JP6348392B2 - Method for producing purified chlorogenic acid-containing composition - Google Patents

Description

  The present invention relates to a method for producing a purified chlorogenic acid-containing composition.

  It has been reported that chlorogenic acids have an excellent blood pressure lowering effect, and application to supplements and foods and drinks is expected. Coffee beans can be mentioned as a material containing a large amount of chlorogenic acids, and caffeine is contained in the coffee beans. For this reason, methods for selectively removing caffeine from chlorogenic acid-containing compositions containing caffeine have been studied.

  For example, a method in which an aqueous solvent extract of green coffee beans is brought into contact with a strongly acidic cation exchange resin (Patent Document 1), and after adjusting the pH of the coffee bean extract to 0.5 to 4.0, solid-liquid separation is performed. A method is known in which a liquid is brought into contact with a synthetic adsorbent, and an alkaline aqueous solution is passed through to elute chlorogenic acids (Patent Document 2). In addition, a method is also proposed in which a chlorogenic acid-containing composition is brought into contact with a cation exchange resin, then the treatment liquid is brought into contact with an anion exchange resin, and then the desorption liquid is brought into contact with the anion exchange resin (Patent Document). 3)

Japanese Patent Laid-Open No. 4-145048 JP 2008-94758 A JP 2013-27388 A

  The subject of this invention is providing the manufacturing method of the refinement | purification chlorogenic acid containing composition which can reduce caffeine efficiently, without impairing chlorogenic acids.

  Therefore, as a result of various investigations in view of the above problems, the present inventors brought the raw material chlorogenic acid-containing composition into contact with the cation exchange resin, and then brought the treatment liquid into contact with the anion exchange resin, and then a specific temperature. Purified chlorogenic acid-containing composition in which caffeine is further reduced without damaging chlorogenic acids by washing the anion exchange resin with the above water and then bringing the specific anion exchange resin into contact with the anion exchange resin. Was found to be obtained in good yield.

That is, the present invention includes a step A in which a raw material chlorogenic acid-containing composition is contacted with a cation exchange resin;
Contacting the liquid obtained in step A with a weakly basic anion exchange resin; and
Step C in which water at 35 ° C. or higher is brought into contact with the weakly basic anion exchange resin after Step B;
Step D in which an acidic aqueous solution or an alkaline aqueous solution is brought into contact with the weakly basic anion exchange resin after Step C
A method for producing a purified chlorogenic acid-containing composition is provided.

  According to the present invention, a purified chlorogenic acid-containing composition in which caffeine is further reduced can be produced by a simple operation without impairing chlorogenic acids.

  The method for producing a purified chlorogenic acid-containing composition of the present invention comprises Step A, Step B, Step C and Step D. Hereinafter, each step will be described in detail.

(Process A)
Step A according to the present invention is a step of bringing the raw material chlorogenic acid-containing composition into contact with a cation exchange resin.

  Although it will not specifically limit as a raw material chlorogenic acid containing composition if chlorogenic acids are contained, The extract of the plant containing chlorogenic acids can be used. Examples of such plant extracts include sunflower seeds, apple immature fruits, coffee beans, Simon leaves, pine cones, pine seed shells, sugar cane, southern leaves, burdock, eggplant skin, Examples include those extracted from ume fruit, dandelion, and vines. In addition, an extraction method and extraction conditions are not specifically limited, A well-known method and conditions are employable.

  Among these, as the raw material chlorogenic acid-containing composition, an extract of coffee beans is preferable from the viewpoint of chlorogenic acid content and the like. Further, the coffee beans used for extraction may be raw coffee beans or roasted coffee beans, and these can be used in combination. However, from the viewpoint of the content of chlorogenic acids, etc., raw coffee beans and shallow roasted coffee beans can be used. One or more selected from beans are preferred, and green coffee beans are more preferred. The L value of the lightly roasted coffee beans is preferably 27 or more, more preferably 29 or more, and more preferably less than 62, more preferably 60 or less, and even more preferably 55 or less from the viewpoint of the content of chlorogenic acids. preferable. The range of the L value of the shallow roasted coffee beans is preferably 27 or more and less than 62, more preferably 29 to 60, and still more preferably 29 to 55. Here, “L value” in this specification is a value obtained by measuring the brightness of roasted coffee beans with a color difference meter, with black as L value 0 and white as L value 100.

  The type of coffee tree may be any of Arabica, Robusta, Revelica and Arabsta. Moreover, although the production region of coffee beans is not particularly limited, examples include Brazil, Colombia, Tanzania, Mocha, Kilimanjaro, Mandelin, Blue Mountain, Guatemala, Vietnam, Indonesia, and the like. The extraction method and extraction conditions are not particularly limited, but are described in, for example, JP-A-58-138347, JP-A-59-51763, JP-A-62-111671, JP-A-5-236918, and the like. This method can be adopted. In addition, it is also possible to use ethanol or a mixed solvent of ethanol and water instead of water as the extraction solvent, and the ethanol concentration in the mixed solvent can be appropriately selected.

