JP2011136760A - Method for preserving alcoholic beverage - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for preserving an alcoholic beverage for a long period of time without spoiling flavor of the alcoholic beverage. <P>SOLUTION: The method for preserving the alcoholic beverage preserves the alcoholic beverage in an oxygen absorbing container using wholly or partly an oxygen absorbing multi-layered body made by piling up at least three layers of an oxygen-permeable layer comprising a thermoplastic resin, an oxygen absorbing resin layer comprising a polyolefin resin, a transition metal catalyst, and a polyamide resin, and a gas barrier layer comprising a gas barrier substance, successively from the inside. In the method for preserving the alcoholic beverage, the polyamide resin is such a resin that is obtained by polycondensation of an aromatic diamine and a dicarboxylic acid and has a terminal amino group concentration of ≤30 μeq/g, and the total content of the transition metal catalyst and the polyamide resin in the oxygen-absorbing resin layer is 15-60 wt.% to the total amount of the oxygen-absorbing resin layer. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a method for preserving an alcoholic beverage for a long period of time by preventing flavor deterioration of the sealed alcoholic beverage.

  There is technology to fill and store alcoholic beverages such as sake, wine and shochu in metal cans and glass bottles, but metal cans and glass bottles are gas barriers due to the problem of incombustible waste disposal and the demand for lighter packaging containers. Transfer to plastic containers such as plastic paper containers has been carried out. Moreover, in a metal can, there also exists a problem which a metal component melt | dissolves in the contents.

  However, when an alcoholic beverage is stored in a gas barrier multilayer body in which ordinary gas barrier films are laminated, no matter how the gas replacement operation is performed, trace oxygen remaining in the packaging container, or trace oxygen dissolved in the alcohol beverage, It is inevitable that flavor deterioration of alcoholic beverages occurs.

  On the other hand, a deoxygenation packaging technique is known as a method for improving food storage stability and preventing flavor changes. In recent years, as one of the deoxygenation packaging technologies, a container is constituted by a multilayer material in which an oxygen absorption layer composed of an oxygen absorption resin composition in which an iron-based oxygen absorber is blended with a thermoplastic resin, and the gas barrier property of the container is increased. Development of a packaging container in which an oxygen absorbing function is imparted to the container itself is being promoted. For example, an oxygen-absorbing multilayer film is a thermoplastic in which an oxygen absorbent is dispersed between a conventional gas-barrier multilayer film in which a heat seal layer and a gas barrier layer are laminated, and optionally through an intermediate layer made of a thermoplastic resin. It is used as a resin layer with an oxygen absorption layer added to the outside to prevent oxygen permeation, and to absorb oxygen in the container. It is manufactured using a method (see Patent Document 1).

  However, those using oxygen absorbers such as iron powder are detected by metal detectors used to detect foreign substances such as food, the internal visibility is insufficient due to the problem of opacity, the contents are alcoholic beverages In some cases, an aldehyde is generated by the reaction between iron and alcohol, which causes a problem that a bad odor is generated.

  In addition, in a composition comprising a polymer and having an oxygen scavenging property, a resin composition comprising a polyamide, particularly a xylylene group-containing polyamide and a transition metal, is known as an oxidizable organic component. There are also examples of oxygen absorbers obtained by molding the resin composition, packaging materials, and multilayer laminated films for packaging (see Patent Documents 2 to 6).

  However, a resin composition containing a transition metal catalyst and oxidizing a polyamide resin or the like to develop an oxygen absorbing function oxidizes the xylylene group-containing polyamide resin, resulting in a decrease in strength due to oxidative degradation of the resin, and the packaging container itself There is a problem that the strength of the glass is reduced.

