a purified product of ginger oleoresin obtained by the above production method.

The present invention also provides a purified product of ginger oleoresin, which is a purified product of ginger oleoresin, wherein the Gardner color number of the ethanol solution adjusted to 0.01% by mass of Shogaol is 1 to 4. Is.

  The present invention also provides a purified product of ginger oleoresin, which is a purified product of ginger oleoresin, wherein the absolute viscosity at 20 ° C. of an ethanol solution adjusted to 4% by mass of shogaol is 1 to 30 cP. Is.

  The present invention also provides a method for decoloring ginger oleoresin, characterized in that ginger oleoresin is dispersed in a 60 to 100% by weight organic solvent solution and contacted with activated carbon having a pore size distribution of 15 to 40 mm. To do.

  According to the present invention, it is possible to obtain a purified ginger oleoresin product having reduced viscosity components and coloring components and alleviating odor and improving irritation without significantly losing active ingredients such as gingerol and gingerol. be able to.

The ginger oleoresin used in the present invention refers to a product obtained by extracting and concentrating ginger family ginger (Zingiber officinale ROSC.) With an organic solvent such as ethanol, acetone or hexane. It is used as a seasoning.
Examples of commercially available products include “GINGER OLEORESIN FCC” (trade name) manufactured by Gibodan, “GINGER OLEORESIN” (trade name) manufactured by Bos Natural Flavors, and the like.

  Ginger oleoresin used in the present invention is dark brown and highly viscous (gum-like) in nature, has strong irritation peculiar to ginger, and contains about 5% by mass of shogaol.

The organic solvent solution used in the production of the purified ginger oleoresin of the present invention has an organic solvent concentration of 60 to 100% by mass, that is, an organic solvent only solution or an organic solvent containing 0 to 40% by mass of water. It is a solution.
As the said density | concentration, Preferably it is 60-90 mass%, More preferably, it is 60-85 mass%, More preferably, it is 60-80 mass%.

  Examples of the organic solvent include lower alcohols having 1 to 4 carbon atoms such as methanol, ethanol and propanol, acetone, dimethyl ether, hexane, chloroform, dichloromethane, toluene, ethyl acetate, acetonitrile and the like. In addition, since the solvent can be easily removed, lower alcohol and acetone are preferable, methanol and ethanol are more preferable, and ethanol is more preferable. You may use these individually or in combination of 2 or more types.

  Although the usage-amount of an organic solvent solution is not limited, Preferably it is 5 mass parts or more with respect to 1 mass part of ginger oleoresin (solid content conversion), More preferably, it is 8-30 mass parts, More preferably, it is 10-20 masses. Part.

  The dispersion of ginger oleoresin in the above organic solvent solution may be performed by bringing ginger oleoresin and the above organic solvent solution in contact with each other. Specifically, if ginger oleoresin is dissolved or suspended in the organic solvent solution. Well, techniques such as stirring and sonication can be employed as necessary.

Next, the dispersion is brought into contact with activated carbon having a pore size distribution of 15 to 40 mm. The activated carbon used is preferably one having a pore size distribution of 15 to 40 mm from the viewpoint of decolorization effect, adsorption effect of viscous substances and the like. 15 to 25 mm is used.
Here, the pore size distribution means the relationship between the pore size and the pore volume, and is usually measured by a gas adsorption method, a mercury intrusion method, or an X-ray small angle scattering method.

  As the activated carbon having the pore size distribution, carbonaceous raw materials such as wood powder (sawdust), coconut husk, coal, pitch, coke, etc. and carbonaceous raw materials of mineral substances are carbonized to have a predetermined pore size distribution, Inactivated ones are listed. Especially, what uses plant materials, such as wood flour (sawdust) and a coconut shell, is preferable, and it is more preferable to use wood flour (sawdust).

  Any carbonization and inactivation method may be used as long as it can form a predetermined pore size distribution. For example, when obtaining activated carbon having a pore size distribution of 15 to 25%, a raw material of wood flour (sawdust) is obtained by a steam method. Carbonization and activation (see Non-Patent Document 2), and when obtaining activated carbon having a pore size distribution of 25 to 40%, the raw material of wood flour (sawdust) is carbonized and activated by the zinc chloride method (chemical activation method) (See Non-Patent Document 2).

  Moreover, as a commercially available product, for example, those having a pore size distribution of 15 to 25%, white birch A, white birch B, white birch M, white birch P, granular white birch (all are trade names of Nippon Environmental Chemicals); Type, Taiho P type (both are trade names of Futura Chemical Co., Ltd.); In addition, as having a pore size distribution of 25 to 40 mm, carborafine, strong white rabbit, refined white rabbit, special white rabbit (all are trade names of Nippon Environmental Chemicals); Dazai S type (brand name of Nimura Chemical Co., Ltd.), etc. Is mentioned.