  Moreover, you may use a commercially available chlorogenic acid containing formulation as a raw material chlorogenic acid containing composition, for example, flavor holder RC (made by Hasegawa Incense Co., Ltd.) is mentioned. In addition, as a form of raw material chlorogenic acid containing composition, various things, such as a liquid, a slurry, a semi-solid, a solid, are mentioned, for example.

  It is preferable that the raw material chlorogenic acid-containing composition to be brought into contact with the cation exchange resin is in the form of an aqueous solution. The raw material chlorogenic acid-containing composition in the form of an aqueous solution may be used, for example, by diluting or concentrating, if necessary, an extract extracted with water from a plant containing chlorogenic acids. Moreover, you may use the liquid which melt | dissolved the dry substance which removed the extraction solvent chosen from water and ethanol from the obtained extract again in water.

  The chlorogenic acid content in the aqueous solution in which the raw material chlorogenic acid-containing composition is dissolved can be appropriately selected, but from the viewpoint of purification efficiency, 0.1% by mass or more is preferable, 0.5% by mass or more is more preferable, 1 mass% or more is still more preferable, 20 mass% or less is preferable, 10 mass% or less is more preferable, and 5 mass% or less is still more preferable. The range of the content of such chlorogenic acids is preferably 0.1 to 20% by mass, more preferably 0.5 to 20% by mass, still more preferably 0.5 to 10% by mass, and still more preferably 1 to 5%. % By mass. Here, “chlorogenic acids” in the present specification means 3-caffeoylquinic acid, 4-caffeoylquinic acid and monocaffeoylquinic acid of 5-caffeoylquinic acid, 3-ferlaquinic acid and 4-ferlaquina. Acid and 5-ferlaquinic acid monoferlaquinic acid and 3,4-dicaffeoylquinic acid, 3,5-dicaffeoylquinic acid and 4,5-dicaffeoylquinic acid dicaffeoylquinic acid In the present invention, at least one of the above nine types may be contained. The content of chlorogenic acids is defined based on the total amount of the nine types.

  As the cation exchange resin, both strong acid cation exchange resins and weak acid cation exchange resins can be used. Examples of the resin matrix of the cation exchange resin include a styrene resin, an acrylic acid resin, and a methacrylic acid resin. Of these, styrene resins are preferable, and styrene-divinylbenzene copolymers are more preferable. Examples of the resin structure of the cation exchange resin include a gel type and a porous type. As used herein, the term “gel type” refers to those having only micropores that are pores generated by swelling, and the “porous type” refers to physical fines that do not disappear even in a dry state in addition to micropores. It has a macropore which is a hole. Examples of the functional group of the cation exchange resin include a sulfonic acid group, a carboxyl group, and a phosphoric acid group. Among them, a sulfonic acid group is preferable.

  Commercially available products may be used as such cation exchange resins. Examples of strongly acidic cation exchange resins include Diaion SK1B, SK1BH, SK102, SK116, PK208, PK212 (Mitsubishi Chemical Corporation), Amberlite. 200CT, IR118, IR120B, IR124 (manufactured by Dow Chemical Company) and the like can be mentioned. Examples of the weakly acidic cation exchange resin include Diaion WK10, WK40L (manufactured by Mitsubishi Chemical Corporation), Amberlite IRC76 (manufactured by Dow Chemical Company), and the like.

  Especially, as a cation exchange resin used at this process, a strong acidic cation exchange resin is preferable and the H-type cation exchange resin is still more preferable from the point of removal of a foreign material. Examples of the H-type cation exchange resin include a cation exchange resin obtained by substituting an Na-type cation exchange resin with an H-type, and examples of commercially available products include Diaion SK1BH. The cation exchange resin is preferably washed with water in advance to remove the cation exchange resin raw material monomer and impurities in the raw material monomer.

  The contact method with the cation exchange resin may be a batch method or a column method, but the column method is preferred from the viewpoint of purification efficiency. In the case of the column type, an aqueous solution in which the raw material chlorogenic acid-containing composition is dissolved may be passed through a column filled with a cation exchange resin.

