JP2016144787A - Absorbent and filter used for wine production, and production method of wine using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: an adsorbent and a filter for producing wine from fruit juice having strong acid taste and/or bitter taste, the wine having moderate acid taste and bitter taste in good balance, a rich flavor, and excellent palatability; and a production method of wine using the same.SOLUTION: Provided are: an absorbent composed of a resin comprising an ethylene-vinyl alcohol-based copolymer as a substrate and having amino groups introduced; a filter comprising the absorbent and a binder; and a production method of wine using the same.SELECTED DRAWING: None

Description

  The present invention relates to an adsorbent and a filter used for wine production, and a wine production method using them. More specifically, an adsorbent composed of an ethylene-vinyl alcohol copolymer, which is a highly hydrophilic polymer, and a resin having an amino group introduced therein, a filter comprising such an adsorbent, and The present invention relates to a wine manufacturing method using them.

  When wine is produced using organic wines such as citric acid and naringin, which is a bitter component, for example, grapefruit juice as a raw material, the yeast activity decreases mainly due to the effects of organic acids. However, a delay in fermentation time was inevitable. In addition, only wines with very strong acidity and bitterness and poor palatability could be produced. For this reason, many alcoholic beverages with the grapefruit name are now liqueur type, and full-fledged brewed liquor produced by fermenting yeast with grapefruit juice (the “fruit wine” referred to in the liquor tax law) is a market. Then you can hardly see.

  The so-called deoxidation method for reducing the sourness of wine is mainly a neutralization method. The neutralization method is the simplest method, and is performed by adding a basic salt of a weak acid such as calcium carbonate. There are a method of adding at the stage of fruit juice and a method of adding at the stage of produced wine, but the former method is considered to be good considering the quality of the produced wine. In any case, however, this method produces neutralized salts such as calcium tartrate and malate in wine, and mainly calcium citrate in citrus, and these salts have an undesirable effect on the quality of the liquor, especially the taste. give. In addition, these salts are often poorly soluble in water and alcohol, and when stored at low temperatures, they precipitate as crystals, which often cause consumers to dislike “contamination”. . As a method for preventing the precipitation of crystals, it is generally practiced to cool the liquor before bottling and forcibly precipitate the crystals. However, it requires equipment and time, which increases costs and increases productivity. It was the cause of the decline.

  Moreover, most of bitterness removal (bitter taste removal) is performed by enzyme treatment. In this enzyme treatment, naringinase is used if the bitter component is naringin. However, since the function of naringinase is reduced in the presence of alcohol, it is usually treated at the stage of raw material juice. However, in the case of treating with an enzyme, it must be kept at a temperature of 40 to 70 ° C. for a certain period of time. Therefore, the risk of microbial contamination and the problem of wine oxidation cannot be avoided. For this reason, the brewed liquor produced using fruit juice having a strong acidity and a strong bitterness like grapefruit is further emphasized in its character and has a very poor palatability.

  For example, Japanese Patent Application Laid-Open No. 7-284387 describes a wine production method in which fermentation time is brought into contact with an anion exchange resin and / or an adsorption resin to shorten fermentation time. The adsorption resin used in this document is an adsorption resin whose base material is styrene and has no functional group, or an adsorption resin in which the base material is styrene and various functional groups are introduced to impart hydrophilicity.

JP-A-7-284387

  An object of the present invention is to provide an adsorbent and a filter for producing wine having a good balance of acidity and bitterness in a balanced manner, rich in flavor, and excellent taste from fruit juice having a strong acidity and / or bitterness, and It is providing the manufacturing method of wine using.

  In order to solve the above-mentioned problems, the present inventors have intensively studied a material containing an amino group, and as a result, have reached the present invention.

  The inventors of the present invention, by contacting the juice (boiled) or produced wine during fermentation with an adsorbent or a filter containing an adsorbent, compared to methods of removing acidity and bitterness that have been attempted variously in the past, It has been found that wine with good taste can be produced. The resin constituting the adsorbent of the present invention is based on an ethylene-vinyl alcohol copolymer, which is a highly hydrophilic polymer, and has amino groups introduced therein. That is, in the ethylene-vinyl alcohol copolymer, an amino group is chemically bonded, or a component having an amino group is dispersed without a chemical bond. By using such resins for wine production, high affinity with fruit juice or produced wine and rapid adsorption of sour and bitter components are realized.

The present invention includes the following preferred embodiments.
[1] An adsorbent composed of a resin having an amino group introduced using an ethylene-vinyl alcohol copolymer as a base material and used for wine production.
[2] The adsorbent according to [1], wherein the amino group introduction amount is 2.0 mmol / g to 15 mmol / g with respect to the mass of the resin.
[3] The adsorbent according to [1] or [2], wherein the adsorbent is a particle having a particle diameter of 10 to 3000 μm.
[4] The adsorbent according to any one of [1] to [3], which is porous and has an average diameter of pores formed on the surface of 0.01 to 50 μm.
[5] A filter used for wine production, comprising 2 to 10 parts by mass of a binder with respect to 100 parts by mass of the resin constituting the adsorbent according to any one of [1] to [4].
[6] A housing in which the filter according to [5] is loaded.
[7] A wine production method using the adsorbent according to any one of [1] to [4] or the filter according to [5].