  The amount of the activated carbon used is not particularly limited as long as it does not exceed the adsorption capacity. However, since the loss of active ingredients is reduced and the efficiency of removing unnecessary components such as coloring components is not reduced, ginger oleoresin (solid Preferably, the amount is 0.001 to 1 part by mass, more preferably 0.0625 to 0.5 part by mass, and still more preferably 0.1 to 0.5 part by mass with respect to 1 part by mass. is there.

  Examples of the activated carbon include granular and powder forms, and any activated carbon may be used, but may be appropriately selected depending on the contact treatment.

As a means for contacting the dispersion and activated carbon, any method such as a patch method or a continuous treatment using a column may be used. For example, adding powdered activated carbon to a dispersion containing ginger oleoresin, stirring, selectively adsorbing unnecessary components, and then obtaining a filtrate from which unnecessary components have been removed by filtration, or granular activated carbon, etc. Examples thereof include a method of selectively adsorbing unnecessary components by continuous treatment using a packed column and eluting active components. Since ginger oleoresin can be purified continuously, it is preferably performed by a method such as continuous treatment using an activated carbon column.
Operation temperature at this time becomes like this. Preferably it is 5-60 degreeC, More preferably, it is 20-40 degreeC.

Further, in order to increase the recovery rate of the active ingredient, activated carbon that has been brought into contact with the ginger oleoresin dispersion may be further brought into contact with an organic solvent solution, and the resulting eluate may be collected.
The organic solvent solution used for elution here is preferably the same as the solution used for the dispersion.

The obtained ginger oleoresin may be further purified repeatedly by the above method, or may be purified by combining known methods such as an organic solvent precipitation method such as ethanol.
Moreover, you may remove an organic solvent suitably by methods, such as vacuum concentration and thin film concentration.

  The purified product of ginger oleoresin thus obtained can be used as it is after being concentrated or diluted.

  By using the method of the present invention, as described in Examples below, a viscous component, without significant loss of active ingredients such as shogaol and gingerol contained in ginger oleoresin, particularly hydrophobic active ingredients, The coloring component can be reduced. At the same time, the pungent odor can be reduced. That is, the purified product of ginger oleoresin thus obtained can be used even for the conventional ginger oleoresin that could not be blended in large quantities due to coloring, irritation, viscosity and the like.

  Therefore, the purified product of ginger oleoresin can be used in a wide range of products as food additives, flavorings, flavorings, etc., and examples of products include oral compositions (mouthwash, spray, toothpaste). Agents, tablets, etc.), foods such as chewing gum and refreshing confectionery in the mouth, oral hygiene devices (dental floss, cloth, etc.) and the like.

Also, the Gardner color number of Ginger oleoresin obtained by the method of the present invention (Shogaol 0.01% by mass ethanol solution) (see “JIS K0071-3 Color Test Method for Chemical Products, Part 2, Gardner Color Number”) is , Preferably it is 1-4, More preferably, it is 1-3, More preferably, it is 1-2.
If the Gardner color number of the purified ginger oleoresin in an ethanol solution adjusted so that the Shogaol content is 0.01% by mass is 1 to 4, it is advantageous in terms of formulation.

Further, the viscosity (absolute viscosity) of the purified ginger oleoresin obtained by the method of the present invention (Shogaol 4% by mass ethanol solution, temperature 20 ° C.) is preferably 1 cP to 30 cP, more preferably 5 cP to 25 cP, more preferably 10 cP to 25 cP.
If the absolute viscosity at 20 ° C. of a purified ginger oleoresin product in an ethanol solution adjusted to 4% by mass of shogaol is 1 to 30 cP, handling becomes easy and the blending is superior.

  The content, viscosity, and coloration of the active ingredient of ginger oleoresin may be measured using known means. For example, when measuring the content of the active ingredient, high performance liquid chromatography (HPLC) may be used. Examples of the detection means at this time include a UV detection device and an LC-Mass detection device. When measuring the coloration of ginger oleoresin, in addition to visual observation, the measurement method described in “JIS K0071-3 Color test method for chemical products, Part 2, Gardner color number”, the visible part (360 nm to 830 nm) should be used. A measurable device such as a spectrophotometer or a colorimeter may be used. Further, when measuring the viscosity of ginger oleoresin, it may be measured using an apparatus capable of measuring absolute viscosity, for example, a vibration viscometer “VM-1A” manufactured by Yamaichi Electric Co., Ltd.

