JP2018126072A - Method for manufacturing polyphenol-reduced beverage - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing beverage reduced in a polyphenol content, in which a polyphenol removal efficiency is excellent and in which handling of an adsorption material is easy.SOLUTION: The method for manufacturing beverage reduced in a polyphenol content characterized in that polyphenol-containing beverage or a raw material thereof is brought into contact with a polymer base material prepared by graft-polymerizing with a polymerizable monomer containing at least one kind of an acrylamide base monomer and the like.SELECTED DRAWING: None

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 from their structures, and various techniques have been disclosed so far for methods for reducing and removing polyphenols using their properties. As a representative technique, a technique is known in which polyvinylpolypyrrolidone (PVPP) is added to a polyphenol-containing beverage, and polyphenol is reduced and removed by PVPP (see, for example, Patent Documents 1 and 2).

  However, PVPP is an insoluble powder, and it is not easy to handle because it is swellable. Also, in the polyphenol reduction / removal technology using PVPP, PVPP is added to a beverage containing polyphenol and fixed. It was necessary to remove the PVPP adsorbed with polyphenol from the beverage by contact with the mixture for a time. For this reason, in the method of reducing and removing polyphenols using PVPP, the manufacturing process is complicated, and the manufacturing efficiency is not necessarily good. In addition, the above method requires dedicated equipment such as a filtration device and a centrifuge for completely removing PVPP from the beverage, and further, PVPP is not an inexpensive adsorbent, which increases the cost. .

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 is excellent in polyphenol removal efficiency and easy to handle an adsorbing material, and a method for reducing polyphenol content in a polyphenol-containing beverage. .

  The present inventors have 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 and a green tea extract. It has been found that the nylon fiber body obtained by graft polymerization has an excellent catechin removal effect and has a small fluctuation range of the beverage pH after the treatment. The present inventors have also confirmed that the polyphenol removal effect of the graft-polymerized nylon fiber body is exhibited in polyphenol-containing beverages other than green tea extract. The present inventors further confirmed that the fiber body can be repeatedly used by subjecting the graft-polymerized nylon fiber body adsorbed with polyphenol 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 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 by 1 or 2 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.)
The manufacturing method of the drink by which polyphenol content was reduced including making the polymeric base material formed by graft-polymerizing the polymerizable monomer containing 1 type, or 2 or more types of compounds represented by these.
[2] 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 the above [1], which is one or more selected.
[3] The production method according to the above [1] or [2], wherein the polymerizable monomer further comprises N-vinyl-alkylamide.
[4] The beverage according to any one of the above [1] to [3], wherein the pH of the beverage after contacting with the polymer substrate or the raw material thereof is within a range of ± 0.3 with respect to the pH before contact. Manufacturing method.
[5] The production method according to any one of [1] to [4], wherein the polymer substrate is a polyolefin resin, a polyamide resin, cellulose, or urethane.
[6] The production method according to any one of [1] to [5], wherein the polymer substrate is in the form of a fiber, a hollow fiber, a nonwoven fabric, or a bead.
[7] The production method according to any one of [1] to [6], wherein the polymer substrate is a polymer substrate subjected to a regeneration treatment.
[8] The production method according to [7], wherein the regeneration treatment is performed by bringing the polymer substrate adsorbed with polyphenol into contact with a neutral regeneration agent, an alkaline regeneration agent, or an acidic regeneration agent.
[9] A polyphenol-containing beverage is green tea, black tea, oolong tea, blended tea, brewed liquor, distilled liquor, vegetable beverage, fruit beverage, fruit / vegetable mixed juice, coffee beverage, cereal milk, vinegar beverage or non-alcoholic beer-taste beverage or The production method according to any one of [1] to [8], which is a combination of these.
[10] The production method according to any one of [1] to [9], wherein the polyphenol-containing beverage is a container-packed beverage.
[11] The following formula (I):

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

  ADVANTAGE OF THE INVENTION According to this invention, the drink by which the polyphenol content was reduced with the high polyphenol removal rate can be manufactured only by making a polyphenol containing drink or its raw material liquid contact the polymeric base material formed by graft polymerization. The polymer base material can be processed into various shapes such as a fiber shape, and can be easily produced with a reduced polyphenol content without any handling problems.