  The adsorbent of the present invention used for wine production is excellent in wine refining, particularly in the adsorption rate of substances to be removed (citric acid and naringin components, etc.). Furthermore, a filter comprising such an adsorbent is excellent in handleability, and by using such a filter, wine purification can be performed with high efficiency and low cost by a simple operation.

  The present invention is described in detail below. The adsorbent of the present invention used for wine production is composed of a resin in which an amino group is introduced as an adsorption functional group of a substance to be removed (such as citric acid and naringin component) based on an ethylene-vinyl alcohol copolymer. The

(Ethylene-vinyl alcohol copolymer)
The ethylene-vinyl alcohol copolymer that is the base material of the adsorbent of the present invention is not particularly limited as long as the desired performance is obtained. For example, the ethylene content is 10 to 60 based on the entire copolymer. It may be about mol% and is preferably about 20 to 50 mol%. By setting the ethylene content within the above range, it is possible to obtain an adsorbent that is excellent in water resistance and is not difficult to produce.

  The saponification degree of the ethylene-vinyl alcohol copolymer is preferably 90 mol% or more, more preferably 95 mol% or more, and particularly preferably 99 mol% or more. By setting the degree of saponification to the above value or more, it is possible to obtain an adsorbent having good moldability and water resistance.

  The melt flow rate (MFR) (210 ° C., load 2160 g) of the ethylene-vinyl alcohol copolymer is not particularly limited, but is preferably 0.1 g / min or more, and more preferably 0.5 g / min or more. By setting the melt flow rate to the above value or more, it is possible to obtain an adsorbent having good water resistance and strength. The upper limit of the melt flow rate may be in a range that is usually used, and may be, for example, 25 g / min or less.

  The said ethylene-vinyl alcohol-type copolymer may contain another unsaturated monomer unit in the range which does not impair the effect of this invention. The content of the unsaturated monomer unit is preferably 10 mol% or less, more preferably 5% mol or less, based on the entire copolymer.

  Such ethylene-vinyl alcohol copolymers can be used alone or in combination of two or more.

(Amino group)
The amino group contained in the resin constituting the adsorbent of the present invention may be in a state of being chemically bonded to the ethylene-vinyl alcohol copolymer, and the component having an amino group is an ethylene-vinyl alcohol copolymer. The polymer may be dispersed without any chemical bond. Hereinafter, preferred embodiments will be described for each.

  As a method for introducing an amino group in a state of being chemically bonded to an ethylene-vinyl alcohol copolymer, for example, by copolymerizing a monomer having an amino group at the time of forming an ethylene-vinyl alcohol copolymer. Examples thereof include a method of introducing, an ethylene-vinyl alcohol copolymer, and a method of chemically modifying the copolymer as a base material with a compound having an amino group. From the viewpoint of forming amino groups on the resin surface with high density, a method of chemically modifying with an amino group-containing compound using the copolymer as a base material after the formation of an ethylene-vinyl alcohol copolymer is preferred. From the same viewpoint, the amino group is preferably introduced into the graft chain (branched polymer) using an ethylene-vinyl alcohol copolymer as a backbone polymer.

  As a method for introducing a graft chain having an amino group into an ethylene-vinyl alcohol copolymer, (1) an unsaturated monomer having a halogenated alkyl group such as chloromethylstyrene or chloroethyl (meth) acrylate, or glycidyl A method in which an unsaturated monomer having an epoxy group such as methacrylate is previously graft-polymerized from an ethylene-vinyl alcohol copolymer as a starting point, and the graft chain is reacted with a compound having an amino group; And a method of graft-polymerizing an unsaturated monomer having an ethylene-vinyl alcohol copolymer as a base point to produce a graft polymer. From the viewpoint of easy reaction, the method (1) is preferred. As the method, various known methods are possible. For example, a method of introducing a graft chain using radical polymerization using a polymerization initiator, a radical is generated using ionizing radiation, and a graft chain is introduced. And the like. Among these, from the viewpoint of high graft chain introduction efficiency, a method of introducing a graft chain using ionizing radiation is preferably used.

  As a method of graft polymerization of an unsaturated monomer to an ethylene-vinyl alcohol copolymer using ionizing radiation, radiation is irradiated in the presence of the ethylene-vinyl alcohol copolymer and the unsaturated monomer. Both of the mixed irradiation method and the pre-irradiation method in which only the ethylene-vinyl alcohol copolymer is irradiated with radiation in advance and then the unsaturated monomer and the ethylene-vinyl alcohol copolymer are brought into contact with each other are possible. The pre-irradiation method, which is the latter method, has a feature that it is difficult to generate side reactions other than graft polymerization.

