JP2008266144A - Method for producing purified chlorogenic acid inhibited in secondary precipitation - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for simply and industrially producing purified chlorogenic acid having a good flavor without causing secondary precipitation. <P>SOLUTION: This method for producing purified chlorogenic acid is characterized by concentrating a raw or roasted coffee bean extract in a refractive sugar content (20°C) of Bx8° to Bx60° as a solid content concentration and then bringing the concentration product into contact with acid clay and/or activated clay. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a method for producing purified chlorogenic acid useful as a natural antioxidant for foods and drinks, health hygiene and pharmaceuticals, and more specifically, purification in which secondary precipitation does not substantially occur over time in the state of an extract. The present invention relates to a method for producing chlorogenic acid.

  It is becoming clear that coffee has many functional and physiological effects, not just as a favorite product, and chlorogenic acids have attracted attention as functional components. The functions of chlorogenic acids have been known to be antioxidant (Patent Documents 1 and 2), antimutagenicity (Non-Patent Document 1), carcinogenesis suppression (Non-Patent Document 2), and active oxygen scavenging ability (Non-Patent Document 3). Etc. are known. Several proposals for extracting and purifying chlorogenic acids from coffee beans have already been made. For example, an aqueous slurry of raw coffee bean flour is treated in the presence of a proteolytic enzyme and / or a fibrinolytic enzyme, and the aqueous extract is extracted. A concentrated solution, or freeze-dried or spray-dried method for producing a natural edible antioxidant substance (Patent Document 3), aqueous coffee bean powder extracted with water under reflux, and aqueous extract produced A concentrated solution, or freeze-dried or spray-dried, a method for producing an edible natural antioxidant (Patent Document 4), raw coffee beans are coarsely pulverized, defatted, and then the average particle size Finely pulverize to 100 μm or less, or immediately pulverize the green coffee beans to an average particle size of 100 μm or less, then degrease, extract the resulting fine powder with hot water, and concentrate and / or dry the extract as necessary. A method for producing a natural antioxidant for foods (Patent Document 5), etc., comprising drying is proposed. Furthermore, coffee contains caffeine as a component other than chlorogenic acids, but as a method for producing chlorogenic acids with reduced caffeine, an aqueous solvent extract of coffee beans is brought into contact with a strong cation exchange resin. A method of purifying chlorogenic acid characterized by removing caffeine (Patent Document 6), contacting an aqueous solvent extract of green coffee beans with a synthetic adsorbent resin, and desorbing the adsorbing portion with a dilute alkaline aqueous solution A characteristic purification method of chlorogenic acid (Patent Document 7), a method of purifying chlorogenic acid by performing chromatography using molecular sieves composed of modified polysaccharides obtained by cross-linking extracts such as fresh coffee beans and cowberry leaves (patent) Reference 8), green coffee beans are extracted with hydrous ethanol, the extract is hydrolyzed with hydrochloric acid, and concentrated, and the concentrate is made alkaline. After solvent neutralization and neutralization, chlorogenic acids are adsorbed on the porous polymer resin and desorbed with ethanol, and ethanol is concentrated and removed to purify chlorogenic acids (Patent Document 9), including chlorogenic acids obtained from plants A method for producing a composition containing a high concentration of chlorogenic acids, comprising a step of eluting an adsorbate adsorbed on activated carbon with an organic solvent or an aqueous solution containing them after treating the water-soluble extract with activated carbon (Patent Document 10) ) Etc. have been proposed.

  However, the extracts obtained by the prior arts described in Patent Documents 3 to 5 are extracted with all components soluble in an aqueous solvent. As a result, the purity of chlorogenic acid is low, and it contains an off-flavor odor and coloring substances. The oxidizer was not satisfactory. In addition, the methods described in Patent Documents 6 to 10 have long processes and are complicated in operation, and are not necessarily satisfactory in practical use.

  Therefore, as a method of removing caffeine from a coffee extract by a simple method, a method of selectively removing caffeine from an aqueous solution by bringing the aqueous solution containing caffeine into contact with activated clay or acidic clay (Patent Document) 11) has been proposed. In addition, it is also known that other impurities are removed by the method in which the coffee extract is brought into contact with activated clay or acidic clay (Patent Documents 12 and 13).

Nuyen V. C. Araki Y., et al. Jinnouchi T. and Murai H .; : ASIC, 16 Colloque, Kyoto, 88-93 (1995) T.A. Tanaka and H.M. Mori: Proceedings of the 16th International Scientific Colloquium on Coffee 1995, Vol. 1, pp. 79-87 Araki Y. and Nguyen V.M. C. : ASIC, 16 Colloque, Kyoto, 104-108 (1995) JP-A-4-27374 JP-A-6-38723 JP 58-138347 A Japanese Patent Publication No. 61-30549 Japanese Patent Laid-Open No. 62-111671 Japanese Patent Laid-Open No. 4-145048 JP-A-4-145049 JP-T63-502434 Japanese Patent No. 2983386 JP 2005-263632 A JP-A-6-142405 JP 2006-87306 A Japanese Patent Laid-Open No. 2006-117431

  However, all of the above inventions focus on the extraction efficiency of chlorogenic acid, the purity in the extract, and impurities, but they do not focus on secondary precipitation.