In the case of contacting by a column type, the liquid flow rate of the raw material chlorogenic acid-containing composition can be appropriately selected, but the space velocity (SV) is preferably 0.1 [hr ⁻¹ ] or more, 0.2 [Hr ^-1 ] or more is more preferable, 0.5 [hr ^-1 ] or more is more preferable, 50 [hr ^-1 ] or less is preferable, 10 [hr ^-1 ] or less is more preferable, and 8 [hr ^-1 ] is more preferable. The following is more preferable, and 5 [hr ⁻¹ ] or less is more preferable. The scope of such a space velocity (SV), preferably 0.1~50 [hr ^-1], and more preferably 0.1~10 [hr ^-1], and more preferably 0.2 to 8 [hr ^-1 ], More preferably, it is 0.5-5 [hr < ^-1 >].
In addition, the flow rate of the raw material chlorogenic acid-containing composition can be appropriately selected, but the flow rate multiple (BV) with respect to the filling capacity of the cation exchange resin is preferably 0.5 (mL / mL) or more. more preferably 5 (mL / mL) or more, more preferably 10 (mL / mL) or more, and more preferably 100 (mL / mL) or less, and 80 (mL / mL) or less. Is more preferable, 60 (mL / mL) or less is still more preferable, and 40 (mL / mL) or less is still more preferable. As a range of such liquid passing multiples, preferably 0.5 to 100 (mL / mL), more preferably 1 to 80 (mL / mL), still more preferably 5 to 60 (mL / mL), and still more preferably. 10 to 40 (mL / mL).

  Moreover, when making it contact in a batch type, the usage-amount of the raw material chlorogenic acid containing composition with respect to 1 mass part of cation exchange resins, as a solid content mass of a raw material chlorogenic acid containing composition, Preferably it is 0.021-4.3 mass. Parts, more preferably 0.042 to 3.5 parts by mass, still more preferably 0.21 to 2.6 parts by mass, and still more preferably 0.42 to 1.8 parts by mass.

  The pH (20 ° C.) of the liquid obtained in step A is preferably less than 4 and more preferably 3.5 or less from the viewpoints of caffeine reduction, the yield of the purified chlorogenic acid-containing composition, and the purity of chlorogenic acids. 3 or less is more preferable, 0.5 or more is preferable, and 1 or more is more preferable. The pH range of the liquid is preferably 0.5 or more and less than 4, more preferably 0.5 or more and 3.5 or less, and still more preferably 1 or more and 3 or less. Here, in the present specification, the “liquid obtained by step A” is a liquid after the raw material chlorogenic acid-containing composition is brought into contact with a cation exchange resin in the case of a batch type, and in the case of a column type. This is a liquid obtained by passing a raw material chlorogenic acid-containing composition through a column filled with a cation exchange resin.

(Process B)
Step B according to the present invention is a step of bringing the liquid obtained in Step A into contact with a weakly basic anion exchange resin. Thereby, the purity and yield of chlorogenic acids can be increased.

Examples of the resin base of the weakly basic anion exchange resin include styrene resins, acrylic resins, and methacrylic resins, and among them, acrylic resins are preferable. Examples of the resin structure of the weakly basic anion exchange resin include a gel type and a porous type. Examples of the functional group of the weakly basic anion exchange resin include a primary amino group, a secondary amino group, and a tertiary amino group. Examples of the primary amino group include a methylamino group. Examples of the secondary amino group include a dimethylamino group. Examples of the tertiary amino group include a dimethylaminomethyl group.
Commercially available products may be used as such a weakly basic anion exchange resin. For example, Diaion WA10, WA20, WA21J, WA30 (manufactured by Mitsubishi Chemical Corporation), Amberlite IRA67, IRA743, IRA96SB, XE583, XT6050RF ( Dow Chemical Co.). The weakly basic anion exchange resin is preferably washed with water in advance to remove the raw material monomer of the adsorbent and impurities in the raw material monomer.

  The contact method with the weakly basic anion exchange resin may be a batch method or a column method, but the column method is preferable from the viewpoint of purification efficiency. In the case of the column type, the liquid obtained in step A may be passed through a column filled with a weakly basic anion exchange resin.

  Moreover, when performing by a column type, the column filled with the cation exchange resin and the column filled with the weak basic anion exchange resin may be connected, and the process A and the process B may be performed continuously.