  Although it does not specifically limit as a dose irradiated with ionizing radiation, 5-230 kGy is preferable, 10-200 kGy is more preferable, 15-180 kGy is further more preferable. 20-160 kGy is most preferred. By making the dose within the above range, the grafting rate is secured and there is no need to worry about excessive process costs and resin deterioration due to excessive irradiation, and the target removal target substances (citric acid and naringin components, etc.) have good removal performance. An adsorbent can be obtained.

  When conducting graft polymerization to introduce a graft chain having an amino group, the unsaturated monomer is not limited to the unsaturated monomer having a functional group such as alkyl halide and epoxy as described above, and performance is impaired. Other unsaturated monomers may be used in combination as long as they are not present. For example, divinylbenzene, ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, 1- (acryloyloxy) -3- (methacryloyloxy) -2-propanol, bismethylene acrylamide and the like can be used.

  Examples of the compound having an amino group to be reacted with the graft chain include ethylenediamine, trimethylenediamine, 2-methyl-1,3-propanediamine, propylenediamine, tetramethylenediamine, 3-methylaminopropylamine, 1, 3-diamino-2-propanol, 2-methyl-1,2-propanediamine, N-methylethylenediamine, N, N′-dimethylethylenediamine, 1,4-butanediamine, 1,3-pentanediamine, 1,4- Cyclohexanediamine, 1,3-cyclohexanediamine, trans-1,2-cyclohexanediamine, 2-methyl-1,5-pentanediamine, 1,5-pentanediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, deca Methylenedia Min, N- (2-aminoethyl) piperazine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentamethylenehexamine, hexamethyleneheptamine, polyvinylamine, polyallylamine, polyethyleneimine, 2-aminobenzylamine, 3-amino Benzylamine, 4-aminobenzylamine, benzylamine, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 4- (methylamino) pyridine, 4-amino (2-methyl) pyridine, 4-amino (3 -Methyl) pyridine, 2-picolylamine, 3-picolylamine, 4-picolylamine, 4- (ethylaminomethyl) pyridine, 3- (2-aminomethyl) pyridine, 2- (2-aminoethyl) pyridine, bis (3-pyridylmethyl) a , Bis (2-pyridylmethyl) amine, 2-amino-4-methylpyridine, 3-amino-4-methylpyridine, imidazole compounds (2-aminoimidazole, 1- (3-aminopropyl) imidazole, 2- Aminobenzoimidazole, etc.), triazole compounds (4-amino-1,2,4-triazole, 3-amino-1H-1,2,4-triazole, etc.), benzotriazole compounds (1-hydroxybenzotriazole, 1 -Aminobenzotriazole etc.), 4-aminoindole, 5-aminoindole, 6-aminoindole, histamine, tryptamine, tryptophan, polyvinylamine, polyallylamine, polyethyleneimine and the like. Among these, polyvalent amines are particularly preferable from the viewpoints of ease of production and adsorption performance of substances to be removed (citric acid and naringin components and the like).

  As a method for introducing an amino group in a state where the component having an amino group is dispersed in the ethylene-vinyl alcohol copolymer without a chemical bond, a compound having an amino group and an ethylene-vinyl alcohol copolymer are used. And a method of removing the solvent after molding, and a method of melt-kneading the compound having an amino group and the ethylene-vinyl alcohol copolymer. In the present invention, mixing by melt kneading, which does not require a solvent and can be easily molded, is preferred. In the case of mixing by melt kneading, as the compound having an amino group, an amine polymer having an amino group in a repeating unit is preferably used.

  The amino group of the amine polymer may be any one of a primary amino group, a secondary amino group, and a tertiary amino group, and is preferably a primary amino group or a secondary amino group. The repeating unit having an amino group may be one type or two or more types. Therefore, the amine-based polymer may be a polymer in which two or more kinds of repeating units having an amino group are random, block, alternating, or graft copolymerized. Moreover, the repeating unit which does not have an amino group may be included in the range which does not inhibit the effect of this invention.

  The amine-based polymer having an amino group in the repeating unit is not particularly limited, and examples thereof include polyvinylamine, polyvinylalkylamine, polyalkyleneimine, polyaniline, and salts thereof. At least one selected from this group is preferably used. More preferably, at least one selected from the group consisting of polyvinyl alkylamines, polyalkyleneimines, and salts thereof is used.

  The amount of amino groups introduced, that is, the number of moles of amino groups per unit mass of the resin constituting the adsorbent of the present invention is not particularly limited, but the removal performance of substances to be removed (citric acid and naringin components, etc.) From the viewpoint, it is preferably 2.0 mmol / g to 15 mmol / g, more preferably 3.0 mmol / g to 12 mmol / g, and still more preferably 4.0 mmol / g to 10 mmol / g. By setting the amino group introduction amount within the above range, the adsorption performance of the substances to be removed (citric acid and naringin components, etc.) is excellent, and the swelling and shrinkage of the resin is not significant (that is, there is no fear of collapse of the adsorbent due to volume change). It is possible to obtain an adsorbent that is not difficult to manufacture.