  Furthermore, there is an example of MXD6, which is a polyamide obtained by polycondensation of metaxylylenediamine and adipic acid, as an example showing an oxidation reaction with a polyamide resin and a transition metal catalyst. In a system in which transition metal is mixed with MXD6, For use as an oxygen-absorbing resin composition and preserving the material to be stored well, the oxygen-absorbing ability may be low. In addition, a system in which transition metal is mixed with MXD6 usually uses a blend of a polyester resin such as polyethylene terephthalate (hereinafter referred to as PET) or a resin having a relatively high melting point such as nylon 6.

Japanese Patent Laid-Open No. 9-234832 Japanese Patent Laid-Open No. 5-140555 JP 2001-252560 A JP 2003-341747 A JP 2005-119893 A JP 2001-179090 A

  An object of the present invention is to provide a method capable of storing an alcoholic beverage for a long period of time without impairing the flavor of the alcoholic beverage.

  That is, the present invention comprises an alcohol beverage, in order from the inside, an oxygen permeable layer made of a thermoplastic resin, an oxygen absorbing resin layer containing a polyolefin resin, a transition metal catalyst, and a polyamide resin, and a gas barrier layer made of a gas barrier material. A method for preserving an alcoholic beverage, which is stored in an oxygen-absorbing container using all or part of an oxygen-absorbing multilayer body formed by laminating three layers, wherein the polyamide resin is composed of an aromatic diamine and a dicarboxylic acid. A terminal amino group concentration obtained by condensation is a polyamide resin having a concentration of 30 μeq / g or less, and the total content of the transition metal catalyst and the polyamide resin in the oxygen-absorbing resin layer is 15 to This is a method for storing an alcoholic beverage that is 60% by weight.

  INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a method capable of storing an alcoholic beverage for a long period of time without impairing the flavor of the alcoholic beverage and generating no off-flavor. In addition, it can replace metal cans and glass bottles, making it possible to reduce the weight of containers and reduce waste and incombustibles. In addition, the packaging container retains strength even after long-term storage.

  The alcoholic beverage of the present invention is a low alcoholic beverage such as a cocktail, distilled liquor (whiskey, rum, cachassa, vodka, gin, tequila, brandy, lac, alac, ouzo, white liquor, shochu, awamori), brewed liquor (beer , Fruit liquor, Shaoxing liquor, Japanese sake), mixed liquor (liqueur), and beverages containing these.

  The oxygen-absorbing multilayer body used in the method for storing an alcoholic beverage according to the present invention comprises an oxygen-permeable layer, an oxygen-absorbing resin layer, and a gas barrier layer laminated in this order, and an oxygen-absorbing resin layer and an aromatic diamine. An oxygen containing a polyamide resin having a terminal amino group concentration of 30 μeq / g or less obtained by polycondensation with a dicarboxylic acid (hereinafter, the polyamide resin is particularly referred to as “polyamide resin A”), a transition metal catalyst, and a polyolefin resin. Absorption multilayer body. The oxygen-absorbing multilayer body of the present invention can also be used for applications that constitute all or part of the container body, lid, and packaging material with the oxygen-permeable layer inside. Details of the oxygen-absorbing multilayer body will be described below.

  The thermoplastic resin used in the oxygen permeable layer of the oxygen-absorbing multilayer body of the present invention includes various materials such as high-density polyethylene, medium-density polyethylene, low-density polyethylene, linear low-density polyethylene, ultra-low-density polyethylene, and polyethylene using a metallocene catalyst. Polypropylenes such as polyethylene, polystyrene, polymethylpentene, propylene homopolymer, propylene-ethylene block copolymer, propylene-ethylene random copolymer can be used alone or in combination. These polyolefin resins include ethylene-vinyl acetate copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, if necessary. A polymer, an ethylene-methyl methacrylate copolymer, or a thermoplastic elastomer may be added. The melt flow rate (hereinafter referred to as MFR) of the thermoplastic resin is 1 to 35 g / 10 min at 200 ° C. and 2 to 45 g / 10 min at 240 ° C., considering the processability of the multilayer body. Preferably used. In addition, MFR as used in this specification is MFR of the said resin measured on the conditions of the load of 2160g in specific temperature using the apparatus based on JISK7210, unless there is particular notice, "g / 10. Expressed with the measured temperature in units of minutes.