  Therefore, an object of the present invention is to provide a simple and industrially advantageous production method of purified chlorogenic acid that is stable in the state of the extract and does not cause precipitation, and that does not generate secondary precipitation even after being subjected to aging. The purpose is to provide.

The present inventors have conducted extensive research in view of such circumstances, and after concentrating the coffee extract as a solid content concentration to a refractive sugar content (20 ° C.) of B × 8 ° or more, contact the acid clay and / or activated clay. As a result, it was found that, immediately after production, no stable precipitation occurred, and that the extract was heat-sterilized, and that secondary precipitation did not occur even when stored for a longer period of time, and the present invention was completed. .
Thus, the present invention is characterized in that the raw or roasted coffee bean extract is concentrated to a refractive sugar content (20 ° C.) of Bx8 ° to Bx60 ° as a solid content, and then contacted with acid clay and / or activated clay. A method for producing purified chlorogenic acid is provided.
Further, the present invention provides the purified chlorogenic acid described above, wherein the contact treatment of the raw or roasted coffee bean extract concentrate with acidic clay and / or activated clay is performed under acidic conditions of pH 2-7. A manufacturing method is provided.
Furthermore, the present invention provides the method for producing the purified chlorogenic acid, wherein substantially no secondary precipitation occurs.
Furthermore, the present invention provides the purified chlorogen as described above, wherein the raw or roasted coffee bean extract is extracted with an aqueous ethanol solution or ethanol under acidic conditions after concentration at a high concentration. A method for producing an acid is provided.
Furthermore, the present invention provides a purified chlorogenic acid characterized in that the purified chlorogenic acid obtained by any one of the above methods is concentrated at a high concentration and then extracted with an aqueous ethanol solution or ethanol under acidic conditions. A method is provided.
The present invention further provides the above-mentioned method for producing purified chlorogenic acid, characterized in that the raw or roasted coffee bean extract is treated with a synthetic adsorption resin under neutral to alkaline conditions.
Furthermore, the present invention also provides a method for producing the above-mentioned purified chlorogenic acid, characterized in that a raw or roasted coffee bean extract has been treated with a cation exchange resin.

  The purified chlorogenic acid extract of the present invention is stable and does not cause precipitation immediately after production, and is stable with no secondary precipitation even when the extract is heat-sterilized or stored for a long period of time. Therefore, when the product of the present invention is produced industrially, it is possible to uniformly fill the product. In addition, when the product of the present invention is used industrially, a large amount of precipitate does not adhere to the bottom of the container, so that the trouble of using the container after shaking it can be saved. Since the flowability from the container is good, there is no need to perform extra work such as scraping with a spatula from the bottom of the container, and the workability is extremely good. Moreover, since the caffeine is reduced in the method of the present invention, it can be used with peace of mind by children and elderly people. Furthermore, the method of the present invention does not reduce chlorogenic acids and trigonelline useful for the human body. Furthermore, in the method of the present invention, since the balance of the organic acid composition is the same as that before the treatment, it is excellent in flavor. In the present invention, a useful method for producing chlorogenic acid having these effects can be provided by a simple method and an industrially advantageous method.

Hereinafter, the present invention will be described in detail according to the embodiment.

  Examples of chlorogenic acid in the present invention include chlorogenic acids such as chlorogenic acid, caffeic acid, ferulic acid, isochlorogenic acid, neochlorogenic acid, and water-soluble salts such as sodium and potassium of these acids.

  The coffee beans used in the present invention may be any of, for example, Arabica, Robusta, and Riberica, and any coffee bean can be used regardless of the type or production area.

  The coffee bean extract used in the present invention may be extracted from coffee beans, but a commercially available coffee extract may be concentrated, and coffee extract powder, instant coffee, etc. can also be used.

  When extracting from coffee beans, considering the content of chlorogenic acid, extraction from green beans is common, but roasted coffee beans can also be used. In particular, when roasting is performed in a range where chlorogenic acids do not substantially decrease relative to green beans, that is, when the L value is 30 to 55, preferably L value 45 to 55, the raw smell peculiar to green beans disappears. Therefore, it can illustrate preferably as a raw material of this invention.

  The L value is an index representing the degree of roasted coffee, and is a value obtained by measuring the lightness of the crushed coffee beans with a color difference meter. Black is represented by an L value of 0 and white is represented by an L value of 100. Accordingly, the deeper the roasted coffee beans, the lower the value and the shallower the value, the higher the value.

  For reference, the L value of roasted beans that are normally used for drinking is approximately the following level. Italian roast: 16-19, French roast: 19-21, Full city roast: 21-23, City roast: 23-25, High roast: 25-27, Medium roast: 27-29. Shallow roasting is less commonly used in normal drinking.

  As the extraction solvent, water is preferable, but a water-containing hydrophilic organic solvent such as methanol, ethanol, 2-methylethylketone, 2-propanol, acetone having a water content of 5% by weight or more, preferably about 5 to about 90% by weight. And water-containing water-miscible organic solvents such as methyl ethyl ketone.