(shape)
There is no restriction | limiting in particular in the shape of the adsorbent of this invention, Although particulate form, fibrous form, etc. are mentioned, Preferably it is particulate form. In the present invention, the term “particle” is a concept including powder. When the adsorbent is particulate, the particle size distribution is not particularly limited, but is preferably 10 to 3000 μm, more preferably 30 to 2500 μm, and even more preferably 40 to 2000 μm. By setting the particle size distribution within the above range, an adsorbent that is not difficult to handle (no problems such as fine powder easily fluttering) and that has good adsorption performance for substances to be removed (such as citric acid and naringin components) can be obtained. Is possible. In addition, a particle diameter shows the value classified by sieving.

  The adsorbent of the present invention may be porous. In the present invention, the term “porous” means that a plurality of pores are present on at least the adsorbent surface. The pores may have a continuous structure or an independent structure. The pores formed on the surface may have an average diameter of about 0.01 μm to 50 μm, preferably 0.05 μm to 20 μm, more preferably about 0.2 μm to 10 μm. By setting the average diameter within the above range, it is possible to obtain an adsorbent having good adsorption performance and mechanical strength for the substances to be removed (citric acid and naringin components and the like). The average diameter of the pores is a value measured by the method described in Examples described later.

  The adsorbent of the present invention may contain additives such as a cross-linking agent, inorganic fine particles, a light stabilizer, and an antioxidant as long as the effects of the present invention are not impaired.

(filter)
The filter of the present invention used for wine production can be preferably molded by mixing the adsorbent and the binder. There is no particular limitation on the type and form of the binder contained in the filter as long as the filter can be held by holding the adsorbent, and examples include fibrous binders, powdered binders, and the like, preferably fibrous binders. More preferably, it is a fibrillated (small fiber) fibrous binder. The fibrous binder can be widely used regardless of whether it is a synthetic product or a natural product. Examples thereof include acrylic fiber, polyethylene fiber, polypropylene fiber, polyacrylonitrile fiber, cellulose fiber, nylon fiber, aramid fiber, and polyester fiber. Can be mentioned. These fibrous binders can be fibrillated by a known method such as beating, and the fibrillated fibrous binder is also available as a commercial product. The fiber length of the fibrous binder is preferably 4 mm or less.

  The form in which the adsorbent is held by the binder is not particularly limited. For example, when the binder is a fibrillated fibrous binder, the adsorbent forms a fibrillated fibrous binder. A form in which it is captured and fixed in a network structure and supported on a fibrous binder is desirable. When the binder is a heat-sealable fibrous binder (eg, polyethylene fiber, polypropylene fiber, polyester fiber, etc.), the adsorbents are bonded together by the molten fibrous binder, and the adsorbent is held by the binder. Is done. In addition, when the binder is a heat-fusion resin powder binder (eg, polyethylene powder, polypropylene powder, polystyrene powder, polyethylene terephthalate powder, etc.) as a powdery binder, the adsorbent is once melted with the powdered binder. Bonded and the adsorbent is held by the binder.

  The compounding ratio of the resin and the binder constituting the adsorbent of the filter of the present invention used for wine production is the resin 100 in terms of the removal effect of substances to be removed (such as citric acid and naringin components), suppression of filter swelling and moldability. It is 2-10 mass parts of binder with respect to a mass part, Preferably it is 3-8 mass parts.

  The production method of the filter of the present invention used for wine production is not particularly limited, and a known molding method using a binder can be employed. A slurry suction method is preferable in terms of efficient production. In the slurry suction method, for example, a double tubular container having an inner tube and an outer tube each having a large number of suction holes is prepared, and a slurry containing an adsorbent and a binder is placed between the inner tube and the outer tube. A filter formed into a hollow cylindrical shape can be obtained by pouring and sucking the slurry from the center (inner tube side). The slurry is preferably prepared by dispersing the adsorbent and the fibrous binder in water so that the solid concentration is 5 to 15% by mass from the viewpoint of efficiently producing the filter.

  In the wine manufacturing method of the present invention, the method of contacting the adsorbent with the substances to be removed of the wine components (citric acid and naringin components, etc.) is not particularly limited. For example, the adsorbent is placed in a container containing fruit juice. In addition, it may be stirred or allowed to stand, or the wine may be passed through a housing loaded with a filter made from an adsorbent.

  The fruit juice that can be used in the wine production method of the present invention may be of any kind as long as it is usually used as a raw material for wine, such as citrus fruits such as grapefruit, grape juice or apple juice. As an example. In the case of a citrus juice having a strong acidity and bitterness such as grapefruit, the effect of the present invention of removing the acidity and / or bitterness components can be remarkably obtained, which is particularly desirable.

  Examples of yeasts that can be used in the wine production method of the present invention include wine yeasts belonging to Saccharomyces cerevisiae, such as W-3 yeast, OC-2 yeast, Montrachet yeast, champagne yeast, sherry yeast, and gaisen. Examples include Heim 74 yeast. Examples of the sour components of the fruit juice and the fermented fruit juice removed by the present invention include organic acids such as citric acid, acetic acid, malic acid, succinic acid, tartaric acid, and lactic acid. Moreover, naringin, limonin, etc. are mentioned as a bitter component of the fruit juice removed in this invention.