  The thermoplastic resin used in the oxygen permeable layer of the oxygen-absorbing multilayer body of the present invention includes color pigments such as titanium oxide, antioxidants, slip agents, antistatic agents, stabilizers, additives such as lubricants, calcium carbonate Further, fillers such as clay, mica and silica, deodorizers and the like may be added. In particular, it is preferable to add an antioxidant in order to recycle and reprocess offcuts generated during production.

In the present invention, the polyolefin resin used in the oxygen-absorbing resin layer includes various polyethylenes such as high-density polyethylene, medium-density polyethylene, low-density polyethylene, linear low-density polyethylene, ultra-low-density polyethylene, and polyethylene using a metallocene catalyst. Polypropylenes such as polystyrene, polymethylpentene, propylene homopolymer, propylene-ethylene block copolymer, propylene-ethylene random copolymer can be used alone or in combination. These polyolefin resins include ethylene-vinyl acetate copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, if necessary. A polymer, an ethylene-methyl methacrylate copolymer, or a thermoplastic elastomer may be added. The polyolefin resin of the oxygen-absorbing resin layer is preferably the same type as the polyolefin resin of the oxygen-permeable layer in view of the processability of the resin and the adhesion with the oxygen-permeable layer. The MFR of the polyolefin resin is preferably 1 to 35 g / 10 minutes at 200 ° C. and 2 to 45 g / 10 minutes at 240 ° C. in consideration of film processability. In terms of oxygen absorption performance, the oxygen permeability coefficient is preferably 80 to 200 cc · mm / (m ² · day · atm) (23 ° C. · 60% RH), and when a polyolefin resin having an oxygen permeability coefficient in this range is used, Good oxygen absorption performance can be obtained.

  In consideration of miscibility with the polyamide resin A, it is particularly preferable to add a maleic anhydride-modified polyolefin resin or an epoxy group-containing modified polyolefin resin to the oxygen-absorbing resin layer. The addition amount of the maleic anhydride-modified polyolefin resin or the epoxy group-containing modified polyolefin resin is preferably 1 to 30 wt%, particularly preferably 3 to 20 wt% with respect to the polyolefin resin.

  The polyolefin resin used in the oxygen-absorbing resin layer of the oxygen-absorbing multilayer body of the present invention includes coloring pigments such as titanium oxide, additives such as antioxidants, slip agents, antistatic agents and stabilizers, calcium carbonate Further, fillers such as clay, mica and silica, deodorizers and the like may be added. In particular, it is preferable to add an antioxidant in order to recycle and reprocess offcuts generated during production.

  Examples of the transition metal catalyst used in the present invention include compounds of a first transition element such as Fe, Mn, Co, and Cu. Further, transition metal organic acid salts, chlorides, phosphates, phosphites, hypophosphites, nitrates and the like alone or a mixture thereof can be cited as examples of transition metal catalysts. Examples of the organic acid include salts of C2-C22 aliphatic alkyl acids such as acetic acid, propionic acid, octanoic acid, lauric acid, stearic acid, or malonic acid, succinic acid, adipic acid, sebacic acid, hexahydrophthalic acid A salt of a dibasic acid, a salt of butanetetracarboxylic acid, benzoic acid, toluic acid, o-phthalic acid, isophthalic acid, terephthalic acid, trimesic acid alone or a mixture thereof. Among the transition metal catalysts, an organic acid salt of Co is preferable from the viewpoint of oxygen absorption, and Co stearate is particularly preferable from the viewpoint of safety and workability.

