JP7231143B2 - Method for producing polyphenol-reduced beverage - Google Patents

Description

The present invention relates to a method for producing a polyphenol-reduced beverage.

Polyphenols are known to interact with various substances and functional groups due to their structures, and various techniques have been disclosed so far for methods of reducing or removing polyphenols using their properties. As a representative technique, a technique of adding polyvinylpolypyrrolidone (PVPP) to polyphenol-containing beverages and reducing or removing polyphenols by PVPP is known (see, for example, Patent Documents 1 and 2).

However, since PVPP is an insoluble powder and has swelling properties, it is not easy to handle. It was necessary to contact for hours and remove the polyphenol-adsorbed PVPP from the beverage. For this reason, the method of reducing or removing polyphenols using PVPP complicates the production process, and the production efficiency is not necessarily good. In addition, the above method requires special equipment such as a filtration device and a centrifugal separator to completely remove PVPP from the beverage, and PVPP is not an inexpensive adsorbent, so there is also the problem of increased costs. .

JP-A-62-61569 JP-A-8-28235

An object of the present invention is to provide a method for producing a beverage with reduced polyphenol content, which has excellent polyphenol removal efficiency and easy handling of the adsorbent material, and a method for reducing the polyphenol content in a polyphenol-containing beverage. .

The present inventors recently contacted a graft polymerized nylon fiber body obtained by polymerizing various polymerizable monomers on a nylon base material by a radiation graft polymerization method with a green tea extract. It was found that a nylon fiber body obtained by graft polymerization has an excellent catechin-removing effect and a small variation in the pH of the beverage after treatment. The present inventors also confirmed that the polyphenol-removing effect of the above-mentioned graft-polymerized nylon fiber material is also exhibited in polyphenol-containing beverages other than the green tea extract. The present inventors have further confirmed that the above-mentioned graft-polymerized nylon fiber having polyphenols adsorbed thereon can be used repeatedly by subjecting it to a regeneration treatment. The present invention is based on these findings.

（上記式中、Ｒ^１は水素原子または炭素数１～４のアルキル基を表し、Ｒ^２は１または２
以上の水酸基により置換されていてもよい炭素数１～４のアルキル基を表し、Ｘは－Ｏ－
または－Ｎ（－Ｒ^３）－を表し、Ｒ^３は水素原子または炭素数１～４のアルキル基を表す
。）
で表される１種または２種以上の化合物を含む重合性モノマーをグラフト重合させてなる
高分子基材とを接触させることを含んでなる、ポリフェノール含有量が低減された飲料の
製造方法。
［２］式（Ｉ）の化合物が、Ｎ－（ヒドロキシメチル）アクリルアミド、Ｎ－（２－ヒド
ロキシエチル）アクリルアミド、Ｎ，Ｎ－ジメチルアクリルアミド、２－ヒドロキシエチ
ルメタクリレートおよびＮ－イソプロピルアクリルアミドからなる群から選択される１種
または２種以上である、上記［１］に記載の製造方法。
［３］重合性モノマーが、Ｎ－ビニル－アルキルアミドをさらに含んでなる、上記［１］
または［２］に記載の製造方法。
［４］高分子基材と接触させた後の飲料またはその原料のｐＨが接触前のｐＨに対して±
０．３の範囲内にある、上記［１］～［３］のいずれかに記載の製造方法。
［５］高分子基材が、ポリオレフィン系樹脂、ポリアミド系樹脂、セルロースまたはウレ
タンである、上記［１］～［４］のいずれかに記載の製造方法。
［６］高分子基材が、繊維状、中空糸状、不織布状またはビーズ状である、上記［１］～
［５］のいずれかに記載の製造方法。
［７］高分子基材が、再生処理に付された高分子基材である、上記［１］～［６］のいず
れかに記載の製造方法。
［８］再生処理が、ポリフェノールを吸着した高分子基材を、中性再生剤、アルカリ性再
生剤または酸性再生剤と接触させることにより行われる、上記［７］に記載の製造方法。
［９］ポリフェノール含有飲料が、緑茶、紅茶、ウーロン茶、ブレンド茶、醸造酒、蒸留
酒、野菜飲料、果実飲料、果実・野菜ミックスジュース、コーヒー飲料、穀物乳、酢飲料
若しくはノンアルコールビールテイスト飲料またはこれらの組合せである、上記［１］～
［８］のいずれかに記載の製造方法。
［１０］ポリフェノール含有飲料が、容器詰め飲料である、上記［１］～［９］のいずれ
かに記載の製造方法。
［１１］下記式（Ｉ）：

（上記式中、Ｒ^１、Ｒ^２およびＸは、上記［１］において定義された内容と同義である。
）
で表される１種または２種以上の化合物を含む重合性モノマーをグラフト重合させてなる
高分子基材を用いることを含んでなる、ポリフェノール含有量を低減する方法。 According to the present invention, the following inventions are provided.
[1] A polyphenol-containing beverage or raw material thereof, and the following formula (I):