  The adsorbent or filter that can be used in the wine production method of the present invention is the adsorbent or filter of the present invention described above. The adsorbent of the present invention has a high affinity with fruit juice or produced wine, a high adsorption rate, and can simultaneously remove both substances of citric acid as a sour component and naringin as a bitter component.

  In the present invention, as a method of contacting the juice and the adsorbent during fermentation, a method of directly adding the adsorbent to the juice during fermentation, a gap that does not leak the adsorbent to the outside, and the liquid is Examples include a method in which an adsorbent or a filter is loaded into a container (for example, a filter housing container or a stainless steel mesh basket) that can freely enter and exit, and this is immersed in fruit juice during fermentation. The method of adding the adsorbent directly to the juice during the former fermentation is the easiest, but after addition of the adsorbent, the adsorbent deposits on the bottom of the fermentation vessel, resulting in insufficient contact with the juice components, Since the adsorptive capacity of the adsorbent does not function, constant stirring is required. In this case, yeast cells that sink to the bottom are rolled up at the same time. As a result, off-flavors such as yeast odor and odor (starch) odor can be transferred to wine, and the quality of the liquor may be reduced. This is not preferable because it is difficult to recover the material.

  On the other hand, in the latter method in which the container is loaded with an adsorbent or filter and immersed in the fruit juice during fermentation, if the container loaded with the adsorbent or filter is retained in the fruit juice, carbon dioxide generated during fermentation Convection occurs in the fruit juice during fermentation, and the fruit juice component and the adsorbent are in sufficient contact by this convection, so there is no need for stirring. In addition, after the treatment, the container loaded with the adsorbent or the filter is pulled up from the fruit juice to recover the adsorbent or the filter, washed with water or alcohol, regenerated and then reused. It is preferable because it has advantages.

  Note that the amount of adsorbent used varies depending on the type of adsorbent and the amount of target sour and / or bitter components to be removed, and it is presumed that other components of fruit juice are also affected. It is desirable to determine by conducting a test. Usually, the adsorbent is about 1 to 10% by volume with respect to the fruit juice volume.

  In the present invention, when an adsorbent or a filter is put in fruit juice by the above method and fermented, the sourness component and / or the bitterness component are removed and the fermentation rate is very high. The reason why such an effect can be obtained is that the yeast is stuck in the gap between the particulate adsorbents and the yeast does not settle to the bottom, and the yeast is retained on the porous adsorbent surface, so that it is always rich in nutrients. It is conceivable that the contact with the fruit juice can be maintained, and that the pH of the fruit juice is increased by removing the acid, and the growth environment of the yeast is improved. Fast fermentation has a positive impact on wine quality as well as productivity. That is, when fermentation is delayed, acetic acid or the like that causes volatile acid odor tends to increase, but the wine obtained by the method of the present invention has good flavor. In addition, in the manufacturing method of this invention, the other raw material used in normal wine manufacture can be used. Examples of such other raw materials include sugars such as sugar, fructose and fructose, pectin-degrading enzymes, sulfite and the like. Moreover, in this invention, wine can be manufactured even if it uses any conventional methods and manufacturing conditions other than said method.

  EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated in detail, this invention is not limited to these Examples. In addition, each numerical value in an Example was measured with the following method.

[Calculation of average pore diameter]
The surface of the particles was observed using a scanning electron microscope. Arbitrary 50 pores were selected from the pores formed on the surface, and the major axis of each pore was measured. The 50 major axes were averaged, and the average value was derived as the average diameter of the pores. However, in the case of 1 nm or less, since it cannot be distinguished from scratches, deposits, etc., it was excluded from the selection.

[Graft ratio]
Calculation was performed according to the following formula.
Graft rate [w / w (%)] = 100 × (weight of attached graft chain) / (weight of substrate)

[Amino group introduction amount]
(When an amino group is chemically introduced into an ethylene-vinyl alcohol copolymer)
Let W be the mass change before and after the reaction for introducing an amino group. Calculation was performed according to the following formula.
Amino group amount [mmol / g] = (number of nitrogen atoms per molecule of reaction substrate [pieces] × W [g] / reaction substrate molecular weight [g / mol]) / (resin mass after reaction [g]) × 1000
(When an amino group is physically introduced into an ethylene-vinyl alcohol copolymer)
The composite ratio of the amine polymer is defined as W (mass%). Calculation was performed according to the following formula.
Amino group amount [mmol / g] = number of nitrogen atoms per amine polymer unit structure [pieces] × (W / 100 [g] / amine polymer unit molecular weight [g / mol]) × 1000