FIG. 1 is a graph showing the relationship between the graft polymer fiber addition rate (%) and the total catechin removal rate (%) when the green tea extract is brought into contact with various graft polymer fibers. The black rhombus is for a fiber body obtained by graft polymerization of N, N-dimethylacrylamide, the black square is for a fiber body obtained by graft polymerization of N- (hydroxymethyl) acrylamide, and the white circle is N-vinyl-2-pyrrolidone and N, N -The result obtained about the fiber body which graft-polymerized dimethylacrylamide is shown, respectively. FIG. 2 is a graph showing the relationship between the graft ratio (%) of the graft polymerized fiber body and the total catechin removal rate (%) when the green tea extract is brought into contact with various graft polymerized fiber bodies. The white circle is a fiber body obtained by graft polymerization of N-vinyl-2-pyrrolidone and N, N-dimethylacrylamide, and the white square is a fiber body obtained by graft polymerization of N-vinyl-2-pyrrolidone and N- (hydroxymethyl) acrylamide. The obtained results are shown for. FIG. 3 is a graph showing the relationship between the contact time (minutes) of the graft polymerized fiber body and the total catechin removal rate (%) when the green tea extract is brought into contact with various graft polymerized fiber bodies. The black rhombus is for a fiber body obtained by graft polymerization of N, N-dimethylacrylamide, the black square is for a fiber body obtained by graft polymerization of N- (hydroxymethyl) acrylamide, and the white circle is N-vinyl-2-pyrrolidone and N, N -For a fibrous body obtained by graft polymerization of dimethylacrylamide, a white square represents a fibrous body obtained by graft polymerization of N-vinyl-2-pyrrolidone and N- (hydroxymethyl) acrylamide, and a black triangle represents N-vinyl-2-pyrrolidone. The results obtained for the fiber bodies obtained by graft polymerization of N- (2-hydroxyethyl) acrylamide are shown. FIG. 4 is a graph showing the relationship between the contact temperature (° C.) of the graft polymerized fiber body and the total catechin removal rate (%) when the green tea extract is brought into contact with various graft polymerized fiber bodies. The black rhombus is for a fiber body obtained by graft polymerization of N, N-dimethylacrylamide, the black square is for a fiber body obtained by graft polymerization of N- (hydroxymethyl) acrylamide, and the white circle is N-vinyl-2-pyrrolidone and N, N -The result obtained about the fiber body which graft-polymerized dimethylacrylamide is shown, respectively.

Detailed description of the invention

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

  Here, “polyphenol” is a general term for compounds having a plurality of phenolic hydroxyl groups in the molecule. Polyphenols are roughly classified into monomeric polyphenols (eg, anthocyanins, isoflavones, catechins (eg, epigallocatechin, epicatechin gallate, epigallocatechin gallate, catechin, gallocatechin, catechin gallate, gallocatechin gallate), etc. Flavonoids, phenylpropanoids represented by caffeic acid, chlorogenic acid, sesamin, and the like, and polymer polyphenols obtained by polymerizing monomer polyphenols. The latter polymers include proanthocyanidins (especially And condensed tannins such as procyanidins obtained by polymerization of catechins) and hydrolyzable tannins such as gallotannins.

  Polyphenols are found in plant leaves, stems, fruits, peels, seeds, roots, etc., and polyphenol-containing beverages are typically tea leaves, malt, hops, grains, vegetables, fruits, coffee, cacao It is a drink manufactured using plant raw materials such as. Examples of the “polyphenol-containing beverage” in the present invention include tea beverages (for example, green tea, black tea, oolong tea, blended tea), brewed sake (for example, malt fermented beverages such as beer and happoshu, Japanese sake, wine and cider fruits, etc. Liquor such as liquor, plum wine), distilled liquor (eg whiskey, shochu, brandy), vegetable drink (eg tomato juice, carrot juice, tomato mix juice, carrot mix juice), fruit drink (eg apple juice, orange juice) , Fruit juice mixed drinks, fruit and vegetable mixed juices, coffee drinks, cereal milk (eg, soy milk, rice milk, coconut milk, almond milk), vinegar drinks (eg fruit vinegar drinks) and non-alcoholic beer-taste drinks. . In addition, the polyphenol-containing beverage provided in the present invention may be a combination of two or more of the above beverages, for example, a combination of a tea beverage such as lemon tea and a fruit beverage.