  These water or water-containing hydrophilic organic solvent is usually used in an amount of about 2 to about 50 parts by weight with respect to 1 part by weight of ground coffee beans, and extraction is performed at a temperature of about 20 ° C to about 100 ° C. For the extraction operation, a conventionally known extraction method such as a batch method or a continuous method using a column can be employed as it is.

  The coffee extract is subsequently concentrated to a solid content concentration of Bx8 ° to Bx60 °, preferably Bx10 ° to 50 °, more preferably Bx10 ° to 40 ° in terms of refractive sugar (20 ° C). When the concentration of the concentrate is lower than this range, the occurrence of secondary precipitation is not sufficiently suppressed after the contact treatment with the acid clay and / or the activated clay. In addition, when the concentration of the concentrate is higher than this range, the viscosity makes the contact treatment with acidic clay and / or activated clay difficult, and the efficiency in terms of workability deteriorates, which is not an industrially advantageous method. . Only when the concentration of the concentrate is within this range, the effect of suppressing the occurrence of secondary precipitation, which is an excellent effect of the present invention, can be obtained. Any concentration method can be used as long as it can be concentrated, and examples thereof include normal pressure concentration, reduced pressure concentration, RO membrane concentration, and freeze concentration. Further, in column extraction, instant coffee dilution, etc., it is possible to make this concentration range without going through the concentration step, in which case the concentration step is unnecessary.

The concentrate is then contacted with acid clay and / or activated clay. The activated clay used in the present invention is obtained by treating a naturally occurring acidic clay (montmorillonite clay) with a mineral acid such as sulfuric acid, and is a compound having a porous structure having a large specific surface area and adsorbing ability. It is known that further treatment of acid clay with an acid treatment changes the specific surface area, improving the decolorization ability and changing the physical properties. Usually, activated clay is mainly used for refining fats and oils and mineral oils because it has the ability to decolorize fats and oils and adsorb impurities. Both activated clay and acidic clay have SiO ₂ , Al ₂ O ₃ , Fe ₂ O ₃ , CaO, MgO, etc. as general chemical components, but when used in the present invention, SiO ₂ / Al ₂ O _3. A ratio of 3.0 to 6.0, preferably 4.0 to 5.0 is suitable. The specific surface area is preferably 50 to 350 m ² / g, and the pH (5% suspension) is preferably in the range of 5 to 10, particularly 6 to 9.8.

  For the contact treatment of the concentrate with the acid clay and / or the activated clay, any method such as a batch process or a continuous process using a column can be adopted. Generally, powdered acid clay and / or activated clay is added, stirred, and filtered to obtain a filtrate from which acid clay and / or activated clay has been removed, or filled with granular acid clay and / or activated clay. A method of continuous processing using the prepared column is employed. The conditions for the above contact treatment can be appropriately selected according to the concentration of the concentrated solution. For example, in the case of a batch-type treatment, the powdered acidic clay and / or activity with respect to the solid content weight of the concentrate. 10 to 200 parts by weight, preferably 20 to 100 parts by weight of clay is added, and after stirring for about 30 minutes to about 5 hours at about 10 ° C. to about 40 ° C., powdered acidic clay and / or by filtration. A method for obtaining a filtrate from which activated clay has been removed can be exemplified.

  In addition, the contact treatment between the coffee bean extract concentrate and the acid clay and / or the activated clay is preferably performed under acidic conditions of pH 2-7. When the treatment is carried out under conditions where the pH exceeds 7 or under pH 2, the generation of secondary precipitation cannot be sufficiently suppressed.

  Before or after the coffee extract concentrate is contact-treated with the acid clay and / or the activated clay, an impurity removal step may be performed by extraction with an aqueous ethanol solution or ethanol under acidic conditions. In general, coffee beans are roasted to produce roasted aroma. This roasted incense is preferable also in terms of fragrance, when chlorogenic acid obtained by extraction from coffee beans is used as an active ingredient for the purpose of stability (antioxidant) of flavors and pigments of beverages. There is no need to remove it. Moreover, it also becomes a cause of flavor deterioration. This roasted aroma is expected to be phenol and polyphenols having a molecular weight of 150 or less. In addition, the caffeine content can be reduced by extraction with an aqueous ethanol solution or ethanol under acidic conditions. Under acidic conditions, extraction with an aqueous ethanol solution or ethanol is carried out by the method described below. First, the coffee extract is concentrated to a high concentration. As the high concentration range, the water content is preferably 50% or less, and can also be used in the form of a dry powder. As the concentration or drying method, any method can be used as long as it can be concentrated to a high concentration, and examples thereof include normal pressure concentration, reduced pressure concentration, RO membrane concentration, freeze concentration, spray drying, vacuum drying, freeze drying and the like. be able to. The preferred range of the ethanol aqueous solution or ethanol water / ethanol weight ratio used for extraction of the highly concentrated coffee extract is 30/70 to 0/100, preferably 20/80 to 0/100, more preferably 10/90 to 0/100 can be mentioned. When the amount of water exceeds this range, the removal rate of impurities that cause deterioration increases, but chlorogenic acid itself is extracted, and the yield decreases. Moreover, as extraction temperature, 20 to 70 degreeC, Preferably 25 to 60 degreeC can be illustrated. If the extraction temperature is lower than this, the removal rate of the deterioration-causing component is lowered and the effect is small. When the extraction temperature is higher than this, the removal rate of the deterioration-causing component is increased, but chlorogenic acid itself is extracted, and the yield is reduced. The amount of ethanol aqueous solution or ethanol used may be about 1 to 10 times the amount of 1 part by weight of highly concentrated coffee extract. When it is added to foods and drinks by this operation and preserved, purified chlorogenic acid is obtained in which quality deterioration hardly occurs and no irritating odor is generated.