When the column method is used, the flow rate of the liquid obtained in step A is preferably 0.1 [hr ⁻¹ ] or more, more preferably 0.2 [hr ⁻¹ ] or more as the space velocity (SV). 0.5 [hr ⁻¹ ], more preferably 50 [hr ⁻¹ ] or less, more preferably 10 [hr ⁻¹ ] or less, further preferably 8 [hr ⁻¹ ] or less, 5 [hr ^{− 1} ] The following is more preferable. The scope of such a space velocity (SV), preferably 0.1~50 [hr ^-1], and more preferably 0.1~10 [hr ^-1], and more preferably 0.2 to 8 [hr ^-1 ], More preferably, it is 0.5-5 [hr < ^-1 >].
Further, the flow rate of the liquid obtained in the step A is preferably 0.5 (mL / mL) or more as a flow rate multiple (BV) with respect to the filling capacity of the weakly basic anion exchange resin, and preferably 1 (mL / mL). mL (mL / mL) or more, more preferably 5 (mL / mL) or more, still more preferably 10 (mL / mL) or more, and preferably 100 (mL / mL) or less, more preferably 60 (mL / mL) or less. Preferably, 45 (mL / mL) or less is more preferable, and 30 (mL / mL) or less is still more preferable. As a range of such liquid passing multiples, preferably 0.5 to 100 (mL / mL), more preferably 1 to 60 (mL / mL), still more preferably 5 to 45 (mL / mL), and still more preferably. 10-30 (mL / mL).

  Moreover, when making it contact by a batch type, although the usage-amount of the liquid obtained by the process A with respect to weak basic anion exchange resin can be selected suitably, for example, 1 mass part of weak basic anion exchange resin The amount of the liquid obtained by the process A is preferably 0.82 to 160 parts by mass, more preferably 1.6 to 98 parts by mass, still more preferably 8.2 to 74 parts by mass, and still more preferably 16 -50 mass parts.

(Process C)
Step C according to the present invention is a step of bringing water at 35 ° C. or higher into contact with the weakly basic anion exchange resin after Step B. By washing the weakly basic anion exchange resin with water of 35 ° C. or higher, caffeine can be further reduced as compared with the case of not washing with water or washing with water of about 25 ° C. .

As water used for washing, for example, tap water, distilled water, ion-exchanged water, natural water and the like can be appropriately selected.
The temperature of the water is 35 ° C or higher, preferably 40 ° C or higher, more preferably 45 ° C or higher, still more preferably 55 ° C or higher, still more preferably 65 ° C or higher, even more preferably 70 ° C or higher, and 100 ° C. The following is preferable, 99 ° C. or lower is more preferable, 98 ° C. or lower is further preferable, and 97 ° C. or lower is still more preferable. The temperature range of such water is preferably 40 to 100 ° C, more preferably 45 to 100 ° C, still more preferably 55 to 99 ° C, still more preferably 65 to 98 ° C, and even more preferably 70 to 97 ° C. is there.

When Step C is performed by a column system, the water flow rate is preferably 0.5 [hr ⁻¹ ] or more, more preferably 1 [hr ⁻¹ ] or more, as the space velocity (SV), 2 [hr]. ^-1 ] is more preferred, and 50 [hr ^-1 ] or less is preferred, 30 [hr ^-1 ] or less is more preferred, 20 [hr ^-1 ] or less is more preferred, and 10 [hr ^-1 ] or less is even more preferred. preferable. The range of the space velocity (SV) is preferably 0.5 to 50 [hr ⁻¹ ], more preferably 1 to 30 [hr ⁻¹ ], still more preferably 2 to 20 [hr ⁻¹ ], and still more. Preferably it is 2-10 [hr < ^-1 >].
In addition, the water flow rate is preferably 0.5 (mL / mL) or more, more preferably 1 (mL / mL) or more, as the flow rate (BV) with respect to the filling capacity of the weakly basic anion exchange resin. 5 (mL / mL) or more is more preferable, 10 (mL / mL) or more is more preferable, 100 (mL / mL) or less is preferable, 60 (mL / mL) or less is more preferable, 45 (mL / mL) mL) or less, more preferably 30 (mL / mL) or less. As a range of such liquid passing multiples, preferably 0.5 to 100 (mL / mL), more preferably 1 to 60 (mL / mL), still more preferably 5 to 45 (mL / mL), and still more preferably. 10-30 (mL / mL).

  In the case of washing with a batch method, the amount of water used can be appropriately selected. The amount of water used is preferably 0.82 to 160 parts by mass with respect to 1 part by mass of the weakly basic anion exchange resin. More preferably, it is 1.6-98 mass parts, More preferably, it is 8.2-74 mass parts, More preferably, it is 16-50 mass parts.

(Process D)
The process D according to the present invention is a process in which the weakly basic anion exchange resin after the process C is brought into contact with an acid aqueous solution or an alkali aqueous solution. By the process D, the purified chlorogenic acid-containing composition of the present invention can be obtained as a detachment liquid containing chlorogenic acids.