  The measurement of the polyphenol content in the polyphenol-containing beverage can be determined according to the nature of the beverage and the type of polyphenol contained in the beverage. For example, in the case of a tea beverage, the amount of tannin can be set as the polyphenol content, and the polyphenol content can be measured using the iron tartrate method, which is a standard for evaluating the polyphenol content of teas. For fermented malt beverages such as beer, the polyphenol content is determined according to the EBC method (EUROPEAN BREWERY CONVENTION. Analytica-EBC), and for beverages and wines such as wine and apple juice, according to the foreign thiocult method. Can be measured. Alternatively, each specific component 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 polymerization of a polymerizable monomer containing an acrylamide monomer or the like as a polyphenol adsorbing material (hereinafter sometimes referred to as “polymer substrate of the present invention”) is used. It is characterized by using.

  In the present invention, the graft polymerization is preferably performed by a radiation graft polymerization method, that is, a method of irradiating a substrate with radiation and polymerizing a polymerizable monomer on 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. Examples include α rays, β rays, γ rays, electron beams, and neutron rays. Gamma rays and electron beams having the ability to do so are preferred. The irradiation condition of radiation is not particularly limited as long as an appropriate functional group density is achieved, but it can be 5 to 200 kGy, preferably 30 to 100 kGy in a deoxygenated state. A method for bringing the reaction system into a deoxygenated state is known to those skilled in the art. For example, a treatment such as bubbling an inert gas such as nitrogen into the reaction system can be performed.

  When ionizing radiation is irradiated to a polymer substrate, 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 radical is used as a starting point for the irradiation. A monomer can be polymerized on the formed substrate. The radiation graft polymerization can be carried out, for example, by immersing the polymer substrate in a solution in which a polymerizable monomer is diluted.

  Here, the polymer substrate is not particularly limited as long as the graft polymerization reaction proceeds and the polymer substrate can be used for the polyphenol reduction treatment. For example, polyolefin resin (for example, polyethylene, polypropylene), polyamide-based polymer Resins (for example, nylon), cellulose, and urethane may be mentioned. In addition, the shape of the polymer base material can be made into a fiber shape, a hollow fiber shape, a nonwoven fabric shape, or a bead shape from the viewpoint of efficiently performing the polyphenol reduction treatment.

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

  In the present invention, examples of the polymerizable monomer subjected to the graft polymerization reaction with the polymer substrate include those containing 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, for example, methyl, ethyl, propyl, butyl, isopropyl, isobutyl. , Tert-butyl, cyclopropyl, cyclobutyl and the like.

  In the present invention, “an alkyl group having 1 to 4 carbon atoms which may be substituted with one or two or more hydroxyl groups” means that one or two or more hydrogen atoms on the alkyl group may be substituted with hydroxyl groups. Means. In this case, the number of hydroxyl groups on the alkyl group can be, for example, 1, 2, or 3, and preferably 1 or 2.

In the 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 which may be substituted with one or two hydroxyl groups, and more preferably substituted with one or two hydroxyl groups. Represents optionally methyl or ethyl.

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

Specific examples of the compound of formula (I) include the following.
A compound of formula (I) (N- (hydroxymethyl) acrylamide) wherein R ¹ represents a hydrogen atom, R ² represents hydroxymethyl and X represents —N (—H) —
A compound of formula (I) (N- (2-hydroxyethyl) acrylamide) in which R ¹ represents a hydrogen atom, R ² represents 2-hydroxyethyl, and X represents —N (—H) —
A compound of formula (I) (N, N-dimethylacrylamide) in which R ¹ represents a hydrogen atom, R ² represents methyl and X represents —N (—CH ₃ ) —
A compound of formula (I) (2-hydroxyethyl methacrylate) in which R ¹ represents methyl, R ² represents 2-hydroxyethyl, and X represents —O—
A compound of formula (I) wherein R ¹ represents a hydrogen atom, R ² represents isopropylacrylamide and X represents —N (—H) — (N-isopropylacrylamide)
A compound of formula (I) (N, N-diethylacrylamide) in which R ¹ represents a hydrogen atom, R ² represents ethyl and X represents —N (—C ₂ H ₅ ) —
A compound of formula (I) wherein R ¹ represents a hydrogen atom, R ² represents tert-butyl and X represents —N (—H) — (N-tert-butylacrylamide)