(Evaluation method for adsorption performance of target substances (citric acid and naringin components, etc.))
(Examples 1-7 and Comparative Examples 1-2)
United States Florida grapefruit juice (total acid 14.0 g / L, naringin 510 mg / L) is dispensed 1 L into two 1 L Erlenmeyer flasks, and sulfite is added to each to 100 ppm. Yeast W-3 was inoculated and cultured at 20 ° C. After the start of fermentation, 15 mL of the adsorbent was loaded into a 100-mesh nylon bag, placed in one Erlenmeyer flask during fermentation, and no adsorbent was added to the other Erlenmeyer flask during fermentation as a control. The amount of adsorbent used was set in a range of 10 to 11 g / L for the total acid and 200 ± 50 mg / L for naringin by preliminary experiments. The fermentation was stopped by cooling when the amount of carbon dioxide produced by fermentation reached 4% (alcohol content: about 5%) and adding sulfurous acid to 100 ppm. The wine solution obtained was measured with an ion chromatography apparatus manufactured by Nippon Dionex Co., Ltd. using column IONPAcICE-AS6, eluent: 0.4 mmol / L heptafluoroacetic acid, flow rate: 1.0 mL / min, organic acid and naringin Etc. were analyzed.
(Examples 8 and 9)
A wine production filter was loaded into a 1.5 L housing, and 45 L of wine solution was passed at a flow rate of SV = 4. Thereafter, the effluent was mixed, and organic acids and naringin were analyzed in the same manner as described above.

[Example 1]
After melt-kneading 90 parts by mass of a commercially available ethylene-vinyl alcohol copolymer (F101, manufactured by Kuraray Co., Ltd.) and 10 parts by mass of a vinyl alcohol polymer (PVA403, manufactured by Kuraray Co., Ltd.) in a lab plast mill. The compound obtained by cooling and solidifying the melt was pulverized and classified using a sieve to obtain particles having a particle diameter of 212 μm to 425 μm. Further, the obtained particles were treated with hot water at 100 ° C. to extract a vinyl alcohol polymer, thereby obtaining porous ethylene-vinyl alcohol copolymer particles. The average diameter of the pores of the porous particles was 0.23 μm. The porous particles were irradiated with 60 kGy ionizing radiation, immersed in and stirred in a nitrogen-substituted glycidyl methacrylate solution at 80 ° C., and graft polymerization was performed. When the graft ratio was evaluated, it was 310%. Further, the particles were immersed in an isopropanol solution of ethylenediamine and reacted, and then crosslinked using ethylene glycol diglycidyl ether. The particles were washed with methanol, dried, and classified into particles having a particle diameter of 300 μm to 500 μm using a sieve to obtain a target adsorbent. About this adsorbent, the adsorption | suction performance of the removal target substance in a wine component was evaluated. The results are shown in Table 1. The amount of amino group introduced into the resin constituting the adsorbent was 6.0 mmol / g.

[Example 2]
After melt-kneading 90 parts by mass of a commercially available ethylene-vinyl alcohol copolymer (F101, manufactured by Kuraray Co., Ltd.) and 10 parts by mass of a vinyl alcohol polymer (PVA205, manufactured by Kuraray Co., Ltd.) in a lab plast mill. The compound obtained by cooling and solidifying the melt was pulverized and classified using a sieve to obtain particles having a particle size of 106 μm to 212 μm. Furthermore, the obtained particles were treated in hot water to extract a vinyl alcohol polymer, thereby obtaining porous ethylene-vinyl alcohol copolymer particles. The average diameter of the pores of the porous particles was 0.27 μm. The porous particles were irradiated with 100 kGy ionizing radiation, immersed in and stirred in a nitrogen-substituted glycidyl methacrylate solution at 80 ° C., and graft polymerization was performed. When the graft ratio was evaluated, it was 374%. Further, the particles were immersed and reacted in an isopropanol solution of diethylenetriamine, and then cross-linked using ethylene glycol diglycidyl ether. The particles were washed with methanol, dried, and classified into particles having a particle diameter of 212 μm to 425 μm using a sieve to obtain a target adsorbent. About this adsorbent, the adsorption | suction performance of the removal target substance in a wine component was evaluated. The results are shown in Table 1. The amount of amino group introduced into the resin constituting the adsorbent was 8.7 mmol / g.

[Example 3]
After pulverizing a commercially available ethylene-vinyl alcohol copolymer (F101, manufactured by Kuraray Co., Ltd.), particles having a particle diameter of 150 μm to 300 μm were prepared using a sieve. No pores were formed in the particles. The particles were irradiated with 150 kGy ionizing radiation, immersed in a 60% by mass isopropanol solution of nitrogen-substituted glycidyl methacrylate at 80 ° C., and stirred for 90 minutes to carry out graft polymerization. Thereafter, the obtained particles were washed with methanol and dried, and then the graft ratio was evaluated to be 210%. Further, the particles were immersed in an isopropanol solution of ethylenediamine and reacted, and then crosslinked using ethylene glycol diglycidyl ether. The particles were washed with methanol, dried, and classified into particles having a particle diameter of 212 μm to 425 μm using a sieve to obtain a target adsorbent. About this adsorbent, the adsorption | suction performance of the removal target substance in a wine component was evaluated. The results are shown in Table 1. The amount of amino group introduced into the resin constituting the adsorbent was 5.4 mmol / g.