As the acid aqueous solution used in this step, one prepared by dissolving an acid in water can be appropriately used. The acid may be an organic acid or an inorganic acid, or a salt thereof. Examples of the salt include alkali metal salts, and specific examples thereof include potassium salts and sodium salts. One or more acids can be selected as appropriate, and the water used when preparing the acidic aqueous solution is, for example, tap water, distilled water, ion-exchanged water, natural water, etc. can do.
The organic acid may be a monobasic acid or a polybasic acid, such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, oxalic acid, malonic acid, fumaric acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, Glutamic acid, aspartic acid, glycolic acid, malic acid, pyruvic acid, tartaric acid, citric acid, lactic acid, succinic acid, maleic acid, glutaric acid, kojic acid, dipicolinic acid, aconitic acid, levulinic acid, hydroxyacrylic acid, α-oxybutyric acid Glyceric acid, tartronic acid, salicylic acid, gallic acid, tropic acid, ascorbic acid, gluconic acid and the like. Examples of inorganic acids include hydrochloric acid, phosphoric acid, sulfuric acid, sulfurous acid, sulfamic acid, and the like. Among these, hydrochloric acid is preferable as the acid from the viewpoints of ease of pH adjustment, purity and yield of chlorogenic acids, use in foods, and the like.

The concentration of the acid aqueous solution is preferably 0.5% by mass or more, more preferably 1% by mass or more, and preferably 15% by mass or less, more preferably 10% by mass or less, from the viewpoints of purity and yield of chlorogenic acids. 5 mass% or less is still more preferable. The concentration range of the acid aqueous solution is preferably 0.5 to 15% by mass, more preferably 1 to 10% by mass, and further preferably 1 to 5% by mass.
The pH (20 ° C.) of the aqueous acid solution is preferably strongly acidic, more specifically, preferably 4 or less, more preferably 3 or less, and preferably 0.5 or more. The pH range is preferably 0.5-4, more preferably 0.5-3.

  Moreover, the aqueous alkali solution used for this process can use suitably what prepared by melt | dissolving an alkali in water. Examples of the alkali include hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide, hydroxides of alkaline earth metals such as magnesium hydroxide, calcium hydroxide and barium hydroxide, sodium carbonate and potassium carbonate. Alkali metal carbonates, Magnesium carbonate, Calcium carbonate, Barium carbonate and other alkaline earth metal carbonates, Sodium bicarbonate, Potassium bicarbonate alkali metal bicarbonates, Magnesium bicarbonate, Calcium bicarbonate, Carbonate Examples include alkaline earth metal hydrogen carbonates such as barium hydrogen, ammonium carbonate, ammonium hydrogen carbonate, ammonia, tetraalkylammonium hydroxide, and hydrazine. In addition, an alkali can be used 1 type or in combination of 2 or more types. Among these, alkali is preferably an alkali metal hydroxide, more preferably sodium hydroxide, from the viewpoints of ease of pH adjustment, purity and yield of chlorogenic acids. In addition, the water used when preparing alkaline aqueous solution can select suitably tap water, distilled water, ion-exchange water, natural water etc., for example.

The concentration of the alkaline aqueous solution is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and preferably 5% by mass or less, and more preferably 3% by mass or less, from the viewpoints of purity and yield of chlorogenic acids. preferable. The concentration range of the alkaline aqueous solution is preferably 0.1 to 5% by mass, and more preferably 0.2 to 3% by mass.
The pH (20 ° C.) of the alkaline aqueous solution is preferably 10 or more, more preferably 11 or more, and preferably 13.5 or less, more preferably 13 or less. The pH range is preferably 10 to 13.5, and more preferably 11 to 13.

When Step D is performed by a column system, the flow rate of the aqueous acid solution or aqueous alkali solution is preferably 0.5 [hr ⁻¹ ] or more, more preferably 1 [hr ⁻¹ ] or more, as the space velocity (SV). 2 [hr ^-1 ] is more preferred, and 50 [hr ^-1 ] or less is preferred, 30 [hr ^-1 ] or less is more preferred, 20 [hr ^-1 ] or less is more preferred, and 10 [hr ^-1 ] is preferred. The following is even more preferable. The range of the space velocity (SV) is preferably 0.5 to 50 [hr ⁻¹ ], more preferably 1 to 30 [hr ⁻¹ ], still more preferably 2 to 20 [hr ⁻¹ ], and still more. Preferably it is 2-10 [hr < ^-1 >].
In addition, the passing amount of the aqueous acid solution or aqueous alkali solution is preferably 0.5 (mL / mL) or more, more preferably 1 (mL / mL) or more, as the passing ratio (BV) to the weakly basic anion exchange resin. Preferably, 5 (mL / mL) or more is more preferable, 10 (mL / mL) or more is more preferable, 100 (mL / mL) or less is preferable, 70 (mL / mL) or less is more preferable, 50 (mL / ML) or less, more preferably 40 (mL / mL) or less. As a range of such a flow rate multiple, it becomes like this. Preferably it is 0.5-100 (mL / mL), More preferably, it is 1-70 (mL / mL), More preferably, it is 5-50 (mL / mL), More preferably 10 to 40 (mL / mL).