(In the above formula, R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ² represents 1 or 2
Represents an alkyl group having 1 to 4 carbon atoms which may be substituted with a hydroxyl group above, X is -O-
or -N(-R ³ )-, where R ³ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. )
A method for producing a beverage having a reduced polyphenol content, comprising contacting a polymer substrate obtained by graft polymerization of a polymerizable monomer containing one or more compounds represented by:
[2] The compound of formula (I) is from the group consisting of N-(hydroxymethyl)acrylamide, N-(2-hydroxyethyl)acrylamide, N,N-dimethylacrylamide, 2-hydroxyethyl methacrylate and N-isopropylacrylamide The production method according to the above [1], wherein one or two or more are selected.
[3] The above [1], wherein the polymerizable monomer further comprises an N-vinyl-alkylamide
Or the production method according to [2].
[4] The pH of the beverage or its raw material after contact with the polymer substrate is ± with respect to the pH before contact
The production method according to any one of [1] to [3] above, wherein the ratio is within the range of 0.3.
[5] The production method according to any one of [1] to [4] above, wherein the polymer base material is polyolefin resin, polyamide resin, cellulose or urethane.
[6] The above [1]-, wherein the polymer substrate is fibrous, hollow fiber, non-woven fabric or bead-like
The production method according to any one of [5].
[7] The production method according to any one of [1] to [6] above, wherein the polymer substrate is a polymer substrate that has been subjected to a recycling treatment.
[8] The production method according to [7] above, wherein the regeneration treatment is carried out by contacting the polyphenol-adsorbed polymeric substrate with a neutral regenerating agent, an alkaline regenerating agent, or an acidic regenerating agent.
[9] The polyphenol-containing beverage is green tea, black tea, oolong tea, blended tea, fermented liquor, distilled liquor, vegetable drink, fruit drink, mixed fruit/vegetable juice, coffee drink, cereal milk, vinegar drink, or non-alcoholic beer-taste drink, or A combination of these [1] to
The production method according to any one of [8].
[10] The production method according to any one of [1] to [9] above, wherein the polyphenol-containing beverage is a packaged beverage.
[11] Formula (I) below:

(In the above formula, R ¹ , R ² and X have the same meanings as defined in [1] above.
)
A method for reducing polyphenol content, comprising using a polymer substrate obtained by graft polymerizing a polymerizable monomer containing one or more compounds represented by:

According to the present invention, it is possible to produce a beverage with a high polyphenol removal rate and a reduced polyphenol content simply by contacting a polyphenol-containing beverage or its raw material liquid with a polymer base material obtained by graft polymerization. This polymer base material can be processed into various shapes such as fibers, and can easily produce beverages with reduced polyphenol content without handling problems.

FIG. 1 is a diagram showing the relationship between the addition rate (%) of the graft polymerized fiber and the total catechin removal rate (%) when the green tea extract and various graft polymerized fibers were brought into contact. Black rhombuses are N,N-dimethylacrylamide-grafted fibers, black squares are N-(hydroxymethyl)acrylamide-grafted fibers, and white circles are N-vinyl-2-pyrrolidone and N,N. - The results obtained for the fiber bodies grafted with dimethylacrylamide are shown. FIG. 2 is a diagram showing the relationship between the graft ratio (%) of the graft polymerized fiber and the total catechin removal ratio (%) when the green tea extract was brought into contact with various graft polymerized fibers. White circles are fibers obtained by graft polymerization of N-vinyl-2-pyrrolidone and N,N-dimethylacrylamide, and white squares are fibers obtained by graft polymerization of N-vinyl-2-pyrrolidone and N-(hydroxymethyl)acrylamide. The results obtained for each are shown. FIG. 3 is a graph showing the relationship between the contact time (minutes) and the total catechin removal rate (%) when the green tea extract and various graft polymerized fibers were brought into contact with each other. Black rhombuses are N,N-dimethylacrylamide-grafted fibers, black squares are N-(hydroxymethyl)acrylamide-grafted fibers, and white circles are N-vinyl-2-pyrrolidone and N,N. -For the fiber body graft-polymerized with dimethylacrylamide, the open squares are for the fiber body graft-polymerized with N-vinyl-2-pyrrolidone and N-(hydroxymethyl)acrylamide, and the black triangles are for N-vinyl-2-pyrrolidone. The results obtained for each of the fiber bodies graft-polymerized with N-(2-hydroxyethyl)acrylamide are shown. FIG. 4 is a diagram showing the relationship between the contact temperature (° C.) and the total catechin removal rate (%) when the green tea extract and various graft polymerized fibers were brought into contact. Black rhombuses are N,N-dimethylacrylamide-grafted fibers, black squares are N-(hydroxymethyl)acrylamide-grafted fibers, and white circles are N-vinyl-2-pyrrolidone and N,N. - The results obtained for the fiber bodies grafted with dimethylacrylamide are shown.

Specific description of the invention

The production method of the present invention can be used to reduce the polyphenol content in polyphenol-containing beverages. The beverage to be applied is not particularly limited as long as it is a beverage containing polyphenols.

Here, "polyphenol" is a general term for compounds having multiple phenolic hydroxyl groups in the molecule. Polyphenols are broadly classified into monomeric polyphenols (e.g., anthocyanins, isoflavones, catechins (e.g., epigallocatechin, epicatechin gallate, epigallocatechin gallate, catechin, gallocatechin, catechin gallate, gallocatechin gallate) and the like. and phenylpropanoids represented by caffeic acid, chlorogenic acid, sesamin, etc.) and polymer polyphenols formed by polymerizing monomeric polyphenols. , procyanidins obtained by polymerizing catechins), and hydrolyzed tannins such as gallotannins.