  The transition metal catalyst is preferably added to the polyamide resin A and then mixed with the polyolefin resin. The transition metal catalyst is preferably added so that the concentration of all transition metals in the catalyst with respect to the polyamide resin A is 10 ppm to 5000 ppm, preferably 50 ppm to 3000 ppm. In this case, compared with the case where the addition amount is out of the above range, the oxygen absorption performance of the polyamide resin A can be improved, and the deterioration of the resin processability due to the decrease in the viscosity can be prevented.

Another method for producing the oxygen-absorbing resin composition of the present invention is preferably a method for producing an oxygen-absorbing resin composition in which a masterbatch containing a polyolefin resin and a transition metal catalyst and a polyamide resin are melt-kneaded.
The transition metal catalyst is kneaded with the polyolefin resin to produce a master batch, and then melt mixed with the polyamide resin A to obtain an oxygen-absorbing resin composition. The transition metal catalyst is added so that the concentration of all transition metals in the catalyst with respect to the polyolefin resin is preferably 200 ppm to 5000 ppm, more preferably 300 ppm to 3000 ppm. In this case, the oxygen absorption performance of the polyamide resin A can be enhanced as compared with the case where the addition amount is out of the above range. Moreover, when it exceeds 5000 ppm, it may become difficult to manufacture a masterbatch, and it may become impossible to manufacture what has a uniform property. If a transition metal catalyst is added to the polyamide resin A, the resin processability is deteriorated due to a decrease in the viscosity of the polyamide resin A.

  The polyamide resin A of the oxygen-absorbing resin layer is at least a polyamide resin having a terminal amino group concentration of 30 μeq / g or less obtained by polycondensation of aromatic diamine and dicarboxylic acid. Details of the polyamide resin A will be described.

  The oxygen absorption performance of the oxygen absorbing resin layer is considered to be better when there are more polyamide resins to which a transition metal having oxygen absorbing ability is added, but surprisingly, the polyamide resin A, the transition metal and the polyolefin resin are mixed, It has been found that when blended at a certain ratio, it exhibits a high oxygen absorption capacity.

  The polyamide resin A in the present invention is obtained by polycondensation of an aromatic diamine and a dicarboxylic acid. The polycondensation of the aromatic diamine and the dicarboxylic acid can be carried out by melt polymerization in which the aromatic diamine and dicarboxylic acid are melted, solid phase polymerization in which the polyamide resin pellets are heated under reduced pressure, or the like.

  Examples of the aromatic diamine in obtaining the polyamide resin A include orthoxylylenediamine, paraxylylenediamine, and metaxylylenediamine, but paraxylylenediamine, metaxylylenediamine, or these from the viewpoint of oxygen absorption performance. A mixture is preferably used, and metaxylylenediamine is particularly preferably used. In addition, various aliphatic diamines and aromatic diamines may be incorporated as copolymerization components as long as the performance is not affected.

  Examples of the dicarboxylic acid for obtaining the polyamide resin A include adipic acid, azelaic acid, sebacic acid, dodecanoic acid, isophthalic acid, terephthalic acid, and malonic acid. Among these, from the viewpoint of oxygen absorption performance, adipic acid, sebacic acid, isophthalic acid or a mixture thereof is preferable, and a mixture of adipic acid and sebacic acid or a mixture of adipic acid and isophthalic acid is particularly preferable. The molar ratio in the case of using a mixture of adipic acid and sebacic acid is preferably sebacic acid: adipic acid = 0.3-0.7: 0.7-0.3, and 0.4-0.6: 0.6 -0.4 is particularly preferred. Further, when using a mixture of adipic acid and isophthalic acid, adipic acid: isophthalic acid is preferably 0.7 to 0.97: 0.3 to 0.03, and 0.8 to 0.95: 0.2 to 0 .05 is particularly preferred. In addition, various aliphatic dicarboxylic acids and aromatic dicarboxylic acids may be incorporated as copolymerization components as long as the performance is not affected.