In addition, before the coffee extract concentrate is contact-treated with acidic clay and / or activated clay, a known decaffeination treatment such as a synthetic adsorption resin treatment or a cation exchange resin treatment under neutral to alkaline conditions may be performed. good. The following method can be illustrated as a decaffeination processing method by the synthetic adsorption resin under alkaline conditions. In the case of water extraction, the coffee extract is used as it is. In the case of a water-containing hydrophilic organic solvent extract, the content of the organic solvent is, for example, about 5% by weight or less by means such as distillation. Thereafter, the pH of the extract is changed from about 7 to about 12 neutral to alkaline, and then the extracted components such as caffeine and trigonelin in the coffee bean extract are contacted with the synthetic adsorption resin to the synthetic adsorption resin. Adsorb. Examples of the alkaline substance include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate and the like. The synthetic adsorbent resin, for example, a specific surface area of about 300 meters ² / g to about 700m ² / g; the properties of the pores having a radius of about 5nm~ about 130 nm; pore volume from about 0.7 to about 1.1 ml / g Examples thereof include styrene / divinylbenzene-based porous synthetic adsorption resin. Such a synthetic adsorption resin can be easily obtained in the market, for example, Diaion HP10, HP20, HP30, HP40, HP50 ;, SP206, SP207, SP-70 (hereinafter Mitsubishi Chemical). Amberlite XAD-2, XAD-4 (Rohm and Haas); Hitachi Gel # 3010, # 3011, and # 3019 (Hitachi Chemical Co., Ltd.) . Further, a methacrylic ester porous synthetic adsorption resin having a specific surface area, pore volume and pore radius comparable to those of the above styrene / divinylbenzene synthetic adsorption resin can be exemplified. For example, Diaion HP1MG, 2MG (Mitsubishi Chemical Corporation); Amberlite XAD-7, XAD-8i (Rohm and Haas). Such a contact treatment with the synthetic adsorption resin may employ any mode such as a batch type or a continuous treatment with a column, but generally a continuous treatment with a column filled with the synthetic adsorption resin is adopted.

  Moreover, the following method can be illustrated as a decaffeination process method by a cation exchange resin process. In the case of water extraction, the coffee extract is used as it is. In the case of a water-containing hydrophilic organic solvent extract, the content of the organic solvent is reduced to, for example, about 5% by weight or less by means of distillation or the like. Caffeine in the coffee extract can be adsorbed and removed by contact treatment with the exchange resin. Examples of the cation exchange resin include SK-116, SK-1B (above Mitsubishi Chemical Corporation); Amberlite IR-120, 200 (above Rohm and Haas). Such a contact treatment with a cation exchange resin may employ any aspect such as a batch type or a continuous treatment using a column, but generally a continuous treatment using a column filled with the resin is adopted. The conditions for the contact treatment can be appropriately selected according to the type of coffee beans, the concentration of the extract, and the like. For example, the conditions for the continuous treatment by the column are about 1 volume per cation exchange resin. An example of the condition is that 1 volume to about 50 volumes of coffee extract is passed at a liquid temperature of about 10 ° C. to about 30 ° C. and a SV of about 0.5 to about 50. The decaffeinated coffee extract thus obtained is acidified by contact treatment with a cation exchange resin and can be neutralized using a known alkaline substance. Examples of the alkaline substance include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate and the like. In addition, decaffeinated coffee that does not contain a salt produced by neutralization by bringing into contact with an anion exchange resin previously made into OH type to neutralize the liquidity of the solution instead of neutralization treatment. It can be an extract.

  The chlorogenic acid extract purified by contact treatment with acid clay and / or activated clay of the present invention can be obtained by the above-described method and further concentrated under reduced pressure or normal pressure to obtain a concentrate. . In addition, by adding a retention agent such as glycerin, propylene glycol, or ethanol during or after concentration, the state can be stabilized and the content concentration of chlorogenic acids can be adjusted. Further, the concentrated solution is used as it is, or dextrins, starches, natural gums, sugars and other excipients are added and dried by a known method to form powders, granules or any other solid form. You can also.

The purified chlorogenic acid extract thus obtained is stable and does not cause precipitation, and is stable without secondary precipitation even after storage of the extract. In addition, it is stable with no precipitation even after being added to coffee beverages or other soft drinks, and stable even after changes over time due to effects of heat sterilization, storage, light, etc. It is. Moreover, since the caffeine is reduced in the method of the present invention, it can be used with peace of mind by children and elderly people. Furthermore, the method of the present invention does not reduce chlorogenic acids and trigonelline useful for the human body. Furthermore, in the method of the present invention, since the balance of the organic acid composition is the same as that before the treatment, it is excellent in flavor. In the present invention, a useful method for producing purified chlorogenic acid having these effects can be provided by a simple method and industrially advantageous method.
Hereinafter, the present invention will be described more specifically with reference to examples.