Polyphenols are contained in parts such as leaves, stems, fruits, pericarp, seeds, roots, etc. of plants, and polyphenol-containing beverages typically include tea leaves, malt, hops, grains, vegetables, fruits, coffee, cacao. It is a beverage manufactured using plant raw materials such as Examples of "polyphenol-containing beverages" in the present invention include tea beverages (e.g., green tea, black tea, oolong tea, blended tea), brewed alcoholic beverages (e.g., fermented malt beverages such as beer and low-malt beer, sake, fruits such as wine and cider). liquor, liqueur such as plum wine), distilled liquor (e.g. whiskey, shochu, brandy), vegetable beverages (e.g. tomato juice, carrot juice, tomato mix juice,
carrot mixed juice), fruit drinks (e.g. apple juice, orange juice,
fruit juice), mixed fruit/vegetable juice, coffee drinks, grain milk (e.g. soy milk,
rice milk, coconut milk, almond milk), vinegar drinks (e.g. fruit vinegar drinks)
and non-alcoholic beer-taste beverages. The polyphenol-containing beverage provided by the present invention may also be a combination of two or more of the above beverages, for example
Combinations of tea beverages such as lemon tea and fruit beverages are included.

Measurement of the polyphenol content in polyphenol-containing beverages can be determined according to the nature of the beverage and the types of polyphenols contained in the beverage. For example, in the case of tea beverages, the amount of tannin can be used as the polyphenol content, and the polyphenol content can be measured using the iron tartrate method, which is the standard for evaluating the polyphenol content of teas. For fermented malt beverages such as beer, the EBC Law (EUROPEAN BREWERY CONVENTION.
nalytica-EBC), and for wine, apple juice and other fruit juice beverages and fruit wines, the polyphenol content can be measured according to the Folin-Ciocalteu method. Alternatively, individual specific components may be measured using high performance liquid chromatography (HPLC) as described in the Examples below.

In the production method of the present invention, a polymer substrate obtained by graft-polymerizing a polymerizable monomer including an acrylamide-based monomer (hereinafter sometimes referred to as "polymer substrate of the present invention") is used as a polyphenol adsorption material. It is characterized by using

In the present invention, graft polymerization is preferably carried out by a radiation graft polymerization method, that is, a method of irradiating a substrate with radiation and polymerizing a polymerizable monomer onto the substrate using radicals generated on the substrate surface or inside the substrate. can be implemented.

Ionizing radiation can be used as the radiation to irradiate the polymer substrate, and examples thereof include α rays, β rays, γ rays, electron beams, and neutron beams. Gamma rays and electron beams, which have the ability to Radiation irradiation conditions are not particularly limited as long as an appropriate functional group density is achieved, but can be 5 to 200 kGy in a deoxygenated state,
It is preferably 30 to 100 kGy. Methods for deoxygenating the reaction system are known to those skilled in the art, and for example, treatment such as bubbling an inert gas such as nitrogen into the reaction system can be performed.

When a polymer substrate is irradiated with ionizing radiation, radicals are generated on the surface and inside of the polymer substrate, and when the irradiated substrate is brought into contact with a polymerizable monomer, the generated radicals are used as starting points for the irradiation. A monomer can be polymerized onto the coated substrate. Radiation graft polymerization is
For example, it can be carried out by immersing the polymer substrate in a solution in which the polymerizable monomer is diluted.

Here, the polymer substrate is not particularly limited as long as the polymer substrate undergoes a graft polymerization reaction and can be used for polyphenol reduction treatment. Resins (eg, nylon), cellulose and urethanes are included. Moreover, the shape of the polymer substrate can be fibrous, hollow fiber, non-woven fabric, or bead, from the viewpoint of efficient polyphenol reduction treatment.

The proportion of the graft-polymerized polymerizable monomer (functional group density) per unit mass of the graft-polymerized fiber can be arbitrarily set according to the polymerizable monomer and graft polymerization conditions.

In the present invention, the polymerizable monomer to be subjected to the graft polymerization reaction with the polymer substrate includes one or more polymerizable monomers represented by the formula (I).

In the present invention, the "alkyl group having 1 to 4 carbon atoms" may be linear, branched, cyclic or a combination thereof, such as methyl, ethyl, propyl, butyl, isopropyl, isobutyl , tert-butyl, cyclopropyl, cyclobutyl and the like.

In the present invention, "a carbon number of 1 to 4 optionally substituted by 1 or 2 or more hydroxyl groups
The alkyl group of" means that one or more hydrogen atoms on the alkyl group may be substituted with a hydroxyl group. In this case, the number of hydroxyl groups on the alkyl group can be, for example, 1, 2 or 3, preferably 1 or 2.

In formula (I) R ¹ preferably represents a hydrogen atom or methyl.

In formula (I), R ² preferably represents an alkyl group having 1 to 4 carbon atoms optionally substituted by 1 or 2 hydroxyl groups, more preferably substituted by 1 or 2 hydroxyl groups. represents methyl or ethyl, which may be

In formula (I) R ³ preferably represents a hydrogen atom, methyl or ethyl.

Specific examples of compounds of formula (I) include the following.
- R ¹ represents a hydrogen atom, R ² represents hydroxymethyl, and X represents -N(-H)-;
Compounds of formula (I) (N-(hydroxymethyl)acrylamide)
a compound of formula (I) wherein R ¹ represents a hydrogen atom, R ² represents 2-hydroxyethyl and X represents -N(-H)- (N-(2-hydroxyethyl)acrylamide)
^the formula ₍ ^I
) compound (N,N-dimethylacrylamide)
- R ¹ represents methyl, R ² represents 2-hydroxyethyl and X represents -O-,
) compound (2-hydroxyethyl methacrylate)
・R ¹ represents a hydrogen atom, R ² represents isopropylacrylamide, and X is -N(-H)
The compound of formula (I) representing - (N-isopropylacrylamide)
^a _formula ⁽ _{_}
I) compound (N,N-diethylacrylamide)
- R ¹ represents a hydrogen atom, R ² represents tert-butyl, and X represents -N(-H)-,
Compound of formula (I) (N-tert-butylacrylamide)

In the present invention, the polymerizable monomer to be subjected to the graft polymerization reaction with the polymer substrate has the formula (
I), even if it consists of one or more compounds represented by formula (I), one or more compounds represented by formula (I) and compounds other than compounds represented by formula (I) (hereinafter sometimes simply referred to as “another polymerizable monomer”). Other polymerizable monomers include, for example, N-vinylalkylamides and glycidyl methacrylate. In the present invention, when a polymerizable monomer containing one or more compounds represented by the formula (I) and another polymerizable monomer is used, a high polymer obtained by a graft polymerization reaction is used. The molecular base is a copolymer obtained by grafting multiple types of polymerizable monomers.