  The polyamide resin A in the present invention is a polyamide resin having a terminal amino group concentration of 30 μeq / g or less obtained by polycondensation of at least an aromatic diamine and a dicarboxylic acid, but has a terminal amino group concentration of 25 μeq / g or less. And oxygen absorption performance are improved, and it is more preferably 20 μeq / g or less because oxygen absorption performance is further improved. Thus, the oxygen absorption performance tends to improve as the terminal amino group concentration decreases, and it is preferable to reduce the concentration as much as possible. However, in consideration of economic rationality, the lower limit is 5 μeq / g or more. It is preferable to do. If the terminal amino group concentration is higher than 30 μeq / g, good oxygen absorption performance cannot be obtained.

In order to reduce the terminal amino group concentration of the polyamide resin to 30 μeq / g or less,
1) Method for carrying out polycondensation by adjusting the molar ratio of aromatic diamine and dicarboxylic acid 2) Method for reacting polyamide resin with carboxylic acid to seal the terminal amino group 3) Method for solid-phase polymerization of polyamide resin These methods are preferably carried out, and these methods can be carried out alone or in combination. In particular, the combination of the methods 1), 3), 2) and 3) is preferable because a polyamide resin having better oxygen absorption performance and moldability at the time of producing a multilayer body can be obtained. The following describes these methods.

  1) In the method of carrying out polycondensation by adjusting the molar ratio of aromatic diamine and dicarboxylic acid, dicarboxylic acid is used excessively with respect to aromatic diamine. Specifically, aromatic diamine and dicarboxylic acid are used. The molar ratio (aromatic diamine / dicarboxylic acid) is preferably 0.985 to 0.997, particularly preferably 0.988 to 0.995. When the molar ratio is less than 0.985, it is difficult to increase the degree of polymerization of the polyamide resin.

  2) In the method of reacting the polyamide resin with carboxylic acid to seal the terminal amino group, the terminal amino group concentration of the polyamide resin is reacted with the carboxylic acid to adjust the terminal amino group concentration. The carboxylic acid to be used is not particularly limited, but a carboxylic anhydride is preferable, and specifically, phthalic anhydride, maleic anhydride, benzoic anhydride, glutaric anhydride, itaconic anhydride, citraconic anhydride, acetic anhydride, anhydrous Examples include butyric acid, isobutyric anhydride, trimellitic anhydride, pyromellitic anhydride, and the like. The polyamide resin and the carboxylic acid can be reacted by, for example, a method of adding at the time of melt polymerization or a method of adding a carboxylic acid to the polyamide resin obtained by melt polymerization and then melt-kneading the polyamide resin. In order to increase the degree of polymerization, melt kneading is preferred.

  3) In the method of solid-phase polymerization of polyamide resin, the terminal amino group concentration is adjusted by further subjecting the polyamide resin obtained by melt polymerization to a solid-phase polymerization reaction. Solid phase polymerization proceeds by heating polyamide resin pellets under reduced pressure. The pressure during the solid phase polymerization is preferably 100 torr or less, and more preferably 30 torr or less. Further, the temperature at the time of solid phase polymerization needs to be 130 ° C. or higher, more preferably 150 ° C. or higher, and preferably 10 ° C. or higher, more preferably 15 ° C. or lower than the melting point of the polyamide resin. The solid state polymerization time is preferably 3 hours or more. By performing solid phase polymerization, the terminal amino group concentration of the polyamide resin is decreased, the molecular weight is increased, and the viscosity can be adjusted.

  As the polyamide resin A of the present invention, those having low crystallinity are preferably used. Specifically, those having a low crystallinity with a half-crystallization time of 150 seconds or more, or those having no melting point peak when the melting point is measured by DSC are preferable. When the half crystallization time of the polyamide resin A is 150 seconds or more, higher oxygen absorption performance can be obtained.