[Example 4]
99 parts by mass of a commercially available ethylene-vinyl alcohol copolymer (C109, manufactured by Kuraray Co., Ltd.) and 1 part by mass of a vinyl alcohol polymer (PVA205, manufactured by Kuraray Co., Ltd.) at 210 ° C. After melt-kneading for 3 minutes at a temperature, the compound obtained by cooling and solidifying the melt was pulverized, and particles having a particle diameter of 300 μm to 500 μm were produced using a sieve. Furthermore, the obtained particles were stirred in hot water at 100 ° C. for 2 hours to extract only the vinyl alcohol polymer, thereby obtaining porous ethylene-vinyl alcohol copolymer particles. The average diameter of the pores of the porous particles was 0.13 μm. The porous particles were irradiated with 100 kGy ionizing radiation, immersed in a 40% by mass isopropanol solution of nitrogen-substituted glycidyl methacrylate at 80 ° C., and stirred for 90 minutes to carry out graft polymerization. Thereafter, the obtained particles were washed with methanol and dried, and the graft ratio was evaluated to be 365%. Further, the particles were immersed and reacted in an isopropanol solution of diethylenetriamine, and then cross-linked using ethylene glycol diglycidyl ether. The particles were washed with methanol, dried, and classified into particles having a particle diameter of 500 μm to 710 μm using a sieve to obtain a target adsorbent. About this adsorbent, the adsorption | suction performance of the removal target substance in a wine component was evaluated. The results are shown in Table 1. The amount of amino group introduced into the resin constituting the adsorbent was 8.1 mmol / g.

[Example 5]
An ethylene-vinyl alcohol copolymer (Kuraray Co., Ltd., E105 and F101) and a polyethyleneimine having a weight average molecular weight of 10,000 (Nippon Shokubai Co., Ltd., Epomin SP-200) were used. Two types of ethylene-vinyl alcohol copolymers were mixed at a mass ratio of 1: 1, and melt-kneaded at 210 ° C. with a lab plast mill, to which polyethyleneimine contained 25 parts by mass of polyethyleneimine, ethylene- After mixing so that the content of the vinyl alcohol copolymer was 75 parts by mass and kneading for a predetermined time, the resin composition was taken out. The obtained resin composition was pulverized with a pulverizer to form particles. The particles were cross-linked using ethylene glycol diglycidyl ether, dried, and classified into particles having a particle diameter of 212 μm to 500 μm using a sieve to obtain a target adsorbent. About this adsorbent, the adsorption | suction performance of the removal target substance in a wine component was evaluated. The results are shown in Table 1. The amount of amino group introduced into the resin constituting the adsorbent was 5.7 mmol / g.

[Example 6]
An ethylene-vinyl alcohol copolymer (K101, manufactured by Kuraray Co., Ltd.) and polyallylamine having a weight average molecular weight of 15,000 (manufactured by Nittobo Co., Ltd., PAA-15C) were used. An ethylene-vinyl alcohol copolymer is melt-kneaded at 210 ° C. with a lab plast mill, and polyallylamine is contained therein in an amount of 20 parts by mass, and an ethylene-vinyl alcohol copolymer is 80 in content. After mixing so as to be part by mass and kneading for a predetermined time, the resin composition was taken out. The obtained resin composition was pulverized with a pulverizer to form particles. The particles were cross-linked using ethylene glycol diglycidyl ether, dried, and classified into particles having a particle diameter of 300 μm to 500 μm using a sieve to obtain a target adsorbent. About this adsorbent, the adsorption | suction performance of the removal target substance in a wine component was evaluated. The results are shown in Table 1. In addition, the amino group introduction amount of the resin constituting the adsorbent was 3.5 mmol / g.

[Example 7]
Ethylene-vinyl alcohol copolymer (manufactured by Kuraray Co., Ltd., G156), polyethyleneimine having a weight average molecular weight of 10,000 (manufactured by Nippon Shokubai Co., Ltd., Epomin SP-200), and polyallylamine having a weight average molecular weight of 15,000 (Nitto Co., Ltd.) Spun, PAA-15C) was used. An ethylene-vinyl alcohol copolymer is melt-kneaded at 210 ° C. with a lab plast mill, and polyethyleneimine and polyallylamine are mixed therein, and the total content of polyethyleneimine and polyallylamine is 25 parts by mass (of polyethyleneimine and polyallylamine). The mass ratio of polyethyleneimine to the total is 80%), and three types of polymers are mixed and kneaded for a predetermined time so that the content of the ethylene-vinyl alcohol copolymer is 75 parts by mass. I took it out. The obtained resin composition was pulverized with a pulverizer to form particles. The particles were crosslinked using ethylene glycol diglycidyl ether, dried, and classified into particles having a particle diameter of 212 μm to 425 μm using a sieve to obtain a target adsorbent. About this adsorbent, the adsorption | suction performance of the removal target substance in a wine component was evaluated. The results are shown in Table 1. The amount of amino group introduced into the resin constituting the adsorbent was 5.4 mmol / g.