  Moreover, when making it contact in a batch type, the usage-amount of the acid aqueous solution or alkali aqueous solution with respect to 1 mass part of weak basic cation exchange resins becomes like this. Preferably it is 0.82-160 mass part, More preferably, it is 1.6-110. It is a mass part, More preferably, it is 8.2-82 mass part, More preferably, it is 16-65 mass part.

After Step D, the pH of the obtained purified chlorogenic acid-containing composition may be adjusted from the viewpoint of the stability of the purified chlorogenic acid-containing composition. As a pH adjustment method, for example,
1) Adjustment with acid or alkali,
2) Removal of alkali metal ions or acid by electrodialysis,
3) Removal of alkali metal ions by cation exchange resin
4) The acid can be distilled off by concentration under reduced pressure. Among these, when an alkaline aqueous solution is used as the desorbing liquid in Step D, it is preferable to adjust with a cation exchange resin from the simplicity of the process. As the cation exchange resin, the same cation exchange resin as in step A can be used. On the other hand, when an acidic aqueous solution is used as the desorbing liquid in the step D, it is preferable to distill off the acid by concentration under reduced pressure for the convenience of the process. The pH (20 ° C.) of the purified chlorogenic acid-containing composition after pH adjustment is preferably 2 or more, preferably 7 or less, more preferably 5 or less, and still more preferably 4 or less. The pH range is preferably 2 to 7, more preferably 2 to 5, and still more preferably 2 to 4.

The purified chlorogenic acid-containing composition obtained by the production method of the present invention can have the following characteristics (i) to (v).
(I) The purified chlorogenic acid-containing composition is based on the raw material chlorogenic acid-containing composition, and the yield of chlorogenic acids is preferably 80% by mass or more, more preferably 85% by mass or more, and still more preferably 90% by mass or more. Can be recovered.
(Ii) In the purified chlorogenic acid-containing composition, the purity of the chlorogenic acids in the purified chlorogenic acid-containing composition is preferably 60% by mass or more, more preferably 65% by mass or more, and further preferably 70% by mass or more. .
(Iii) In the purified chlorogenic acid-containing composition, the content of caffeine is preferably 1.8% by mass or less, more preferably 1.5% by mass or less, in the solid content of the purified chlorogenic acid-containing composition. More preferably, it is 1.2 mass% or less. The content of caffeine may be 0% by mass in the solid content of the purified chlorogenic acid-containing composition, but is preferably 0.01% by mass or more from the viewpoint of production efficiency.
(Iv) In the purified chlorogenic acid-containing composition, the content of chlorogenic acid is preferably 60% by mass or more, more preferably 65% by mass or more, and still more preferably 70% in the solid content of the purified chlorogenic acid-containing composition. The mass ratio of caffeine / chlorogenic acids in the composition containing (v) purified chlorogenic acids that is at least% by mass is preferably 0.03 or less, more preferably 0.025 or less, still more preferably 0.02 or less. . The mass ratio of caffeine / chlorogenic acids may be 0, but is preferably 0.0001 or more from the viewpoint of production efficiency.

1. Analysis of chlorogenic acids and caffeine (analytical instrument)
HPLC (manufactured by Hitachi, Ltd.) was used. The model numbers of the constituent units of the apparatus are as follows.
・ Liquid feeding unit (built-in degasser): L-2130
・ Autosampler (with cooler): L-2200
-Column oven: L-2300
Separation column: Cadenza CD-C18, Size: 4.6 mm i. d. × 150mm, 3μm (Intact Corporation)
Detector (ultraviolet visible absorption photometer): L-2420

(Analysis conditions)
Sample injection volume: 10 μL
・ Flow rate: 1.0 mL / min
-UV absorption photometer detection wavelength: 325nm (chlorogenic acids), 270nm (caffeine)
Eluent A: 5% acetonitrile containing 0.05 mol / L acetic acid, 0.01 mol / L sodium acetate, and 0.1 mmol / L HEDPO (1-hydroxyethane-1,1-diphosphonic acid) Eluent B : Acetonitrile

Concentration gradient condition Time Eluent A Eluent B
(Min) (volume%) (volume%)
0.0 100 0
10.0 100 0
15.0 95 5
20.0 95 5
22.0 92 8
50.0 92 8
52.0 10 90
60.0 10 90
60.1 100 0
70.0 100 0

(Retention time of chlorogenic acids)
・ 3-Caffeoylquinic acid (3-CQA): 5.2 min
・ 5-Caffeoylquinic acid (5-CQA): 8.7 min
4-Caffeoylquinic acid (4-CQA): 11.2 min
3-Ferlaquinic acid (3-FQA): 12.6 min
5-Ferlaquinic acid (5-FQA): 19.1 min
4-Ferlaquinic acid (4-FQA): 20.9 min
3,5-dicaffeoylquinic acid (3,5-diCQA): 37.0 min
3,4-dicaffeoylquinic acid (3,4-diCQA): 37.5 min
・ 4,5-dicaffeoylquinic acid (4,5-diCQA): 44.8 min
From the area percentage obtained here, chlorogenic acids were quantified using 5-CQA as a standard substance.