  Further, the polyamide resin A preferably has a low melting point and glass transition temperature (hereinafter referred to as Tg) in consideration of processability and oxygen absorption performance with a polyolefin resin. The melting point of the polyamide resin A is preferably 200 ° C. or lower, more preferably 190 ° C. or lower or a resin having no melting point. Tg is preferably 90 ° C. or lower, and particularly preferably 80 ° C. or lower.

The oxygen permeability coefficient of the polyamide resin A is preferably 0.2 to 1.5 cc · mm / (m ² · day · atm) (23 ° C. · 60% RH), and 0.3 to 1.0 cc · mm / (m ² · day · atm) (23 ° C. · 60% RH) is more preferable. When the oxygen permeability coefficient is 0.2 to 1.5 cc · mm / (m ² · day · atm) (23 ° C. · 60% RH), when the polyamide resin A and the polyolefin resin are blended, higher oxygen absorption performance is obtained. can get.

  When polyamide resin A and polyolefin resin are mixed, considering the processability, the MFR of polyamide resin A is preferably 3 to 20 g / 10 min at 200 ° C. and 4 to 25 g / 10 min at 240 ° C. It is done. In this case, when the resin is processed at a temperature where the difference between the MFR of the polyolefin resin and the MFR of the polyamide resin A is ± 20 g / 10 minutes, preferably ± 10 g / 10 minutes, the kneaded state becomes good, and a film or sheet is obtained. In this case, a processed product having no problem in appearance can be obtained. The MFR of the polyamide resin A can be adjusted by adjusting the molecular weight, for example. Examples of a method for adjusting the molecular weight include a method of adding a phosphorus compound as a polymerization accelerator and a method of solid-phase polymerization after melt polymerization of the polyamide resin A.

  The polyamide resin A obtained by polycondensation of an aromatic diamine and a dicarboxylic acid is preferably synthesized by a method that undergoes two steps of solid phase polymerization after melt polymerization. The number average molecular weight of the polyamide resin A is preferably 18000 to 27000, particularly preferably 20000 to 26000.

  You may add a stabilizer etc. to the polyamide resin A obtained by this invention suitably. In particular, phosphorus compounds are preferably used as stabilizers, and specifically, diphosphites are preferable. The phosphorus compound is preferably not more than 200 ppm, particularly preferably not more than 100 ppm because the polyamide resin A is stable and affects the oxygen absorption performance.

  The total content of the transition metal catalyst and the polyamide resin A in the oxygen absorbing resin layer is 15 to 60% by weight, preferably 17 to 60% by weight, more preferably 20 to 60% by weight, and 25 to 50% by weight. Particularly preferred. When the content of the polyamide resin A containing the transition metal catalyst in the oxygen-absorbing resin composition is less than 15% by weight or exceeds 60% by weight, the oxygen-absorbing ability is lowered. On the other hand, if it exceeds 60% by weight, resin degradation due to oxidation of the polyamide resin A occurs, causing problems such as strength reduction.

  When the master batch of the present invention and the polyamide resin A are melt-kneaded, the content of the polyamide resin A and the transition metal concentration can be adjusted by simultaneously adding the polyolefin resin.

  As the gas barrier material used in the gas barrier layer of the present invention, a gas barrier thermoplastic resin, a gas barrier thermosetting resin, various deposited films such as silica, alumina, and aluminum, and a metal foil such as an aluminum foil can be used. Examples of the gas barrier thermoplastic resin include ethylene-vinyl alcohol copolymer, MXD6, and polyvinylidene chloride. Examples of the gas barrier thermosetting resin include a gas barrier epoxy resin such as “MAXIVE” manufactured by Mitsubishi Gas Chemical Co., Ltd.