In the present invention, N-vinylalkylamide can be represented by the following formula (II).
R ¹¹ -C(=O)-N(-R ¹² )-CH=CH ₂ (II)
(In the above formula, R ¹¹ represents an alkyl group having 1 to 4 carbon atoms, R ¹² represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, or R ¹¹ and R ¹² together 3-5
represents an alkylene group. )

Specific examples of compounds of formula (II) include the following.
a compound of the formula (II) in which R ¹¹ represents a methyl group and R ¹² represents a hydrogen atom (N-vinylacetamide)
- a compound of formula (II) in which R ¹¹ and R ¹² together represent an alkylene group having 3 carbon atoms (
N-vinyl-2-pyrrolidone)
- a compound of formula (II) in which R ¹¹ and R ¹² together represent an alkylene group having 4 carbon atoms (
N-vinylpiperidone)

In the present invention, the polymerizable monomer to be subjected to the graft polymerization reaction with the polymer substrate is N-
(hydroxymethyl)acrylamide, N-(2-hydroxyethyl)acrylamide,
It may contain one or more selected from the group consisting of N,N-dimethylacrylamide, N-isopropylacrylamide, 2-hydroxyethyl methacrylate, N,N-diethylacrylamide and N-tert-butylacrylamide. .

In the present invention, the polymerizable monomers subjected to the graft polymerization reaction with the polymer substrate include N-(hydroxymethyl)acrylamide, N-(2-hydroxyethyl)acrylamide, N,N-dimethylacrylamide, N - One or more selected from the group consisting of isopropylacrylamide, 2-hydroxyethyl methacrylate, N,N-diethylacrylamide and N-tert-butylacrylamide, and other polymerizable monomers (preferably N-vinyl alkylamides, more preferably N-vinyl-2-pyrrolidone), such as N-(hydroxymethyl)acrylamide and N-vinyl-2-pyrrolidone, N-(2-hydroxyethyl ) containing acrylamide and N-vinyl-2-pyrrolidone, containing N,N-dimethylacrylamide and N-vinyl-2-pyrrolidone, N-isopropylacrylamide and N
- containing vinyl-2-pyrrolidone, 2-hydroxyethyl methacrylate and N-
containing vinyl-2-pyrrolidone, containing N,N-diethylacrylamide and N-vinyl-2-pyrrolidone, N-tert-butylacrylamide and N-vinyl-
Examples include those containing 2-pyrrolidone.

The production method of the present invention is characterized by having a step of contacting the polyphenol-containing beverage or raw material thereof with the polymer substrate of the present invention. The contacting step can be carried out by immersing the polymeric substrate of the present invention in a polyphenol-containing beverage or raw material thereof. It can also be carried out by passing the polyphenol-containing beverage or its raw material through the column.

The contact time and contact temperature between the polyphenol-containing beverage or its raw material and the polymer substrate of the present invention can be appropriately determined according to the amount of polyphenols to be removed while referring to the examples described later.

According to the production method of the present invention, a beverage with reduced polyphenol content can be produced. Here, "a beverage with a reduced polyphenol content" means a beverage with a reduced polyphenol content compared to a polyphenol-containing beverage produced without contact with the polymer substrate of the present invention, For example, 90% or less (preferably 80% or less, more preferably 70% or less) of the polyphenol content of the beverage produced without contact with the polymer substrate of the present invention
of polyphenol content.

In the production method of the present invention, p of the beverage or its raw material after contact with the polymer substrate of the present invention
It has the feature that the fluctuation range of H is kept small. Specifically, the pH of the beverage or its raw material after contact with the polymer substrate of the present invention is within the range of ±0.3 (preferably within the range of ±0.2) with respect to the pH before contact. can be achieved. If the pH fluctuates greatly in the contacting step, it is necessary to adjust the pH with a pH adjuster or the like in the subsequent steps, and the pH adjuster or the like may affect the flavor of the beverage. Since the fluctuation range of pH after contact with the polymer base material of the invention is small, there is almost no need for pH adjustment with a pH adjuster, and a beverage excellent in flavor can be produced. Here, the fact that the pH variation is within the range of ±0.3 means that, for example, the pH of the beverage or its raw material before being brought into contact with the polymer substrate of the present invention is 5.88.
means that the pH after contact is between 5.58 and 6.18.

In the production method of the present invention, the polyphenol-containing beverage or its raw material is brought into contact with the polymer base material of the present invention.
It can be determined for each beverage in consideration of the removal rate of polyphenols, production efficiency, influence on flavor, and the like. For example, when producing tea or coffee beverages, the tea extract or coffee extract can be brought into contact with the polymeric substrate of the present invention. The tea extract used in the present invention includes not only tea extracts extracted from tea leaves, but also commercially available products such as Polyphenon (manufactured by Mitsui Norin Co., Ltd.), Sunfenon (manufactured by Taiyo Kagaku Co., Ltd.), and Theafuran (manufactured by Itoen Co., Ltd.). Tea extracts and powders can be used, and these extracts and powders dissolved in water or hot water may be used. Furthermore, these concentrated tea extracts and purified tea extracts may be used alone, may be used in combination of multiple types, or may be used in combination with a tea extract.