[Example 8]
A slurry was prepared by dispersing fibrillated acrylic fiber bipal (manufactured by Toyobo Co., Ltd.) as a fibrous binder in water at a ratio of 4 parts by mass with respect to 100 parts by mass of the resin constituting the adsorbent obtained in Example 2. . Next, the obtained slurry was put in a double tube container having an outer diameter of 75 mm, an inner diameter of 29 mm and a height of 255 mm having a large number of pores having a diameter of 3 mm, sucked at 350 mmHg, and then compressed at 120 ° C. without compression. After drying for a time, a hollow cylindrical filter having an outer diameter of 65 mm, an inner diameter of 30 mm, and a height of 250 mm was obtained. This filter was loaded in a plastic housing (Advantech Toyo Co., Ltd., 1PP-1-FV) having a total width of 200 mm and a total height of 340 mm, and evaluated according to the evaluation method described above. The results are shown in Table 1.

[Example 9]
A slurry was prepared by dispersing fibrillated acrylic fiber bipal (manufactured by Toyobo Co., Ltd.) as a fibrous binder in water at a ratio of 5 parts by mass with respect to 100 parts by mass of the resin constituting the adsorbent obtained in Example 5. . Next, the obtained slurry was put in a double tube container having an outer diameter of 75 mm, an inner diameter of 29 mm and a height of 255 mm having a large number of pores having a diameter of 3 mm, sucked at 350 mmHg, and then compressed at 120 ° C. without compression. After drying for a time, a hollow cylindrical filter having an outer diameter of 65 mm, an inner diameter of 30 mm, and a height of 250 mm was obtained. This filter was loaded in a plastic housing (Advantech Toyo Co., Ltd., 1PP-1-FV) having a total width of 200 mm and a total height of 340 mm, and evaluated according to the evaluation method described above. The results are shown in Table 1.

[Comparative Example 1]
A commercially available ethylene-vinyl alcohol copolymer (F101, manufactured by Kuraray Co., Ltd.) was pulverized and then classified into particles having a particle diameter of 212 μm to 425 μm using a sieve to obtain the target adsorbent. About this adsorbent, the adsorption | suction performance of the removal target substance in a wine component was evaluated. The results are shown in Table 1.

[Comparative Example 2]
Polyvinyl alcohol (manufactured by Kuraray Co., Ltd., PVA205) and polyethyleneimine having a weight average molecular weight of 10,000 (manufactured by Nippon Shokubai Co., Ltd., Epomin SP-200) were used. A 5% by mass aqueous solution of polyvinyl alcohol was prepared, and polyethyleneimine was mixed therewith so that the content of polyethyleneimine was 25 parts by mass and the content of polyvinyl alcohol was 75 parts by mass, and cast onto a PET film. Thereafter, the film was dried at 20 ° C. for 1 week, and further dried in a vacuum dryer overnight to obtain a film having a thickness of about 150 μm. The film was pulverized with a pulverizer to form particles. The particles were subjected to a crosslinking treatment using ethylene glycol diglycidyl ether, then dried, and classified into particles having a particle diameter of 150 μm to 300 μm using a sieve to obtain a target adsorbent. However, when the adsorbent was packed in a column and immersed in a thermostatic bath, the volume swelling was remarkable and the particles were dissolved and disintegrated.

  As is clear from Table 1, the adsorbent of the present invention had excellent adsorption performance for substances to be removed (such as citric acid and naringin components). In addition, it was revealed that high performance was exhibited even when processed into a filter shape, and it became possible to provide a filter for wine production with excellent handleability. On the other hand, as in Comparative Example 1, the ethylene-vinyl alcohol copolymer having no amino group did not exhibit the ability to adsorb substances to be removed (such as citric acid and naringin components). When a hydrophilic resin was used as a base material as in Comparative Example 2, the resin swelled and partially dissolved upon contact with wine, and the shape could not be maintained.

  ADVANTAGE OF THE INVENTION According to this invention, the novel adsorption material which can be used industrially which is excellent in the adsorption | suction performance (citric acid, a naringin component, etc.) in the wine component can be provided. The adsorbent can be handled more easily by processing it into a filter, for example.

As described above, the preferred embodiments of the present invention have been described. However, various additions, modifications, or deletions are possible without departing from the spirit of the present invention, and such modifications are also included in the scope of the present invention. It is.

Claims (7)

  An adsorbent comprising an ethylene-vinyl alcohol copolymer as a base material and a resin having an amino group introduced therein, which is used for wine production.   The adsorbent according to claim 1, wherein the amino group introduction amount is 2.0 mmol / g to 15 mmol / g with respect to the mass of the resin.   The adsorbent according to claim 1, wherein the adsorbent is a particle having a particle diameter of 10 to 3000 μm.   The adsorbent according to any one of claims 1 to 3, which is porous and has an average diameter of pores formed on the surface of 0.01 to 50 µm.   The filter used for wine manufacture which comprises 2-10 mass parts of binders with respect to 100 mass parts of resin which comprises the adsorbent in any one of Claims 1-4.   A housing loaded with the filter according to claim 5.   The wine manufacturing method using the adsorbent in any one of Claims 1-4, or the filter of Claim 5.