  Although there is no restriction | limiting in particular in the thickness of an oxygen absorption resin layer, 5-200 micrometers is preferable and 10-100 micrometers is especially preferable. In this case, as compared with the case where the thickness is out of the above range, the oxygen absorbing resin layer can further improve the performance of absorbing oxygen and can prevent the workability and the economy from being impaired. Further, the thickness of the oxygen permeable layer is preferably less because the oxygen permeable layer becomes an isolation layer from the oxygen absorbing resin layer, but is preferably 5 to 200 μm, particularly preferably 10 to 80 μm. In this case, as compared with the case where the thickness is out of the above range, the oxygen absorption rate of the oxygen-absorbing resin layer can be further increased, and the workability can be prevented from being impaired.

  As the gas barrier resin, the thickness when the thermoplastic resin is used for the gas barrier layer is preferably 5 to 200 μm, particularly preferably 10 to 100 μm. Further, when a thermosetting resin such as an amine-epoxy curing agent is used for the gas barrier adhesive layer as the gas barrier resin, 0.1 to 100 μm is preferable, and 0.5 to 20 μm is particularly preferable. When the thickness is within the above range, the gas barrier property can be further improved and the workability and economy can be prevented from being impaired as compared with the case where the thickness is not within the above range.

  Considering the workability of the oxygen-absorbing multilayer body, the thickness ratio of the oxygen-permeable layer and the oxygen-absorbing resin layer is preferably 1: 0.5 to 1: 3, and 1: 1.5 to 1: 2.5. Is particularly preferred. Furthermore, in consideration of processability, it is preferable to interpose an intermediate layer made of polyolefin resin between the gas barrier layer and the oxygen-absorbing resin layer. The thickness of the intermediate layer is preferably substantially the same as the thickness of the oxygen permeable layer in view of workability. In this case, considering variations due to processing, the thickness is the same if the thickness ratio is within ± 10%.

  The oxygen-absorbing multilayer body of the present invention has at least three layers: an oxygen-permeable layer made of a thermoplastic resin, an oxygen-absorbing resin layer containing at least a polyolefin resin, a transition metal catalyst and a polyamide resin A, and a gas barrier layer made of a gas barrier material. Although they are laminated in this order, other layers may be added.

  For example, in order to prevent damage to the gas barrier layer and pinholes, it is preferable to provide a protective layer made of a thermoplastic resin inside and outside the gas barrier layer. Examples of the resin used for the protective layer include polyethylenes such as high density polyethylene, polypropylenes such as propylene homopolymer, propylene-ethylene random copolymer, propylene-ethylene block copolymer, nylon 6, nylon 6,6 and the like. Polyamides, polyesters such as PET, and combinations thereof.

  About the manufacturing method of an oxygen absorption multilayer body, well-known methods, such as a co-extrusion method, various lamination methods, and various coating methods, can be utilized according to the property of various materials, the process objective, a process process, etc. For example, for film or sheet molding, a resin composition melted through a T die, a circular die, or the like is extruded from an attached extruder, or an oxygen absorbing film or sheet is coated with an adhesive. There is a method of manufacturing by bonding to a film or sheet. In addition, by using an injection machine, molten resin can be molded into a multilayer container having a predetermined shape by co-injection or sequential injection into an injection mold through a multilayer multiple die.

  The oxygen-absorbing multilayer body of the present invention can be prepared as a film, processed into a bag shape and a lid material, and used. Moreover, a paper base material can be laminated | stacked on the outer layer of a gas barrier layer, and it can also be used as an oxygen absorptive paper container. In consideration of processability when laminated with a paper base material to obtain a paper container, the inner portion of the gas barrier layer is preferably 60 μm or less, particularly preferably 50 μm or less. When the internal thickness is larger than that of the gas barrier layer, a problem arises in processability to a container when a paper base material is laminated and formed into a container shape.

  Further, the oxygen-absorbing multilayer body of the present invention is produced as a sheet and thermoformed into an oxygen-absorbing container having a predetermined shape such as a tray, a cup, a bottle, or a tube by a forming method such as vacuum forming, pressure forming, or plug assist forming. can do. Moreover, the obtained oxygen absorptive container can perform 80-100 degreeC boil sterilization process, 100-135 degreeC semi-retort sterilization process, a retort sterilization process, and a high retort sterilization process.