Example 1
Fill a 5 L column with 1000 g of coffee beans crushed to a L value of 51.5 (column inner diameter 14.5 cm, height 31 cm), and feed 3700 g of soft water heated to 95 ° C. from the top of the column for 1 hour. After the placement, the extract was extracted to obtain an extract (yield 2500 g, Bx 11.5 °). After cooling the obtained coffee extract to 25 ° C., 143.8 g (50% of the solid content in terms of Bx) of Mizuka Ace No600 (Mizusawa Chemical Co., Ltd.) was added to the extract and stirred at 25 ° C. for 30 minutes. Later, no. 26 (210 mm) filter paper (Toyo Filter Paper Co., Ltd.) was suction filtered through a Nutsche pre-coated with 50 g of diatomaceous earth to obtain 2450 g of filtrate (B × 10.0 °). The filtrate was concentrated under reduced pressure using a rotary evaporator to obtain 490 g of Bx50 ° concentrate (Product 1 of the present invention).

Comparative Example 1
Fill a 5 L column with 1000 g of coffee beans crushed to a L value of 51.5 (column inner diameter 14.5 cm, height 31 cm), and feed 3700 g of soft water heated to 95 ° C. from the top of the column for 1 hour. After the placement, the extract was extracted to obtain an extract (yield 2500 g, Bx 11.5 °). The obtained coffee extract was designated as No.1. 26 (210 mm) was suction filtered through a Nutsche pre-coated with 50 g of filter paper diatomaceous earth to obtain 2450 g of filtrate (B × 11.2 °). The filtrate was concentrated under reduced pressure using a rotary evaporator to obtain 549 g of a Bx50 ° concentrate (Comparative product 1).

Comparative Example 2
Fill a 5 L column with 1000 g of coffee beans crushed to a L value of 51.5 (column inner diameter 14.5 cm, height 31 cm), and feed 7400 g of soft water heated to 95 ° C. from the top of the column for 1 hour. After the placement, the extract was extracted to obtain an extract (yield 6200 g, Bx5.2 °). After cooling the obtained coffee extract to 25 ° C., 161.2 g (50% of the solid content in terms of Bx) of Mizuka Ace No600 (Mizusawa Chemical Co., Ltd.) was added to the extract and stirred at 25 ° C. for 30 minutes. Later, no. 26 (210 mm) was suction filtered through a Nutsche pre-coated with 50 g of filter paper diatomaceous earth to obtain 6100 g of filtrate (Bx4.5 °). The filtrate was concentrated under reduced pressure using a rotary evaporator to obtain 549 g of a Bx50 ° concentrate (Comparative product 2).

Example 2
The product 1 of the present invention or the comparative product is sterilized by heating at 90 ° C. for 10 minutes and then filled into a 100 ml transparent container, and stored under two conditions of 5 ° C. dark place for 6 months and 50 ° C. dark place for 3 months. The condition was observed. The results are shown in Table 1.

  As shown in Table 1, the comparative product 1 in which the coffee bean extract was only concentrated and added as it was did not precipitate immediately after production, but started to precipitate immediately after the start of the storage test. On the other hand, the product 1 of the present invention and the comparative product 2 subjected to the acid clay were clearly less precipitated than the comparative product 1. Comparative product 2 was treated with acidic clay at a concentration of Bx5.2 ° of the extract, but comparative product 2 showed a tendency to precipitate upon storage. On the other hand, in the beverage to which the product 1 of the present invention was added, no precipitation was observed at 5 ° C. in the dark for 1 month and 50 ° C. in the dark for 3 weeks. Precipitation was slight even in months, and it was confirmed that the storage stability was good.

Example 3
Extraction in exactly the same manner as in Example 1 was repeated 10 times to obtain 25,000 g of extract (Bx11.7 °). The obtained extract was concentrated by a rotary evaporator to obtain 5800 g of a Bx50 ° concentrated solution. Dilute this concentrate to 25,000 g of Bx1 ° dilution, 5,000 g of Bx5 ° dilution, 2,500 g of Bx10 ° dilution, 1,250 g of Bx20 ° dilution, 833 g of Bx30 ° dilution, A Bx40 ° diluted solution of 625 g (equivalent to 862 g of each coffee bean) was prepared. After making 500 g of these diluted solutions or Bx50 ° concentrated solution to a temperature of 25 ° C., 125 g (50% of the solid content in terms of Bx) of Mizuka Ace No600 (Mizusawa Chemical Co., Ltd.) was added to each extract at 25 ° C. After stirring for 30 minutes, no. 26 (210 mm) was suction filtered through a Nutsche pre-coated with 50 g of filter paper diatomaceous earth to obtain a filtrate. Each filtrate was concentrated under reduced pressure using a rotary evaporator to obtain a Bx50 ° concentrate. Treated product from Bx1 ° diluted solution is Comparative product 3, Treated product from Bx5 ° diluted solution is Comparative Product 4, Treated product from Bx10 ° diluted solution is Invention Product 2, Treated product from Bx20 ° diluted solution Inventive product 3, treated product from Bx 30 ° diluted solution was treated with inventive product 4, and treated product from Bx 40 ° diluted solution was designated with inventive product 5. However, the treatment from Bx50 ° was very time consuming to filter the acid clay, the workability was very poor, and it was not efficient.
Table 2 shows analysis values of various components of the respective products.