In the case of producing brewed liquor such as fermented malt beverages and fruit liquors, the pre-fermented liquid or post-fermented fermented liquid can be brought into contact with the polymer base material of the present invention. It is preferred that the liquid is brought into contact with the polymeric substrate of the present invention. Moreover, when producing a fruit drink or a vegetable drink, a concentrated fruit juice or a concentrated vegetable juice can be brought into contact with the polymer base material of the present invention.

The production method of the present invention can be carried out according to a normal procedure for producing beverages, except that the polyphenol-containing beverage or raw material thereof is brought into contact with the polymer substrate of the present invention.

For example, when producing a tea beverage or a coffee beverage, the tea extract or coffee extract brought into contact with the polymer base material of the present invention may, if necessary, be used for the production of a normal tea beverage or coffee beverage. Tea beverages and coffee beverages can be produced by adding the blended ingredients. Examples of the above compounding ingredients include food additives such as sweeteners, acidulants, flavors, pigments, bittering agents, preservatives, antioxidants, thickeners, emulsifiers, dietary fibers, pH adjusters, enzymes, and enhancers. agents include, but are not limited to.

In addition, when producing brewed liquor such as fermented malt beverages and fruit liquors, the fermented liquor after brewing that has been brought into contact with the polymer base material of the present invention may, if necessary, be used for the production of ordinary brewed liquor. Brewed liquor can be produced by adding the blending ingredients. Examples of the above compounding ingredients include:
Food additives such as sweeteners, acidulants, flavorings, pigments, foaming/foam retention improvers, bittering agents, preservatives, antioxidants, thickening stabilizers, emulsifiers, dietary fibers, pH adjusters, enzymes, reinforcing agents, etc. agents include
It is not limited to these.

A beverage with a reduced polyphenol content produced by the present invention can be provided as a packaged beverage after undergoing steps such as a filling step and a sterilization step in addition to the above-described blending step. For example, the blended liquid obtained in the above blending step can be sterilized by a conventional method and filled into a container. Sterilization may be before or after filling the container. The filling process and the sterilization process are known in the art, and can be appropriately determined according to the liquid type.

The container used for the beverage produced according to the present invention may be any container that is commonly used for filling beverages, and can be appropriately selected according to the type of liquid. Examples of containers include metal cans, barrels, plastic bottles (e.g., PET bottles, cups), paper containers, bottles, pouch containers, and the like. Metal cans/barrels, plastic bottles ( For example, PE
T bottle), bottles. Although container-packed beverages have a problem that turbidity and sedimentation occur even after long-term storage, the production method of the present invention can efficiently remove polyphenols, so it is suitable for the production of container-packed beverages.

In the production method of the present invention, a polymer substrate having a regenerated polyphenol adsorption function is prepared by subjecting the polymer substrate used for polyphenol adsorption to a regeneration treatment, and the polymer substrate subjected to the regeneration treatment is prepared. The material may again be used for adsorption of polyphenols. That is, the production method of the present invention may include a step of contacting a polymeric substrate after polyphenol adsorption with a regenerating agent, and then obtaining a polymeric substrate having regenerated polyphenol adsorption capacity. The method may further include a step of recovering polyphenols eluted from the polymer substrate after the polymer substrate after adsorption of polyphenols is brought into contact with the regenerant. The regenerant for desorbing polyphenols from the used polymeric base material may be any of neutral regenerant, alkaline regenerant and acidic regenerant as long as it is acceptable from the standpoint of food sanitation. Examples of the neutral regenerating agent include ion-exchanged water, and examples of the alkaline regenerating agent include one or more alkaline components such as sodium hydroxide, sodium silicate, sodium hydrogencarbonate and sodium carbonate. Examples of the acidic regenerant include an aqueous solution containing the main component, and examples of the acidic regenerant include phosphoric acid, hydrochloric acid, nitric acid, sulfuric acid,
Examples include aqueous solutions containing one or more acids such as citric acid and hypochlorous acid as main components. As described above, the polymer base material used in the production method of the present invention can be recycled, so that it can be used repeatedly and does not need to be discarded, which is advantageous in that the production cost can be reduced.

The polymer substrate used in the production method of the present invention can also be processed into various shapes such as fibers, so that beverages with reduced polyphenol content can be easily produced without handling problems. can. In addition, since the maintenance step and the filtering step are not required in the step of contacting with the polymer base material of the present invention, the steps are simplified and the manufacturing efficiency is improved. Furthermore, since the polymer base material of the present invention is solid, it is advantageous in that there is no swelling problem.

According to another aspect of the present invention, polyphenol comprising using a polymer substrate obtained by graft-polymerizing a polymerizable monomer containing one or more compounds represented by formula (I) A method for reducing content is provided. The method for reducing the polyphenol content of the present invention can be used for polyphenol-containing substances such as polyphenol-containing beverages and raw materials thereof. For example, according to the present invention, a polyphenol-containing beverage or its raw material and the formula (
I) (In the formula, R ¹ , R ² and X have the same meanings as defined in [1] above.
), comprising contacting a polymer substrate obtained by graft polymerizing a polymerizable monomer containing one or more compounds represented by the polyphenol-containing beverage or its raw material to reduce the polyphenol content A method is provided. The polyphenol content reduction method of the present invention can be carried out according to the description of the production method of the present invention.