(Caffeine retention time)
18.8min
Caffeine was quantified from the area percentage determined here using the reagent caffeine as a standard substance.

2. Yield of chlorogenic acids The yield of chlorogenic acids was calculated by dividing the amount of chlorogenic acids contained in the purified chlorogenic acid-containing compositions obtained in each Example and Comparative Example by the amount of chlorogenic acids contained in the raw material chlorogenic acids-containing composition. Was determined by

3. Caffeine content The caffeine content is the amount of caffeine contained in the purified chlorogenic acid-containing composition obtained in each Example and Comparative Example, and the purified chlorogenic acid-containing composition obtained in each Example and Comparative Example. Was obtained by dividing by the total mass of.

4). Chlorogenic acid content rate Chlorogenic acid content rate is the amount of chlorogenic acid contained in the purified chlorogenic acid-containing composition obtained in each example and comparative example, and the purified chlorogenic acid-containing composition obtained in each example and comparative example. Was obtained by dividing by the total mass of.

5. Mass ratio of caffeine / chlorogenic acids The mass ratio of caffeine / chlorogenic acids is determined by the amount of caffeine contained in the purified chlorogenic acid-containing composition obtained in each example and comparative example. It calculated | required by remove | dividing by the amount of chlorogenic acids contained in the refine | purified chlorogenic acid containing composition obtained.

6). Purity of chlorogenic acids The purity of chlorogenic acids was determined by dividing the mass of chlorogenic acids contained in the solid content of the purified chlorogenic acid-containing composition by the solid content mass of the purified chlorogenic acid-containing composition.
As used herein, “solid content” refers to a residue obtained by drying a sample for 3 hours with an electric thermostatic dryer at 105 ° C. to remove volatile substances.

7). Measurement of L value The sample was measured using a color difference meter (Spectrophotometer SE2000, manufactured by Nippon Denshoku).

Preparation Example 1
Robusta-type raw coffee beans were extracted with hot water and dried to obtain a powdery raw material chlorogenic acid-containing composition. The raw material chlorogenic acid-containing composition had a chlorogenic acid content of 38.2% by mass, a caffeine content of 9.93% by mass, and a mass ratio of caffeine / chlorogenic acids of 0.26. Next, the raw material chlorogenic acid-containing composition was dissolved in ion-exchanged water so that the chlorogenic acid content was 1.2% by mass to prepare “Solution A”. The pH of this solution was 5.7.

Example 1
(Process A)
Solution A obtained in Preparation Example 1 was placed in a column packed with an H-type cation exchange resin (trade name: SK1BH, manufactured by Mitsubishi Chemical Corporation) at a space velocity of 25 ° C. and SV = 1 [hr ⁻¹ ]. 20 (mL / mL) was passed through the filling volume of the resin. The pH of the solution after passing through was 2.3.
(Process B)
The liquid obtained in step A was applied to a column filled with a weakly basic anion exchange resin (trade name IRA67, manufactured by Dow Chemical Co., Ltd.) at 25 ° C. and a space velocity of SV = 1 [hr ⁻¹ ]. 15 (mL / mL) was passed through to the filling volume.
(Process C)
Washing water at 90 ° C. was passed through the weakly basic anion exchange resin after Step B at a space velocity of SV = 5 [hr ⁻¹ ] by 15 (mL / mL) with respect to the resin filling capacity.
(Process D)
The weakly basic anion exchange resin after Step C is charged with an alkaline aqueous solution (0.5 mass% NaOH aqueous solution, pH 12.4) at 25 ° C. and a space velocity of SV = 5 [hr ⁻¹ ]. Liquid (25 mL / mL).
The liquid obtained in step D was passed through a column packed with an H-type cation exchange resin (trade name: SK1BH, manufactured by Mitsubishi Chemical Corporation) to adjust the pH to 3.1, and “Purified chlorogenic acid-containing composition” " The H-type cation exchange resin used here was 1.2 (mL / mL) with respect to the filling capacity of the weakly basic anion exchange resin. Subsequently, the purified chlorogenic acid-containing composition was analyzed. The results are shown in Table 1.

Examples 2-4
A purified chlorogenic acid-containing composition was obtained in the same manner as in Example 1 except that the washing water having the temperature shown in Table 1 was used in Step C. Subsequently, the purified chlorogenic acid-containing composition was analyzed. The results are shown in Table 1.