Analytical method Chlorogenic acid analysis method:
An appropriate amount of sample (about 0.05 g) is precisely weighed into a 100 ml volumetric flask and made up to 100 ml with ion-exchanged water. 5 ml of the solution is placed in a 100 ml volumetric flask, diluted with ion-exchanged water to 100 ml, and the absorbance of the diluted solution at a wavelength of 325 nm is measured. When the absorbance measured here is A and the sampled amount is B, the amount of chlorogenic acid is calculated according to the following formula (calculating the absorption coefficient of chlorogenic acid at 325 nm as 52000).
Chlorogenic acid (g) = {A × (100 ÷ 5) × (50 ÷ B)} ÷ 52000
Analytical method for caffeine, trigonelline and organic acids: HPLC method As shown in Table 3, the yield and caffeine content are reduced by the acid clay treatment, but other components are slightly increased. Since the minutes decreased, it is thought to have increased relatively. Moreover, the composition of the organic acids did not change so much as that before the treatment, and the composition ratio was almost the same as that of the untreated one.

Example 4 (sensory evaluation)
Any one of the present invention products 2 to 5, comparative product 1, comparative product 3 or comparative product 4 was added to water by 0.2%, and sensory evaluation was performed by 10 well-trained panelists. The results of sensory evaluation are shown in Table 3.

As shown in Table 3, the comparative product 3 subjected to the acid clay treatment at Bx1 ° and the comparative product 4 performed at Bx5 ° seemed to have a taste, but the product 2 of the present invention performed at Bx10 ° to Bx40 °, All of 3, 4, and 5 were clean and clear.
Therefore, the purified chlorogenic acid of the product of the present invention can give useful effects that chlorogenic acid has without giving any taste to various beverages and foods.

Example 5
Each of the present invention products 2 to 5, comparative product 1, comparative product 3 or comparative product 4 is sterilized by heating at 90 ° C. for 10 minutes and then filled into a 100 ml transparent container, and 5 ° C. dark place for 6 months and 50 ° C. dark place for 3 months 2 It was stored under conditions, and the state of precipitation over time was observed. The results are shown in Table 4.

  As shown in Table 4, compared with Comparative Product 3 or Comparative Product 4 which was subjected to acid clay treatment at Bx1 ° or Bx5 °, the present invention products 2-5 which were performed at Bx10 °, Bx20 °, Bx30 ° and Bx40 ° Clearly had less precipitation. Therefore, it was recognized that by treating with acid clay in a state where the coffee extract was concentrated to a certain concentration or higher, it was possible to produce purified chlorogenic acid that did not cause secondary precipitation and that was refreshing in flavor.

Example 6
Filled 5 L column with 1000 g of coffee beans roasted to L value 51.5 (column inner diameter 14.5 cm, length 31 cm), and 3700 g of soft water heated to 95 ° C. was fed from the top of the column for 1 hour. After standing, the extract was extracted to obtain an extract (extracted solution yield 2500 g, B × 11.7 °). The obtained coffee extract was cooled to 20 ° C. and concentrated with a rotary evaporator to obtain a highly concentrated coffee extract of Bx 72.5 ° (yield 401.8 g, solid content 60.4%, pH 5.74, Chlorogenic acid 16.7%, caffeine 5.9%). About 35.0 g of 4N hydrochloric acid was added to the concentrated solution to adjust the pH to 4.5, and then 11.5 g of water was further added to obtain Bx 66.0 ° (total liquid amount 448.3 g, water content 45.0%). . While stirring this at room temperature, 583.0 g of primary 95% ethanol (Japan alcohol sales, ethanol content 92 W / W%) was added dropwise over 30 minutes, and stirring was continued for further 60 minutes (final water / ethanol = 29.2 / 70.8). Thereafter, the insoluble material was suction filtered with a filter paper (No. 2, 150 mm) to obtain 935.2 g of a filtrate. The filtrate was concentrated with a rotary evaporator to obtain 218.6 g of concentrate (Bx 78.0 °, solid content 65%, chlorogenic acid 26.8%, caffeine 5.4%). Water was added to the concentrate to dilute to Bx20 ° (Bx20 ° diluted solution amount 852.5 g), Mizusuka Ace No600 (Mizusawa Chemical Co., Ltd.) was added 85.2 g (50% of the solid content in terms of Bx), and 25 ° C. After stirring for 30 minutes, no. 26 (210 mm) was suction filtered with a Nutsche pre-coated with 50 g of filter paper diatomaceous earth to obtain 806.1 g of filtrate (B × 17.4 °). The filtrate was concentrated under reduced pressure using a rotary evaporator to obtain 350.6 g of a Bx50 ° concentrate (Product 6 of the present invention: solid content 40.0%, chlorogenic acid 15.7%, caffeine 2.6%).