  In the present invention, the polymerizable monomer subjected to the graft polymerization reaction with the polymer base material may be composed of one or more compounds represented by the formula (I). And one or more compounds represented by the formula (I) and a polymerizable monomer other than the compound represented by the formula (I) (hereinafter sometimes simply referred to as “other polymerizable monomers”). May be. Examples of other polymerizable monomers include N-vinyl alkylamide 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 polymerization yield is obtained. The molecular substrate is a copolymer obtained by grafting a plurality of 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 represent the number of carbon atoms. Represents an alkylene group of 3 to 5.)

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

  In the present invention, the polymerizable monomer subjected to the graft polymerization reaction with the polymer base material is N- (hydroxymethyl) acrylamide, N- (2-hydroxyethyl) acrylamide, N, N-dimethylacrylamide, N-isopropyl. One or more selected from the group consisting of acrylamide, 2-hydroxyethyl methacrylate, N, N-diethylacrylamide and N-tert-butylacrylamide may be included.

  In the present invention, the polymerizable monomer subjected to the graft polymerization reaction with the polymer substrate is 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) ) Acrylamide and N-vinyl-2-pi Those containing lidon, those containing N, N-dimethylacrylamide and N-vinyl-2-pyrrolidone, those containing N-isopropylacrylamide and N-vinyl-2-pyrrolidone, 2-hydroxyethyl methacrylate and N-vinyl-2 Examples include those containing -pyrrolidone, those containing N, N-diethylacrylamide and N-vinyl-2-pyrrolidone, and those containing N-tert-butylacrylamide and N-vinyl-2-pyrrolidone.

  The production method of the present invention includes a step of bringing a polyphenol-containing beverage or a raw material thereof into contact with the polymer substrate of the present invention. The contacting step can be performed by immersing the polymer substrate of the present invention in a polyphenol-containing beverage or its raw material, but the filter is filled with the polymer substrate of the present invention or the polymer substrate of the present invention. It can also be carried out by passing a 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 polyphenol to be removed while referring to the examples described later.

  According to the production method of the present invention, a beverage having a reduced polyphenol content can be produced. Here, the “beverage with 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, a beverage having a polyphenol content of 90% or less (preferably 80% or less, more preferably 70% or less) of the polyphenol content of a beverage produced without being brought into contact with the polymer substrate of the present invention. .

  The production method of the present invention is characterized in that the fluctuation range of the pH of the beverage after being brought into contact with the polymer substrate of the present invention or its raw material can be suppressed to a small value. Specifically, the pH of the beverage or its raw material after contact with the polymer substrate of the present invention is within ± 0.3 (preferably within ± 0.2) relative to the pH before contact. Can be achieved. If there is a large variation in pH in the contact step, it is necessary to adjust the pH with a pH adjuster or the like in the subsequent step, and the flavor of the beverage may be affected by the pH adjuster or the like. Since the fluctuation range of the pH after contact with the polymer substrate of the invention is small, there is almost no need for pH adjustment with a pH adjuster, and a beverage with excellent flavor can be produced. Here, the fluctuation of the pH is within a range of ± 0.3, for example, when the pH of the beverage or its raw material before being brought into contact with the polymer base material of the present invention is 5.88. It means that later pH is 5.58-6.18.

  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, but whether to contact the polyphenol-containing beverage or its raw material depends on the polyphenol removal rate, production efficiency, It can be determined for each beverage in consideration of the influence on the flavor and the like. For example, when producing a tea beverage or a coffee beverage, the tea extract or the coffee extract can be brought into contact with the polymer substrate of the present invention. The tea extract used in the present invention is not only a tea extract extracted from tea leaves, but also commercially available products such as polyphenone (manufactured by Mitsui Norinsha), sunphenon (manufactured by Taiyo Kagaku Co., Ltd.) and tear furan (manufactured by ITO EN). Tea extracts and powders can be used, and those 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, or may be used by mixing a plurality of types, or may be used by mixing with a tea extract.