Example 1 Types of Polymerizable Monomers and Catechin Removal Properties in Green Tea (1) Preparation of Green Tea Extract To 10 g of green tea leaves, 400 g of hot water at 70° C. was added and extracted for 10 minutes. After the extraction, it was passed through a mesh with an opening of 100 μm and rapidly cooled to 20° C. on ice to obtain a green tea extract.

(2) Preparation of graft-polymerized nylon fiber body After generating radicals by irradiating the nylon fiber as the base material with an electron beam of 40 kGy, various polymerizable monomer aqueous solutions (10% (v / v)) at 40° C. for 6 hours to obtain a graft-polymerized nylon fiber. N,N-dimethylacrylamide, N-(hydroxymethyl)acrylamide, N-vinyl-2-pyrrolidone and N,N
- dimethylacrylamide, N-vinyl-2-pyrrolidone and N-(hydroxymethyl)acrylamide, N-vinyl-2-pyrrolidone and N-(2-hydroxyethyl)acrylamide, N-vinyl-2-pyrrolidone and 2-hydroxyethyl The graft ratios of the fibers graft-polymerized with methacrylate and N-vinyl-2-pyrrolidone are respectively 1.
79%, 224%, 226%, 210%, 160%, 139% and 78%. again,
Functional group densities of fibers obtained by graft polymerization of glycidyl methacrylate, triethylenediamine, sodium iminodiacetate, and dimethylaminoethyl methacrylate are 4.5.
0 mmol/g, 2.0 mmol/g, 1.9 mmol/g and 2.5 mmol/g.

The graft rate is the mass increase rate of the grafted chain polymerized by the monomer with respect to the base material nylon, and is calculated according to the following formula.

The functional group density is the amount of functional groups per mass of graft-polymerized fiber, and is calculated according to the following formula.

(3) Treatment of graft polymerized fiber material on green tea extract liquid The green tea extract obtained in (1) above is added with the graft polymerized fiber material obtained in (2) above so as to be 1% by mass of the extract liquid. and shaken at a predetermined temperature (20° C.) for 1 to 3 hours. Thereafter, the graft-polymerized fibrous body was removed to obtain a green tea treatment liquid.

(4) Measurement of total catechin concentration The green tea treatment liquid obtained in (3) above was filtered through a membrane filter (DISMIC Hydrophilic P
After filtering with TFE, 0.45 μm, manufactured by Advantech), high performance liquid chromatography (HPLC) was performed under the HPLC analysis conditions shown in Table 1 to measure the total catechin concentration.

The term "total catechins" as used herein refers to the sum of catechins generally present in green tea, including epicatechin (EC), epigallocatechin (EGC), epicatechin gallate (ECg), epigallocatechin gallate (EGCg), Catechin (C), gallocatechin (GC), catechin gallate (Cg), and gallocatechin gallate (GCg) are the total of eight types.

From the total catechin concentration of the green tea extract before and after the graft polymerized fiber treatment, the total amount of catechins adsorbed to the graft polymerized fiber was calculated as the total catechin removal rate.

The total catechin concentration of the green tea extract before graft polymerized fiber treatment was 188-272 mg/10.
0 ml.

(5) pH measurement Each of the green tea-treated liquids obtained in (3) above was measured using a pH meter (manufactured by Kubota Corporation), and the change in pH before and after the graft polymer fiber treatment was calculated as ΔpH. The green tea extract had a pH of 5.66 to 5.88 before the graft polymer fiber treatment.

(6) Results Table 2 shows the total catechin removal rate, ΔpH, and comprehensive evaluation of various graft polymerized fibers.

Among various polymerizable monomers, N,N-dimethylacrylamide, N-(hydroxymethyl)acrylamide, N-vinyl-2-pyrrolidone and N,N-dimethylacrylamide, N-vinyl-2-pyrrolidone and N-(hydroxy methyl) acrylamide, N
- A fibrous body obtained by polymerizing vinyl-2-pyrrolidone and N-(2-hydroxyethyl)acrylamide, N-vinyl-2-pyrrolidone and 2-hydroxyethyl methacrylate, and N-vinyl-2-pyrrolidone has catechin adsorption ability. It was found that the pH was high and the pH fluctuation after contact was small, and good results were obtained. When manufacturing green tea as a packaged beverage, pH
Since the additives for adjusting the pH affect the flavor, it is desirable to select a polymerizable monomer with a small pH fluctuation of the treatment liquid in order to produce a beverage with a good flavor. N,N
- dimethylacrylamide, N-(hydroxymethyl)acrylamide, N-vinyl-2
-pyrrolidone and N,N-dimethylacrylamide, N-vinyl-2-pyrrolidone and N-(hydroxymethyl)acrylamide, N-vinyl-2-pyrrolidone and N-(
2-Hydroxyethyl)acrylamide, N-vinyl-2-pyrrolidone, 2-hydroxyethyl methacrylate, and N-vinyl-2-pyrrolidone polymerized fibrous body have small pH fluctuation and high catechin removal rate, It has been found to be very advantageous compared to other polymeric fibrous bodies.

Example 2 Addition rate of graft polymer fiber and catechin removal properties in green tea (1) Preparation of green tea extract A green tea extract was obtained in the same manner as in Example 1 (1).

(2) Preparation of graft-polymerized nylon fiber body In the same manner as in (2) of Example 1, the nylon fiber serving as the base material was irradiated with an electron beam of 40 kGy to generate radicals. Polymerizable monomer solution (10% (v/v)
) at 40° C. for 6 hours to obtain a graft-polymerized nylon fiber.

