JPH04145048A - Production method of purified chlorogenic acid - Google Patents

Abstract

PURPOSE:To industrially and advantageously obtain high-purity purified chlorogenic acid without containing unnecessary ingredients such as caffeine or trigonelline using a simple means by subjecting an extract separated from raw coffee beans with an aqueous solvent to contact treatment with a strong acidic cation exchange resin. CONSTITUTION:Raw coffee beans are extracted with a hydrous water-miscible organic solvent, preferably hydrous ethanol to provide an extract separated from the raw coffee beans with the aqueous solvent. The resultant extract is then subjected to contact treatment with a strongly acidic cation exchange resin, e.g. SK-116, SK-1B (Mitsubishi Chemical Industries Ltd,) Amberlite IR-120(R) or Amberlite IR-200(R) (Rohm & Haas Co.) to industrially and advantageously remove caffeine using a simple means. Thereby, the objective purified chlorogenic acid, useful as a safe natural antioxidant excellent in persistence for food and drinks, health and sanitation, medicines, etc., especially a fading inhibitor and a flavor deterioration inhibitor for the food and drinks without containing any unnecessary ingredients such as the caffeine is obtained in high purity and yield.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for producing lorogenic acid, which is useful as a natural antioxidant in foods and beverages, health and medicine, etc. This invention relates to a method for producing purified chlorogenic acid.

[Prior Art] It is known that green coffee beans contain antioxidant substances such as chlorogenic acid, caffeic acid, ferulic acid, p-coumaric acid, and rJ tocopherol. In addition, several proposals have been made to extract these antioxidant components from green coffee beans, for example, by treating an aqueous slurry of green coffee bean flour in the presence of proteolytic enzymes and/or fibrinolytic enzymes, A method for producing edible natural antioxidants, which comprises concentrating the aqueous extract to form a concentrated solution, or freeze-drying or spray-drying it (Japanese Patent Laid-Open No. 58-1383
47), or an edible natural antioxidant characterized by extracting green coffee bean powder with water under reflux and concentrating the resulting aqueous extract to form a concentrated solution, or freeze-drying or spray-drying. (Japanese Patent Publication No. 61-30549), the green coffee beans are coarsely ground, defatted, and then the average particle size is 1.
00 μm or less, or immediately pulverize green coffee beans to an average particle size of 100 μm or less, then defatting, extracting the resulting fine powder with hot water, and concentrating and/or drying the extract as necessary. A method for producing a natural anti-inflammatory agent for foods (Japanese Unexamined Patent Publication No. 111671/1983) has been proposed.

[Problems to be Solved by the Invention] However, in the extracts obtained by the above-mentioned prior art, all the components soluble in the aqueous solvent are extracted, and in all cases, the purity of the antioxidant components is extremely low. , it also contained an interesting odor and colored substances, and was completely unsatisfactory as an antioxidant. Furthermore, caffeine, which accounts for most of the impurities, has a serious problem in that it often becomes a limiting factor in the use of the antioxidant due to its strong physiological activity.

On the other hand, in other fields, the extract obtained by extracting unroasted coffee beans with an aqueous medium is used to generate chlorogen by using an anion exchange resin with volatile carboxylic acid anions added. A method has been proposed to reduce the chlorogenic acid content in green coffee bean extract, which adsorbs and removes acids, and then to reduce the chlorogenic acid content in unroasted coffee, which is dried together with the green coffee beans (in particular, Kaisho 59-1358
No. 40), but this publication does not specifically disclose a method for purifying chlorogenic acid.

In addition, Japanese Patent Application Publication No. 63-502434 discloses that chlorogenic acid is separated and recovered by extracting plant materials such as green coffee beans and lingonberry leaves, and the resulting extract is used to create a molecular compound consisting of a cross-linked modified polysaccharide. A method has been disclosed in which chlorogenic acid is separated from impurities by filtration chromatography using sheep, and the chlorogenic acid and/or an extract that does not contain chlorogenic acid is recovered, but this method is complicated and is not a practical method. I can't say that.

[Means for solving the problem] By a conventionally known method, an aqueous solvent extract of green coffee beans is contacted with a synthetic resin adsorbent to adsorb chlorogenic acid, etc., and then methanol, ethanol, acetone, When eluted with propylene glyfur or the like, not only antioxidant substances such as chlorogenic acid but also caffeine and all other substances adsorbed to the resin are desorbed, making it impossible to obtain highly pure chlorogenic acid.

The present inventors have conducted extensive research to solve many of the problems described above. As a result, by contacting an aqueous solvent extract of green coffee beans with a strongly acidic cation exchange resin (hereinafter sometimes simply referred to as cation exchange resin), caffeine is adsorbed and removed by the resin. The present invention was completed by discovering that nearly pure lorogenic acid can be obtained industrially and with great advantage by easy means.

Therefore, an object of the present invention is to provide highly purified purified chlorogenic acid that does not contain unnecessary components such as caffeine and trigonelline.

The present invention will be explained in detail below.

The green coffee beans used in the present invention may be, for example, Arabica, Robusta, Liberica, or the like, and any coffee beans can be used regardless of their type or origin.

Examples of aqueous solvents for extracting chlorogenic acid from coffee beans include water or water-containing water-miscible organic solvents, such as methanol, ethanol, and ethanol having a water content of 5% by weight or more.
- Water-containing water-miscible organic solvents such as propatool, acetone, methyl ethyl ketone and the like can be mentioned. Particularly preferred is aqueous ethanol.

These water or water-containing water-miscible organic solvents are usually used in an amount of, for example, about 2 to about 50 parts by weight per 1 part by weight of ground coffee beans, and extraction is carried out at a temperature of about 20 to about 80°C.