  In the case of producing brewed liquor such as fermented malt beverage and fruit liquor, the fermentation solution before fermentation or after fermentation can be brought into contact with the polymer base material of the present invention. It is preferable to contact the liquid with the polymer substrate of the present invention. Moreover, when manufacturing a fruit drink and a vegetable drink, concentrated fruit juice and concentrated vegetable juice can be made to contact with the polymer base material of this invention.

  In the manufacturing method of this invention, it can implement according to the manufacturing procedure of a normal drink except making a polyphenol containing drink or its raw material and the polymer base material of this invention contact.

  For example, when producing a tea beverage or a coffee beverage, the tea extract or the coffee extract brought into contact with the polymer base material of the present invention is used for producing a normal tea beverage or a coffee beverage, if necessary. Tea drinks and coffee drinks can be produced by adding the blended ingredients. Examples of the above ingredients include sweeteners, acidulants, fragrances, pigments, bitterings, preservatives, antioxidants, thickening stabilizers, emulsifiers, dietary fibers, pH adjusters, enzymes, and reinforcing agents. Although an agent is mentioned, it is not limited to these.

  In addition, when producing brewed liquor such as fermented malt beverage and fruit liquor, it is used for the production of ordinary brewed liquor, if necessary, in the fermented liquor after brewing brought into contact with the polymer base material of the present invention. The brewed liquor can be produced by adding the blended ingredients. Examples of the ingredients include sweeteners, acidulants, fragrances, pigments, foaming / foaming improvers, bitterings, preservatives, antioxidants, thickening stabilizers, emulsifiers, dietary fibers, pH adjusters, Although food additives, such as an enzyme and a fortifier, are mentioned, it is not limited to these.

  The beverage with reduced polyphenol content produced according to the present invention can be provided as a container-packed beverage through steps such as a filling step and a sterilizing step in addition to the blending step. For example, the blended liquid obtained in the blending step can be sterilized according to a conventional method and filled into a container. Sterilization may be before filling the container or after filling. The filling step and the sterilizing step 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 usually used for filling beverages, and can be appropriately selected according to the liquid type. Examples of containers include metal cans, barrel containers, plastic bottles (for example, PET bottles, cups), paper containers, bottles, pouch containers, etc., preferably metal can / cask containers, plastic bottles ( For example, a PET bottle) and a bottle are mentioned. Although the container-packed beverage has a problem that turbidity, precipitation, etc. occur even after long-term storage, the production method of the present invention is suitable for the production of a container-packed beverage because polyphenol can be efficiently removed.

  In the production method of the present invention, a polymer substrate having a polyphenol adsorption function regenerated is prepared by subjecting the polymer substrate used for polyphenol adsorption to regeneration treatment, and the polymer group subjected to regeneration treatment is prepared. The material may again be used for polyphenol adsorption. That is, the production method of the present invention may include a step of bringing the polymer substrate after polyphenol adsorption into contact with a regenerant, and then obtaining a polymer substrate with regenerated polyphenol adsorption ability. Moreover, after making the polymer base material after polyphenol adsorption | suction contact with a regeneration agent, the process of collect | recovering the polyphenol eluted from the polymer base material may be further included. The regenerant that removes polyphenol from the used polymer base material may be any of a neutral regenerator, an alkaline regenerator, and an acidic regenerator as long as it is acceptable for food hygiene. Examples of the neutral regenerant include ion-exchanged water, and examples of the alkaline regenerator include one or more alkali components such as sodium hydroxide, sodium silicate, sodium bicarbonate, sodium carbonate, and the like. Examples of the acidic regenerant include aqueous solutions containing one or more acids such as phosphoric acid, hydrochloric acid, nitric acid, sulfuric acid, citric acid, and hypochlorous acid. Can be mentioned. Thus, since the polymer substrate used in the production method of the present invention can be recycled, it can be used repeatedly and does not require disposal, which is advantageous in that the production cost can be reduced.