Example 5
A purified chlorogenic acid-containing composition was obtained in the same manner as in Example 1 except that the washing water having a flow rate as shown in Table 1 was used in Step C. Subsequently, the purified chlorogenic acid-containing composition was analyzed. The results are shown in Table 1.

Example 6
(Process A)
The solution A obtained in Preparation Example 1 was charged into a column packed with an H-type cation exchange resin (trade name SK1BH, manufactured by Mitsubishi Chemical Corporation) at a space velocity of SV = 1 [hr ⁻¹ ]. 20 (mL / mL) was passed through. The pH of the solution after passing through was 2.3.
(Process B)
The liquid obtained in step A is packed in a column filled with a weakly basic anion exchange resin (trade name IRA67, manufactured by Dow Chemical Co., Ltd.) at a space velocity of SV = 1 [hr ⁻¹ ]. 15 (mL / mL) was passed through.
(Process C)
Washing water at 90 ° C. was passed through the weakly basic anion exchange resin after Step B at a space velocity of SV = 5 [hr ⁻¹ ] by 15 (mL / mL) with respect to the resin filling capacity.
(Process D)
To the weakly basic anion exchange resin after Step C, an acid aqueous solution (1.8 mass% HCl aqueous solution, pH 0.5) is applied to the column at a space velocity of SV = 5 [hr ⁻¹ ] with respect to the resin packing capacity. 25 (mL / mL).
The liquid obtained in Step D was concentrated under a reduced pressure of 20 torr, and HCl remaining in the solution was distilled off to obtain a “purified chlorogenic acid-containing composition”. Subsequently, the purified chlorogenic acid-containing composition was analyzed. The results are shown in Table 1.

Comparative Example 1
A “purified chlorogenic acid-containing composition” was obtained in the same manner as in Example 1, except that 25 ° C. washing water was used in Step C. Subsequently, the purified chlorogenic acid-containing composition was analyzed. The results are shown in Table 1.

Comparative Example 2
A “purified chlorogenic acid-containing composition” was obtained in the same manner as in Example 1 except that Step C was not performed. Subsequently, the purified chlorogenic acid-containing composition was analyzed. The results are shown in Table 1.

Comparative Example 3
A “purified chlorogenic acid-containing composition” was obtained in the same manner as in Example 1, except that a strongly basic anion exchange resin was used in Step B. Subsequently, the purified chlorogenic acid-containing composition was analyzed. The results are shown in Table 1.

  From Table 1, the raw material chlorogenic acid-containing composition was sequentially brought into contact with a cation exchange resin and a weakly basic anion exchange resin, and further contacted with a weakly basic anion exchange resin with water at 35 ° C. or higher, followed by an acid aqueous solution. Alternatively, it can be seen that by eluting with an alkaline aqueous solution, a purified chlorogenic acid-containing composition in which caffeine is further reduced can be obtained without impairing the chlorogenic acids.

Claims (7)

Contacting the raw material chlorogenic acid-containing composition with a cation exchange resin; and
Contacting the liquid obtained in step A with a weakly basic anion exchange resin; and
Step C in which water at 35 ° C. or higher is brought into contact with the weakly basic anion exchange resin after Step B;
Step D of contacting the acid aqueous solution to a weakly basic anion exchange resin after step C
A method for producing a purified chlorogenic acid-containing composition. The method for producing a purified chlorogenic acid-containing composition according to claim 1, wherein water having a temperature of 40 ° C or higher is brought into contact in Step C.   The method for producing a purified chlorogenic acid-containing composition according to claim 1 or 2, wherein the cation exchange resin used in step A is an H-type cation exchange resin.   Any of Claims 1-3 which make a raw material chlorogenic acid containing composition contact in the liquid flow conditions of the flow ratio (BV) = 0.5-100 (mL / mL) with respect to the capacity | capacitance of a cation exchange resin in the process A. A method for producing the purified chlorogenic acid-containing composition according to claim 1.   In the step B, the liquid obtained in the step A is brought into contact under a liquid passing condition (BV) = 0.5 to 100 (mL / mL) with respect to the capacity of the weakly basic anion exchange resin. The manufacturing method of the refinement | purification chlorogenic acid containing composition as described in any one of -4.   In the step C, water is contacted under a liquid flow condition of a liquid flow ratio (BV) = 0.5 to 100 (mL / mL) with respect to the filling capacity of the weakly basic anion exchange resin. A method for producing a purified chlorogenic acid-containing composition according to one item.   The manufacturing method of the refinement | purification chlorogenic acid containing composition as described in any one of Claims 1-6 whose pH of acid aqueous solution is 4 or less.