The extraction operation can be carried out either batchwise or continuously using a column. For example, in the case of batch-type extraction, conditions such as stirring extraction for about 1 to 4 hours are often adopted, and in the case of column-type extraction,
This can be carried out by filling a column with ground coffee beans and circulating the water-containing water-miscible organic solvent as described above under the same conditions as in a batch system.

Next, by contacting the obtained extract with a strongly acidic cation exchange resin, the caffeine in the green coffee bean extract is almost completely adsorbed and removed by the resin, resulting in an extract containing highly pure chlorogenic acid. can be obtained.

Such strongly acidic cation exchange resins include, for example, 5K
-116,5K-IB, (Mitsubishi Kasei); Amberlite J R-120, 200 (Rohm & Haa
S), etc.

The contact treatment between the green coffee bean extract and the cation exchange resin in the present invention can be carried out in any manner such as a batch process or a continuous process using a column. Continuous processing is employed. Conditions for such contact treatment can be appropriately selected depending on the type of coffee beans, the concentration of the extract, etc., but for example, the conditions for continuous treatment using a column are approximately Examples of conditions include passing 1 to about 50 volumes of coffee extract at a flow rate of about 10 to about 50° C. and an SV of about 0.1 to about 5.

In another embodiment of the invention, the aqueous solvent extract of the green coffee beans is subjected to a styrene-divinylbenzene-based or methacrylic acid ester-based synthesis process in advance by a conventionally known method before the aqueous solvent extract of the green coffee beans is contacted with a cation exchange resin. It can also be preliminarily purified by contact treatment with a porous resin adsorbent.

As a preliminary purification treatment using such a porous resin adsorbent,
The aqueous solvent extract of green coffee beans is contacted with a porous resin to remove unadsorbed impurities, and after washing with water, the adsorbed chlorogenic acid, caffeine, and other components are removed using methanol, ethanol, etc. by a known method. This can be done by elution.

Examples of the porous resin adsorbent include styrene-divinylbenzene, such as Diaion HP10. Same website
20. Same HP30. Same HP40. Same HP50; Same 5P2
06. Same S P 207 (Mitsubishi Kasei); AI+I
berlite XAD-2, berlite XAD-4, etc. (Rhom
& Haas): Hitachi gel group 301 sail # 301
1. There are similar products such as #3019 (Hitachi Chemical), etc.
Examples of methacrylic acid ester polymer resins include Diaion HPIMG and 2MG (Mitsubishi Kasei);
Amberlite XAD-7, Amberlite XAD-8i
(Rhom & Haas).

Furthermore, during the contact treatment with the porous polymer resin as described above, a substance having a salting-out effect, such as common salt, can be added to increase the adsorption effect.

The extract thus obtained is substantially free of caffeine and can be used as a natural antioxidant with high purity of chlorogenic acid. Furthermore, if desired, the cation exchange resin treated solution can be concentrated under reduced pressure or normal pressure to obtain a concentrated solution. Alternatively, dextrins, starches, natural gums, sugars and other excipients may be added to the treatment liquid or its concentrate and dried by spray drying, vacuum drying or other known methods to form powders or granules. It can also be in any other form.

Hereinafter, preferred embodiments of the present invention will be explained in more detail with reference to Examples.

[Example] Example 1 1000 g of 70% ethanol to 200 g of green coffee beans
was added, and the mixture was stirred and extracted at 75°C for 3 hours. After cooling, solid/liquid separation was performed, and the separated extract was distilled under reduced pressure to recover ethanol. Water and 40 g of common salt were added and dissolved in the concentrated solution to give a total amount of 400 g. This solution is absorbed into an adsorption resin (S P
-207) The liquid was passed through a column packed with 150+a (2 to adsorb coffee extract. After washing the column with water, 60+a
Chlorogenic acid, caffeine, etc. were eluted using 400 g of % ethanol. The obtained eluate was passed through a column packed with cation exchange resin (SK-I B) 25ON at SV-1,Q to adsorb and remove caffeine. The eluate was dried under reduced pressure to obtain purified chlorogenic acid 12 of the present invention.
I got g. As a result of analyzing this antioxidant, caffeine,
Trigonelline and the like were not detected, but chlorogenic acid and its congeners were detected.

Example 2 Ground coffee beans (Java Robusta) 7 per 100g
400 g of 0% methanol was added, stirred and extracted at 70°C for 3 hours, and after cooling, solid/liquid separation was performed. The separated extract was passed through a column packed with 200 si (l) of cation exchange resin (SK-IB) at s V -1.0. The eluate was dried under reduced pressure to obtain 12 g of purified chlorogenic acid. No impurities such as caffeine were detected in this product.

[Effects of the Invention] According to the present invention, caffeine can be removed industrially very advantageously by a simple means of contacting an aqueous solvent extract of green coffee beans with a strongly acidic cation exchange resin. , it is possible to obtain chlorogenic acid with high purity and high yield.

The purified chlorogenic acid obtained by the present invention does not contain caffeine or other undesirable impurities, so there are no restrictions on usage or amount of addition as with conventional products.
It can be added to medicines to provide safe and long-lasting antioxidant properties. It is particularly useful as a natural antioxidant that has excellent effects as an anti-fading agent and anti-deterioration agent in foods and drinks.

Patent applicant: Hasegawa Fragrance Co., Ltd.

Claims (1)

[Claims] A method for producing purified chlorogenic acid, which comprises contacting an aqueous solvent extract of green coffee beans with a strongly acidic cation exchange resin.