  The polymer base material used in the production method of the present invention can also be processed into various shapes such as fibers, so that it is possible to easily produce a beverage with a reduced polyphenol content without any handling problems. it can. Moreover, since the maintenance process and the filtration process are unnecessary in the contact process with the polymer base material of the present invention, it is advantageous in that the process is simplified and the production efficiency is improved. Furthermore, since the polymer base material of the present invention is solid, it is advantageous in that there is no problem of swelling.

According to another aspect of the present invention, a polyphenol comprising using a polymer base material obtained by graft polymerization of a polymerizable monomer containing one or more compounds represented by the formula (I) A method of reducing the content is provided. The polyphenol content reduction method of the present invention can be used for polyphenol-containing products such as polyphenol-containing beverages and raw materials thereof. For example, according to the present invention, a polyphenol-containing beverage or a raw material thereof and the formula (I) (wherein R ¹ , R ² and X have the same meaning as defined in the above [1]). A method for reducing polyphenol content in a polyphenol-containing beverage or a raw material thereof, comprising contacting a polymer base material obtained by graft polymerization of a polymerizable monomer containing one or more compounds represented 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: Type of polymerizable monomer and catechin removal characteristics in green tea (1) Preparation of green tea extract 400 g of hot water at 70 ° C. was added to 10 g of green tea leaves and extracted for 10 minutes. After extraction, a mesh having an opening of 100 μm was passed through 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 nylon fiber as a substrate with 40 kGy electron beam, various polymerizable monomer aqueous solutions (10% (v / v)) was immersed under conditions of 40 ° C. for 6 hours to obtain a graft-polymerized nylon fiber body. N, N-dimethylacrylamide, N- (hydroxymethyl) acrylamide, N-vinyl-2-pyrrolidone and N, N-dimethylacrylamide, N-vinyl-2-pyrrolidone and N- (hydroxymethyl) acrylamide, N-vinyl- The graft ratio of the fiber body obtained by graft polymerization of 2-pyrrolidone, N- (2-hydroxyethyl) acrylamide, N-vinyl-2-pyrrolidone, 2-hydroxyethyl methacrylate, and N-vinyl-2-pyrrolidone was 179%. 224%, 226%, 210%, 160%, 139%, and 78%. The functional group densities of the fiber bodies obtained by graft polymerization of glycidyl methacrylate, triethylenediamine, sodium iminodiacetate, and dimethylaminoethyl methacrylate are 4.0 mmol / g, 2.0 mmol / g, 1.9 mmol / g, 2 0.5 mmol / g.

The graft ratio is a mass increase rate of graft chains in which a monomer for nylon as a base material can be polymerized, 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) Graft-polymerized fiber treatment to green tea extract The graft-polymerized fiber obtained in (2) above is added to the green tea extract obtained in (1) above at 1% by mass with respect to the extract. And contacted with shaking at a predetermined temperature (20 ° C.) for 1 to 3 hours. Thereafter, the graft polymerized fiber body was removed to obtain a green tea treatment liquid.

(4) Measurement of total catechin concentration After the green tea treatment liquid obtained in (3) above was filtered with a membrane filter (DISMIC hydrophilic PTFE, 0.45 μm, manufactured by Advantech), the HPLC analysis conditions shown in Table 1 were used. It used for the high performance liquid chromatography (HPLC), and measured the total catechin density | concentration.

  The total catechin here is the total of catechins generally present in green tea, epicatechin (EC), epigallocatechin (EGC), epicatechin gallate (ECg), epigallocatechin gallate (EGCg), The total of eight types of catechin (C), gallocatechin (GC), catechin gallate (Cg), and gallocatechin gallate (GCg).

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

  The total catechin concentration of the green tea extract before the graft polymerization fiber treatment was 188 to 272 mg / 100 ml.

(5) pH measurement About the green tea processing liquid obtained by said (3), it measured using the pH meter (made by Kubota), respectively, and the pH change before and after the graft polymerization fiber body process was computed as (DELTA) pH. The pH of the green tea extract before the graft polymerization fiber treatment was 5.66 to 5.88.