(3) Graft polymer fiber treatment to green tea extract The graft polymer fiber obtained in (2) above is added to the green tea extract at different addition rates, and is shaken and contacted at a predetermined temperature (20°C) for 3 hours. After drying, the graft polymer fiber was removed to obtain a green tea treatment liquid.

(4) Measurement of total catechin concentration The total catechin concentration was measured in the same manner as in Example 1 (4), and the total catechin removal rate was calculated. The total catechin concentration of the green tea extract before graft polymerized fiber treatment was 267.2 mg/100 ml.

(5) Results Table 3 shows the graft ratios, addition ratios, and total catechin removal ratios after treatment of various graft-polymerized fibers. In addition, the addition rate (%) of the graft polymerized fiber and the total catechin removal rate (%
) was as shown in FIG.

It was found that the removal rate of total catechins increased as the addition rate of the graft polymerized fiber increased.

Example 3 Graft ratio of graft polymer fiber and catechin removal property in green tea (1) Preparation of green tea extract A green tea extract was obtained in the same manner as in Example 1 (1).

(2) Preparation of graft polymerized nylon fiber body In the same manner as in (2) of Example 1, the nylon fiber serving as the base material was irradiated with an electron beam of 40 kGy to generate radicals. Polymerizable monomer solution (10% (v/v)
) at 40° C. for a predetermined time to obtain graft-polymerized nylon fibers with different graft ratios.

(3) Treatment of graft polymerized fiber material on green tea extract liquid The green tea extract obtained in (1) above is added with the graft polymerized fiber material obtained in (2) above so as to be 1% by mass of the extract liquid. and shaken at a predetermined temperature (20° C.) for 3 hours, and then the graft polymer fiber was removed to obtain a green tea treatment liquid.

(4) Measurement of total catechin concentration The total catechin concentration was measured in the same manner as in Example 1 (4), and the total catechin removal rate was calculated. The total catechin concentration of the green tea extract before graft polymerized fiber treatment was 271.5 mg/100 ml.

(5) Results Table 4 shows the graft ratio of various graft-polymerized fibers and the total catechin removal ratio after treatment. The relationship between the graft ratio (%) of the graft-polymerized fiber and the total catechin removal ratio (%) was as shown in FIG.

It was found that the removal rate of total catechins increased as the graft ratio of the graft polymerized fiber increased.

Example 4: Contact time and catechin removal properties in green tea (1) Preparation of green tea extract A green tea extract was obtained in the same manner as in Example 1 (1).

(2) Preparation of graft-polymerized nylon fiber body In the same manner as in (2) of Example 1, the nylon fiber serving as the base material was irradiated with an electron beam of 40 kGy to generate radicals. Polymerizable monomer solution (10% (v/v)
) at 40° C. for 6 hours to obtain a graft-polymerized nylon fiber.

(3) Treatment of graft polymerized fiber material on green tea extract liquid The green tea extract obtained in (1) above is added with the graft polymerized fiber material obtained in (2) above so as to be 1% by mass of the extract liquid. and brought into contact with the green tea extract while shaking at a predetermined temperature (20° C.) for various contact times.

(4) Measurement of total catechin concentration The total catechin concentration was measured in the same manner as in Example 1 (4), and the total catechin removal rate was calculated. The total catechin concentration of the green tea extract before graft polymer fiber treatment is 210-287 mg/100 ml.
Met.

(5) Results Table 5 shows the graft ratio, contact time, and total catechin removal rate after treatment of various graft-polymerized fibers. Also, the relationship between the contact time (minutes) of the graft polymerized fiber and the total catechin removal rate (%) was as shown in FIG.

It was found that the longer the contact time of the grafted fiber, the higher the total catechin removal rate.

Example 5: Contact temperature and catechin removal properties in green tea (1) Preparation of green tea extract A green tea extract was obtained in the same manner as in Example 1 (1).

(2) Preparation of graft polymerized nylon fiber body In the same manner as in (2) of Example 1, the nylon fiber serving as the base material was irradiated with an electron beam of 40 kGy to generate radicals, and then various Polymerizable monomer solution (10% (v/v)
) at 40° C. for 6 hours to obtain a graft-polymerized nylon fiber.

(3) Treatment of graft polymerized fiber material on green tea extract liquid The green tea extract obtained in (1) above is added with the graft polymerized fiber material obtained in (2) above so as to be 1% by mass of the extract liquid. , and after shaking and contacting for 3 hours under various temperature conditions, the graft polymer fiber was removed to obtain a green tea treatment liquid.

(4) Measurement of total catechin concentration The total catechin concentration was measured in the same manner as in Example 1 (4), and the total catechin removal rate was calculated. The total catechin concentration of the green tea extract before graft polymerized fiber treatment was 267.2 mg/100 ml.

(5) Results Table 6 shows the graft ratio, contact temperature, and total catechin removal rate after treatment of various graft-polymerized fibers. Also, the relationship between the contact temperature (° C.) of the graft polymerized fiber and the total catechin removal rate (%) was as shown in FIG.

It was found that the influence of the contact temperature of the graft-polymerized fiber on the total catechin removal rate had different characteristics depending on the monomers introduced.

Example 6: Regeneration treatment conditions and polyphenol removal properties (1) Preparation of green tea extract A green tea extract was obtained in the same manner as in Example 1 (1).

(2) Preparation of graft-polymerized nylon fiber body In the same manner as in (2) of Example 1, the nylon fiber serving as the base material was irradiated with an electron beam of 40 kGy to generate radicals. Polymerizable monomer solution (10% (v/v)
) at 40° C. for 6 hours to obtain a graft-polymerized nylon fiber.