Example 7
585 g of the present invention product 3 (Bx50 °) was prepared (equivalent to 1000 g of coffee beans) and concentrated with a rotary evaporator to obtain a highly concentrated coffee extract of Bx72.5 ° (yield 403.4 g, solid content 60.4). %, PH 5.74, chlorogenic acid 16.6%, caffeine 5.9%). About 29.9 g of 4N hydrochloric acid was added to the concentrated liquid to adjust the pH to 4.5, and then 6.1 g of water was further added to obtain Bx 66.0 ° (total liquid amount 381.1 g, water content 45.0%). . While stirring this at room temperature, 571.7 g of primary 95% ethanol (Japanese alcohol sales, ethanol content 92 W / W%) was added dropwise over 30 minutes, and stirring was continued for further 60 minutes (final water / ethanol) = 29.2 / 70.8). Thereafter, the insoluble material was suction filtered with a filter paper (No. 2, 150 mm) to obtain 915.4 g of a filtrate. The filtrate was concentrated with a rotary evaporator to obtain 407.6 g of Bx 50 ° concentrate (Product 7 of the present invention: solid content 39.8%, chlorogenic acid 14.4%, caffeine 2.8%).

Example 8
Filled 5 L column with 1000 g of coffee beans roasted to L value 51.5 (column inner diameter 14.5 cm, length 31 cm), and 3700 g of soft water heated to 95 ° C. was fed from the top of the column for 1 hour. After standing, the extract was extracted to obtain an extract (extracted solution yield 2500 g, B × 11.7 °). The obtained coffee extract was cooled to 20 ° C. 26 (210 mm) was suction filtered with a Nutsche pre-coated with 50 g of filter paper diatomaceous earth to obtain 2450 g of filtrate. To this extract, 58 g of a 10% aqueous sodium hydroxide solution was added to adjust the pH to 10. This solution was passed through a column packed with 600 ml of a synthetic adsorption resin (SP-70) at SV = 2.5 to adsorb caffeine. In order to make the obtained passing solution acidic, the solution was passed through a column packed with 200 ml of cation exchange resin (SK-116) (sodium ions were also removed), further pushed with water, and 2750 g of decaffeinated coffee extract. (Bx 7.7 °, pH 4.2, chlorogenic acid 2.28%, caffeine not detected). Subsequently, the mixture was concentrated on a rotary evaporator to obtain 1058 g of a Bx20 ° concentrated solution (pH 4.4, chlorogenic acid 5.93%, caffeine not detected). Then, 105.8 g (50% of the solid content in terms of Bx) of Mizuka Ace No. 600 (Mizusawa Chemical Industry Co., Ltd.) was added and stirred at 25 ° C. for 30 minutes. 26 (210 mm) was suction filtered with a Nutsche pre-coated with 50 g of filter paper diatomaceous earth to obtain 1015 g of filtrate (B × 17.4 °). The filtrate was concentrated under reduced pressure using a rotary evaporator to obtain 353.2 g of Bx50 ° concentrate (present product 8: solid content 39.6%, chlorogenic acid 15.2%, caffeine not detected, pH 4.5). It was.

Example 9
In Example 8, the same operation as in Example 8 was performed except that the cation exchange resin treatment was not performed, and 362.4 g of Bx50 ° concentrate (present product 9: solid content 40.0%, chlorogenic acid 14 9%, no caffeine detected, pH 10.2).

Example 10
Filled 5 L column with 1000 g of coffee beans roasted to L value 51.5 (column inner diameter 14.5 cm, length 31 cm), and 3700 g of soft water heated to 95 ° C. was fed from the top of the column for 1 hour. After standing, the extract was extracted to obtain an extract (extracted solution yield 2500 g, B × 11.7 °). The obtained coffee extract was cooled to 20 ° C. 26 (210 mm) was suction filtered with a Nutsche pre-coated with 50 g of filter paper diatomaceous earth to obtain 2450 g of filtrate. This extract was passed through a column packed with 1500 ml of cation exchange resin (SK-116) to remove caffeine, and further pushed with water to give 2855 g of decaffeinated coffee extract (Bx 7.5 °, pH 2.2, chlorogen). Acid 2.35%, no caffeine detected). Subsequently, the mixture was concentrated on a rotary evaporator to obtain 1070 g of coffee extract of Bx20 ° (pH 2.2, chlorogenic acid 6.1%, caffeine not detected). After adding 103.5 g (50% of the solid content in terms of Bx) of Mizuka Ace No.600 (Mizusawa Chemical Industry Co., Ltd.) to the concentrate and stirring at 25 ° C. for 30 minutes, 26 (210 mm) was suction filtered with a Nutsche pre-coated with 50 g of filter paper diatomaceous earth to obtain 1020 g of filtrate (B × 17.4 °). The filtrate was concentrated under reduced pressure using a rotary evaporator to obtain 358.6 g of a Bx50 ° concentrate (present product 10: solid content 40.0%, chlorogenic acid 15.4%, caffeine not detected).

Example 11
In Example 10, exactly the same as Example 9 except that the decaffeinated coffee extract (pH 2.2) was adjusted to pH 10.0 with 10% aqueous sodium hydroxide solution with cation exchange resin (SK-116). Thus, 370.5 g of a Bx50 ° concentrate (Product 11 of the present invention: solid content 40.0%, chlorogenic acid 15.1%, caffeine not detected, pH 10.6) was obtained.