(6) Results Table 2 shows the total catechin removal rate, ΔpH, and overall evaluation with various graft polymer 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-vinyl-2-pyrrolidone and N- (2-hydroxyethyl) acrylamide, N-vinyl-2-pyrrolidone, 2-hydroxyethyl methacrylate, and N-vinyl-2-pyrrolidone polymerized body. It has been found that good results can be obtained with high catechin adsorption ability and small pH fluctuation after contact. When manufacturing green tea as a container-packed beverage, the additive for adjusting the pH affects the flavor. Therefore, in order to produce a beverage having a good flavor, a polymerizable monomer having a small variation in pH of the treatment liquid. It is desirable to select. N, N-dimethylacrylamide, N- (hydroxymethyl) acrylamide, N-vinyl-2-pyrrolidone and N, N-dimethylacrylamide, N-vinyl-2-pyrrolidone and N- (hydroxymethyl) acrylamide, N-vinyl- A fibrous body obtained by polymerizing 2-pyrrolidone, N- (2-hydroxyethyl) acrylamide, N-vinyl-2-pyrrolidone, 2-hydroxyethyl methacrylate, and N-vinyl-2-pyrrolidone has a small pH variation, and catechin. Since the removal rate was also high, it turned out that it was very advantageous compared with other polymer fiber bodies.

Example 2: Addition rate of graft polymerized 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 (1) of Example 1.

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

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

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

(5) Results The graft ratio, the addition ratio, and the total catechin removal ratio after the treatment of various graft polymerized fiber bodies are as shown in Table 3. Moreover, the relationship between the addition rate (%) of the graft polymerized fiber body and the total catechin removal rate (%) was as shown in FIG.

  It has been found that the removal rate of total catechins increases as the addition rate of the graft polymerized fiber increases.

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

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

(3) Graft-polymerized fiber treatment to green tea extract The graft-polymerized fiber obtained in (2) above is added to the green tea extract obtained in (1) above at 1% by mass with respect to the extract. And then brought into contact with shaking at a predetermined temperature (20 ° C.) for 3 hours, and then the graft polymerized fiber was removed to obtain a green tea treatment liquid.

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

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

  It has been found that the removal rate of total catechin increases as the graft rate of the graft polymerized fiber increases.

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

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

(3) Graft-polymerized fiber treatment to green tea extract The graft-polymerized fiber obtained in (2) above is added to the green tea extract obtained in (1) above at 1% by mass with respect to the extract. After being brought into contact with the green tea extract with shaking so as to have various contact times at a predetermined temperature (20 ° C.), the graft polymerized fiber body was removed to obtain a green tea treatment solution.

(4) Measurement of total catechin concentration As in (4) of Example 1, the total catechin concentration was measured and the total catechin removal rate was calculated. The total catechin concentration of the green tea extract before the graft polymerization fiber treatment was 210 to 287 mg / 100 ml.

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

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

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

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

(3) Graft-polymerized fiber treatment to green tea extract The graft-polymerized fiber obtained in (2) above is added to the green tea extract obtained in (1) above at 1% by mass with respect to the extract. And contacted with shaking under various temperature conditions for 3 hours, and then the graft polymerized fiber was removed to obtain a green tea treatment solution.

(4) Measurement of total catechin concentration As in (4) of Example 1, the total catechin concentration was measured and the total catechin removal rate was calculated. The total catechin concentration of the green tea extract before the 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 the various graft-polymerized fiber bodies. Further, the relationship between the contact temperature (° C.) of the graft polymerized fiber body and the total catechin removal rate (%) was as shown in FIG.

  It has been found that the influence of the contact temperature of the graft polymerized fiber on the removal rate of total catechin has different characteristics depending on the monomer to be introduced.

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

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

(3) Graft-polymerized fiber treatment to green tea extract The graft-polymerized fiber obtained in (2) above is added to the green tea extract obtained in (1) above at 1% by mass with respect to the extract. And then brought into contact with the green tea extract under shaking at a predetermined temperature (20 to 24 ° C.) for a predetermined time, and then the graft polymerized fiber was removed to obtain a green tea treatment liquid.