Example 1
In a 100 mL glass screw vial, 2 g of ginger oleoresin (manufactured by Givodan) was added as a raw material and dissolved in 50 mL of a 95% by mass ethanol aqueous solution.
2 g of various activated carbons (Shirakaba WH2C, Shirasagi P, carborafine, all manufactured by Nippon Enviro Chemicals) were added to each ginger oleoresin dispersion. After stirring for 2 hours at room temperature using a shaker to adsorb the colored, viscous, and odorous components to the activated carbon, the solution is filtered with a 0.45 μm filter, and the filtrate is HPLC (column: inertosyl-ODS-3 (GL-Science, 2.1 × 150 mm), 0.1% TFA (0 min) → 100% MeCN (30 min) → 100% MeCN (40 min), 0.2 mL / min, 40 ° C., UV254 nm) (FIG. 1). At this time, the concentration of shogaol when ginger oleoresin was dispersed in 50 mL of a 95% by mass ethanol aqueous solution was set to 100%.
Further, 1.5 mL of the filtrate was put into a 2 mL glass screw vial, and a panel (two persons) was used to compare the odor (irritating odor) level and the degree of color reduction with the ginger oleoresin solution.
At this time, the coloration and odor when ginger oleoresin was dispersed in 50 mL of 95% by mass ethanol aqueous solution were used as a reference.
Here, “odor” means a strong irritating odor peculiar to ginger.

Table 1 below shows the Shogaol recovery rate, visual color reduction degree, and odor level in each processed product obtained as a result of HPLC analysis.
As shown here, the Shogaol recovery rate was the same for all three types, but the white WH2C of less than 15% showed almost no color removal effect, and the pungent odor mitigating effect was only slightly effective.
On the other hand, both carborafine (25-40Å) and white cocoon P (15-25Å) showed a color removal effect and an irritating odor mitigation effect, and carborafine (25-40Å) was the most excellent in terms of color removal effect. .
Accordingly, the pore diameter distribution of activated carbon was excellent at 15-40 mm.

Example 2
Prepare 6 pieces of ginger oleoresin 2g in a 100mL glass screw vial, each containing 50%, 60%, 70%, 80%, 90%, anhydrous (99.5%) concentration Was dispersed in 50 mL of an aqueous ethanol solution.

  Carbolafine 1.0 g was added to each ethanol aqueous solution, stirred for 2 hours at room temperature, filtered through a 0.45 μm filter, and ginger oleoresin was dispersed in 50 mL of 95 mass% ethanol aqueous solution in the same manner as in Example 1 above. Based on the solution, the recovery rate of Shogaol and the degree of color reduction were compared. The results are shown in Table 2 below.

  Decolorization was clearly observed regardless of the ethanol concentration of the ethanol solution (also referred to as a mother solvent) at the time of dispersion. Moreover, when the odor level of each processed product was judged, all became mild fragrance compared with before processing. However, when the ethanol concentration of the mother solvent reached 50% by mass, the Shogaol recovery rate drastically decreased. On the other hand, when the ethanol concentration of the mother solvent was 60% by mass or more, the Shogaol recovery rate increased to nearly 60%.

As described above, in the case of decolorization by activated carbon treatment, decolorization was effective as the ethanol concentration decreased, as is generally said, but Shogaol, gingerol, etc. which are originally active ingredients of ginger oleoresin Even the hydrophobic component was lost at the same time. However, surprisingly, if an ethanol aqueous solution of 60% by mass or more was used, it was possible to satisfy all of the recovery rate of active ingredients and the degree of color reduction.
Accordingly, when the dispersion was brought into contact with activated carbon, a result that an organic solvent solution of 60% by mass or more was excellent as a dispersion was obtained.

Example 3
2 g of ginger oleoresin was placed in a 100 mL glass screw vial and dissolved in 50 mL of an aqueous ethanol solution having a concentration of 60% by mass, 70% by mass, 80% by mass, 90% by mass, and anhydrous (99.5% by mass). Except for adding 0.25 g of carborafine, the same procedure as in Example 2 was performed, and the recovery rate of shogaol and the degree of color reduction were compared based on a solution in which ginger oleoresin was dispersed in 50 mL of a 95% by weight ethanol aqueous solution. . In addition, carborafine 0.25g was replaced with 0.5g in the same manner. These results are shown in Table 3 below. In addition, the result of the said Example 2 was described for 1.00 mass part of carborafine.

  When 0.25 parts by mass of carborafine is used, the recovery rate of Shogaol is 80% when the ethanol concentration of the mother solvent is 60% by mass or more, and when 0.50 parts by mass of carborafine is used, the ethanol concentration of the mother solvent is 70% by mass or more. This was a high recovery rate.