  Table 5 shows the solid content, chlorogenic acid, and caffeine analysis values of Products 3 and 6-11 of the present invention.

  As shown in Table 5, the coffee extract was concentrated at a high concentration, extracted with an aqueous ethanol solution under acidic conditions, concentrated to Bx20 °, and treated with acid clay, and the product 6 of the present invention and the coffee extract were Bx20 °. The product 7 of the present invention, which is concentrated to a high concentration and extracted with an aqueous ethanol solution under acidic conditions, has a higher chlorogenic acid content than the product 3 of the present invention. The caffeine content was low and chlorogenic acid was purified. In addition, the coffee bean extract was treated with a synthetic adsorption resin under alkaline conditions, decaffeinated, concentrated to Bx20 °, the acid clay-treated product 8 of the present invention and the coffee bean extract were treated with a cation exchange resin, The product 9 of the present invention, which was caffeinated, concentrated to 20 ° C., and treated with acid clay, had a higher chlorogenic acid content than the product 3 of the present invention and contained no caffeine at all. An acid was obtained. In addition, after the decaffeination treatment by the alkaline synthetic adsorbent treatment, the product 9 of the present invention which was subjected to the acid clay treatment without alkaline pH adjustment was subjected to the pH adjustment and was subjected to the acid clay clay treatment. The product 8 and the amount of components were almost the same. The product 9 of the present invention in which the decaffeinated liquid (pH 2.2) treated with the cation exchange resin was treated with the acid clay, and the decaffeinated liquid treated with the cation exchange resin were adjusted to pH 10 with an aqueous sodium hydroxide solution. The amount of components was almost the same for the product 11 of the present invention that had been treated with acid clay.

Example 12
The present invention product 3 or any one of the present product products 6 to 11 was added to water by 0.2%, and sensory evaluation was performed by 10 well-trained panelists. The results of sensory evaluation are shown in Table 6.

表６に示したとおり、本発明品３、本発明品６〜１１はいずれも雑味が無く、すっきりしていた。したがって、本発明品の精製クロロゲン酸は、さまざまな飲料、食品に雑味を与えずに、クロロゲン酸の持つ有用な効果を与えるものと考えられる。

As shown in Table 6, the product 3 of the present invention and the products 6 to 11 of the present invention were both clean and clear. Therefore, the purified chlorogenic acid of the product of the present invention is considered to give a useful effect of chlorogenic acid without giving any taste to various beverages and foods.

Example 13
Each of Invention Product 3 or Invention Products 6 to 11 is sterilized by heating at 90 ° C. for 10 minutes, and then filled into a 100 ml transparent container, stored under 2 conditions of 5 ° C. dark place for 6 months and 50 ° C. dark place for 3 months. The state of general precipitation was observed. The results are shown in Table 7.

  As shown in Table 7, the product 3 of the present invention, which was obtained by concentrating the coffee extract to Bx20 ° and performing only the acid clay treatment, caused slight precipitation upon storage at 50 ° C., 1 month or 5 ° C. for 3 months. However, the acid clay is concentrated to a concentration of coffee extract, extracted with an aqueous ethanol solution under acidic conditions, and then concentrated to Bx20 °, and the product 6 of the present invention treated with acid clay, the coffee extract to Bx20 °. Concentrated, treated with acid clay, concentrated at high concentration, and extracted with ethanol aqueous solution under acidic conditions. The product 7 of the present invention, coffee bean extract was treated with synthetic adsorption resin under alkaline conditions, and decaffeinated. Invented product 8 and coffee beans extract treated with acid clay, concentrated to Bx20 °, and treated with cation exchange resin, decaffeinated, concentrated to Bx20 ° and treated with acid clay, Even when stored, no secondary precipitation occurred and it was confirmed that the sample was very stable.

  On the other hand, the present product 9 and the present product 11 which were subjected to acidic clay treatment under alkaline conditions of pH 10 caused secondary precipitation upon storage.

Claims (7)

  A purified chlorogenic acid characterized in that the raw or roasted coffee bean extract is concentrated to a refractive sugar content (20 ° C.) of Bx8 ° to Bx60 ° as a solid content, and then contacted with acid clay and / or activated clay. Production method.   The method for producing purified chlorogenic acid according to claim 1, wherein the contact treatment of the raw or roasted coffee bean extract concentrate with acidic clay and / or activated clay is performed under acidic conditions of pH 2-7. .   The method for producing purified chlorogenic acid according to claim 1 or 2, wherein substantially no secondary precipitation occurs.   The raw or roasted coffee bean extract is extracted with an aqueous ethanol solution or ethanol under acidic conditions after concentration at a high concentration. A method for producing the purified chlorogenic acid according to Item.   The purified chlorogenic acid obtained by the high-concentration concentration of the purified chlorogenic acid obtained by the method according to any one of claims 1 to 3, and then extracted with an aqueous ethanol solution or ethanol under acidic conditions. Manufacturing method.   The purified chlorogenic acid according to any one of claims 1 to 3, wherein the raw or roasted coffee bean extract is treated with a synthetic adsorption resin under neutral to alkaline conditions. Manufacturing method.   4. The method for producing purified chlorogenic acid according to any one of claims 1 to 3, wherein the raw or roasted coffee bean extract is treated with a cation exchange resin.