(4) Regeneration treatment The graft-polymerized fiber body brought into contact with the green tea extract in (3) above was washed for 5 to 30 minutes at a predetermined temperature using a sodium hydroxide solution and subjected to a regeneration treatment. Furthermore, neutralization washing | cleaning was performed with the ion exchange water of 20-25 degreeC. Each of the graft-polymerized nylon fiber bodies after the regeneration treatment was again brought into contact with the green tea extract before treatment under the same conditions as in (3) above to obtain a green tea treatment solution.

(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 first total catechin removal rate and the total catechin removal rate after regeneration treatment, the adsorption regeneration rate according to the following formula Was calculated.

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

(6) Results The graft ratio, the number of regeneration times, and the regeneration ratio of various graft polymerized fiber bodies are as shown in Table 7.

  It has been found that the polyphenol removal ability is restored almost 100% by carrying out the regeneration treatment of the graft polymerized fiber body using the sodium hydroxide solution.

Example 7: Polyphenol removal characteristics for beverages other than green tea (1) Preparation of black tea extract 400 g of hot water at 90 ° C. was added to 10 g of black tea leaf and extracted for 10 minutes. After extraction, a mesh having an opening of 100 μm was passed through and rapidly cooled to 20 ° C. on ice to obtain a black tea extract, which was used as a sample solution for testing.

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

(3) Graft-polymerized fiber treatment to sample liquid for test The graft-polymerized fiber obtained in (2) above was added to the sample liquid for test obtained in (1) above at 1% by mass with respect to the sample liquid. The mixture was shaken and contacted at a predetermined temperature (20 ° C.) for 3 hours, and then the graft polymerized fiber body 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, the absorbance at 540 nm is measured for a purple component produced by reacting a polyphenol in a liquid with an iron tartrate reagent. The same operation is performed with a standard substance such as ethyl gallate, and the amount of polyphenol is quantified in terms of the compound. The total polyphenol concentration in the black tea extract before the graft polymerization fiber treatment was 246.7 mg / 100 ml.

(5) Results Table 8 shows the graft ratio and polyphenol removal ratio of the various graft-polymerized fiber bodies brought into contact with the test sample (tea).

Claims (11)

A polyphenol-containing beverage or its raw material 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 by 1 or 2 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.)
The manufacturing method of the drink by which polyphenol content was reduced including making the polymeric base material formed by graft-polymerizing the polymerizable monomer containing 1 type, or 2 or more types of compounds represented by these.   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 manufacturing method of Claim 1 which is 1 type, or 2 or more types.   The production method according to claim 1 or 2, wherein the polymerizable monomer further comprises N-vinyl-alkylamide.   The manufacturing method as described in any one of Claims 1-3 in which the pH of the drink after making it contact with a polymer base material or its raw material exists in the range of +/- 0.3 with respect to pH before a contact.   The manufacturing method as described in any one of Claims 1-4 whose polymer base material is polyolefin resin, a polyamide-type resin, a cellulose, or urethane.   The manufacturing method as described in any one of Claims 1-5 whose polymer base material is a fibrous form, a hollow fiber form, a nonwoven fabric form, or a bead form.   The manufacturing method according to any one of claims 1 to 6, wherein the polymer substrate is a polymer substrate subjected to a regeneration treatment.   The production method according to claim 7, wherein the regeneration treatment is carried out by bringing the polymer substrate adsorbed with polyphenol into contact with a neutral regeneration agent, an alkaline regeneration agent or an acidic regeneration agent.   The polyphenol-containing beverage is green tea, black tea, oolong tea, blended tea, brewed liquor, distilled liquor, vegetable beverage, fruit beverage, fruit / vegetable mixed juice, coffee beverage, cereal milk, vinegar beverage or non-alcoholic beer-taste beverage or a combination thereof The manufacturing method according to any one of claims 1 to 8, wherein   The manufacturing method as described in any one of Claims 1-9 whose polyphenol containing drink is a container stuffed drink. The following formula (I):

(In the above formula, R ¹ , R ² and X have the same meaning as defined in claim 1).
A method for reducing the content of polyphenol, comprising using a polymer base material obtained by graft polymerization of a polymerizable monomer containing one or more compounds represented by formula (1).

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