Regarding the decolorization level of each processed product, when 0.25 parts by mass of carborafine was used, the ethanol concentration of the mother solvent was 70% by mass or less, and when 0.50 parts by mass of carborafine was used, the ethanol concentration of the mother solvent was 80% by mass or less. Occasionally, decolorization was clearly observed.
Moreover, when the odor level of each processed product was judged, all became mild fragrance compared with before processing.

As described above, 0.25 parts by mass of carborane fins was most preferable in terms of recovery, and 0.50 parts by mass of carborane fins was most preferable in terms of the effect of reducing coloring.
Therefore, the result that the amount of activated carbon was most excellent in 0.25 mass part-0.50 mass part per 2 g of ginger oleoresin was obtained.

  The shogaol recovery rate shown in the above Table 3 is 80% or more, and the solution recovered by carborafin treatment under conditions of good decolorization level is concentrated under reduced pressure to remove the solution containing the solvent using a rotary evaporator, The results of measuring the Shogaol concentration of each sample under the aforementioned HPLC conditions are shown in Table 4 below. Under any condition, shogaol was concentrated.

  Further, each processed product is diluted with ethanol so that the Shogaol concentration becomes 0.01% by mass, and measured according to the method described in “JIS K0071-3 Color test method for chemical products, Part 2, Gardner color number”. The results are shown in Table 5 below.

  Any of the processed products of the present invention has a Gardner color number significantly lower than that of the raw material oleoresin solution, which is superior in blending.

  Furthermore, each of the above treated products was diluted with ethanol so that the Shogaol concentration was 4% by mass, and 1.5 mL of each sample solution was placed in a 1.5 mL vial, and vibration viscosity manufactured by Yamaichi Denki Co., Ltd. at 20 ° C. The absolute viscosity of each sample was measured using a total of “VM-1A” and shown in Table 6 below.

  Any of the treated products of the present invention has a significantly lower absolute viscosity of about 1/6 to 1/10 than that of the raw oleoresin solution, which facilitates handling and has an advantage in blending.

  Considering the above results, while reducing the loss due to adsorption of activated carbon of shogaol showing various effective physiological actions to 20% or less, reducing coloring to a good level, increasing the concentration of shogaol, and The preferred method for obtaining ginger oleoresin with reduced viscosity is to use activated carbon with a large pore size such as carborane (25-40mm), and when using 0.25 parts by mass activated carbon, the ethanol concentration is 60% by mass. The method of using the mother solvent whose ethanol concentration is 70 mass% or more and 80 mass% or less when using the mother solvent of above 70 mass% or less and using 0.50 mass part activated carbon is mentioned.

The result of the HPLC analysis before the process of various activated carbon before the process of ginger oleoresin is shown.

Claims (13)

A method for producing a purified product of ginger oleoresin, comprising dispersing ginger oleoresin in a 60 to 100% by mass ethanol solution and contacting with activated carbon having a pore size distribution of 15 to 40 mm. The process according to claim 1, wherein the pore size distribution of the activated carbon is 25～40A. The manufacturing method of Claim 1 or 2 using 0.125-0.5 mass part activated carbon with respect to 1 mass part of ginger oleoresin. The manufacturing method of any one of Claims 1-3 using 5-30 mass parts ethanol solution with respect to 1 mass part of ginger oleoresin. The manufacturing method according to any one of claims 1 to 4, wherein the temperature at which the activated carbon is brought into contact is 5 to 60 ° C. The ginger oleoresin refinement | purification thing obtained by the manufacturing method of any one of Claims 1-5 . Shi Yogaoru is ginger oleoresin of claim 6, wherein the Gardner color number of the adjusted ethanol solution to a 0.01 mass% characterized in that it is a 1-4. Ginger oleoresin of claim 6, wherein the absolute viscosity at 20 ° C. of the adjusted ethanol solution as shea Yogaoru becomes 4 mass% is 1～30CP. A method for decoloring ginger oleoresin, comprising dispersing ginger oleoresin in an ethanol solution of 60 to 100% by mass and contacting with activated carbon having a pore size distribution of 15 to 40 mm. The decolorization method according to claim 9 , wherein the activated carbon has a pore size distribution of 25 to 40 mm. The decoloring method according to claim 9 or 10 , wherein 0.125 to 0.5 parts by mass of activated carbon is used with respect to 1 part by mass of ginger oleoresin. The decoloring method according to any one of claims 9 to 11, wherein 5 to 30 parts by mass of an ethanol solution is used with respect to 1 part by mass of ginger oleoresin. The decolorization method according to any one of claims 9 to 12, wherein the temperature at which the activated carbon is brought into contact is 5 to 60 ° C.

Images