(3) Treatment of graft polymerized fiber material on green tea extract liquid The green tea extract obtained in (1) above is added with the graft polymerized fiber material obtained in (2) above so as to be 1% by mass of the extract liquid. was added to the predetermined temperature (20 to 24 ° C.) for a predetermined time,
After contact with the green tea extract while shaking, the graft polymer fiber was removed to obtain a green tea treated liquid.

(4) Regeneration Treatment The graft-polymerized fiber that had been brought into contact with the green tea extract in (3) above was washed with a sodium hydroxide solution at a predetermined temperature for 5 to 30 minutes for regeneration treatment. Furthermore, neutralization washing was carried out with deionized water at 20 to 25°C. The graft polymerized nylon fiber bodies after the regeneration treatment were again brought into contact with the green tea extract liquid before the treatment under the same conditions as in (3) above to obtain the green tea treatment liquid.

(5) Measurement of total catechin concentration In the same manner as in (4) of Example 1, the total catechin concentration was measured, and from the total catechin removal rate of the first time and the total catechin removal rate after the regeneration treatment, the adsorption regeneration rate was calculated according to the following formula. was calculated.

The total catechin concentration of green tea extract before graft polymer fiber treatment is 191-318 g/100.
ml.

(6) Results Table 7 shows the graft ratio, the number of times of regeneration, and the percentage of regeneration of various graft-polymerized fibers.

It was found that the ability to remove polyphenols was recovered by almost 100% by carrying out the regeneration treatment of the graft-polymerized fiber using a sodium hydroxide solution.

Example 7: Polyphenol-removing properties in beverages other than green tea (1) Preparation of black tea extract To 10 g of black tea leaves, 400 g of hot water at 90°C was added and extracted for 10 minutes. After the extraction, it was passed through a mesh with an opening of 100 μm and rapidly cooled to 20° C. on ice to obtain a black tea extract, which was used as a test sample liquid.

(2) Preparation of graft-polymerized nylon fiber body In the same manner as in (2) of Example 1, the nylon fiber serving as the base material was irradiated with an electron beam of 40 kGy to generate radicals, and then a polymerizable monomer solution (10% (v/v)) at 40° C. for 6 hours to obtain a graft-polymerized nylon fiber.

(3) Treatment of the graft polymerized fiber with the sample solution for test The sample solution for test obtained in (1) above was added with the graft polymerized fiber obtained in (2) above in an amount of 1% by mass with respect to the sample solution. After shaking and contacting at a predetermined temperature (20° C.) for 3 hours, the graft polymer fiber was removed to obtain a sample treatment liquid.

(4) Measurement of Polyphenol Concentration The iron tartrate method was used to measure the polyphenol concentration of the black tea extract. In the iron tartrate method, 540 n
Measure the absorbance in m. The same procedure is performed using a standard substance such as ethyl gallate, and the amount of polyphenol is quantified in terms of the compound. The total polyphenol concentration of the black tea extract before graft polymerized fiber treatment was 246.7 mg/100 ml.

(5) Results Table 8 shows the graft ratios and polyphenol removal ratios of the various graft-polymerized fibers that were brought into contact with the test sample (black tea).

Claims (11)

A polyphenol-containing beverage (excluding beer) or a raw material thereof, and the following formula (I):

(In the above formula, R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ² represents an alkyl group having 1 to 4 carbon atoms which may be substituted with one or more hydroxyl groups, and X represents -O- or -N(-R ³ )-, and R ³ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)
A method for producing a beverage having a reduced polyphenol content, comprising contacting a polymer substrate obtained by graft polymerization of a polymerizable monomer containing one or more compounds represented by: The compound of formula (I) is selected from the group consisting of N-(hydroxymethyl)acrylamide, N-(2-hydroxyethyl)acrylamide, N,N-dimethylacrylamide, 2-hydroxyethyl methacrylate and N-isopropylacrylamide The production method according to claim 1, wherein one or two or more are used. The production method according to claim 1 or 2, wherein the polymerizable monomer further comprises N-vinyl-alkylamide. The production method according to any one of claims 1 to 3, wherein the pH of the beverage or its raw material after contact with the polymer substrate is within a range of ±0.3 with respect to the pH before contact. The production method according to any one of claims 1 to 4, wherein the polymer base material is polyolefin resin, polyamide resin, cellulose or urethane. The production method according to any one of claims 1 to 5, wherein the polymeric substrate is bead- shaped. The production method according to any one of claims 1 to 6, wherein the polymeric substrate is a polymeric substrate that has been subjected to a recycling treatment. 8. The production method according to claim 7, wherein the regeneration treatment is carried out by contacting the polyphenol-adsorbed polymeric substrate with a neutral regenerating agent, an alkaline regenerating agent, or an acidic regenerating agent. The polyphenol-containing beverage is green tea, black tea, oolong tea, blended tea, fermented liquor, distilled liquor, vegetable drink, fruit drink, fruit/vegetable mixed juice, coffee drink, grain milk, vinegar drink, non-alcoholic beer-taste drink, or a combination thereof The production method according to any one of claims 1 to 8. The production method according to any one of claims 1 to 9, wherein the polyphenol-containing beverage is a packaged beverage. Formula (I) below:

(In the above formula, R ¹ , R ² and X have the same meanings as defined in claim 1.)
Polyphenol-containing beverages (excluding beer) or raw materials thereof comprising using a polymer substrate obtained by graft polymerizing a polymerizable monomer containing one or more compounds represented by How to reduce the content.

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