  Alcohol drinks are laminated in order from the inside, at least three layers: an oxygen permeable layer made of a thermoplastic resin, an oxygen absorbing resin layer containing a polyamide resin A, a transition metal catalyst and a polyolefin resin, and a gas barrier layer made of a gas barrier material. The oxygen-absorbing multilayer body is sealed in an oxygen-absorbing container using all or part of the oxygen-absorbing multilayer body and stored. Thereby, in addition to oxygen that slightly enters from the outside of the container, oxygen in the container can be absorbed, and deterioration of the contents stored in the container due to oxygen can be prevented. In addition, by using a member having transparency, the contents can be confirmed without opening the packaging container, and the packaging container is easy to handle.

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto. In the examples and comparative examples, various physical property values were measured by the following measuring methods and measuring apparatuses.

(Measurement method of Tg)
Tg was measured according to JIS K7122. The measuring apparatus used was “DSC-60” manufactured by Shimadzu Corporation.

(Measuring method of melting point)
The melting point was determined by measuring the DSC melting peak temperature according to ISO11357. The measuring apparatus used was “DSC-60” manufactured by Shimadzu Corporation.

(Measurement method of number average molecular weight)
The number average molecular weight was measured by GPC-LALLS. As a measuring apparatus, “Shodex GPC-2001” manufactured by Showa Denko KK was used.

(Measurement method of MFR)
The MFR of each resin is measured under a load of 2160 g at a specific temperature using an apparatus in accordance with JIS K7210 (“Melt Indexer” manufactured by Toyo Seiki Seisakusho Co., Ltd.), and the value is described together with the temperature. (Unit: “g / 10 min”). In addition, when MFR was measured based on JISK7210, it was described that much.

(Measurement method of oxygen permeability coefficient)
The oxygen transmission coefficient was measured using “OX-TRAN-2 / 21” manufactured by MOCON under the conditions of 23 ° C., 60% RH and a cell area of 50 cm ² .

(Method for measuring terminal amino group concentration)
0.5 g of sample was dissolved in 30 mL of phenol / ethanol = 4/1 (volume ratio), 5 mL of methanol was added, and an automatic titrator with 0.01 N hydrochloric acid as a titrant (“COM-2000” manufactured by Hiranuma Seisakusho) Titration with The same operation titrated without adding a sample was used as a blank, and the terminal amino group concentration was calculated from the following formula.
Terminal amino group concentration (μeq / g) = (A−B) × f × 10 / C
(A: titer (mL), B: blank titer (mL), f: factor of normal solution, C: sample amount (g)).

(Measurement method of terminal carboxyl concentration)
0.5 g of a sample was dissolved in 30 mL of benzyl alcohol, 10 mL of methanol was added, and titrated with an automatic titration apparatus (“COM-2000” manufactured by Hiranuma Seisakusho) with 0.01 N sodium hydroxide solution as a titrant. The same operation titrated without adding a sample was used as a blank, and the terminal carboxyl concentration was calculated from the following formula.
Terminal carboxyl group concentration (μeq / g) = (A−B) × f × 10 / C
(A: titer (mL), B: blank titer (mL), f: factor of normal solution, C: sample amount (g)).

(Measurement method of semi-crystallization time)
When the pellet is melted at each temperature and the resin is crystallized at each temperature, the time for all to crystallize is called the crystallization time, and the time for reaching 50% crystallization is called the semi-crystallization time. The half crystallization time was measured by the depolarized intensity method. That is, when the sample pellets are irradiated with light and the sample pellets are crystallized, the amount of light transmission decreases and becomes stable when the amount of light transmission is stabilized. The time is defined as the crystallization time, and the amount of light transmission is 50%. The time to reach was defined as the half crystallization time. Although the crystallization time and the half crystallization time differ depending on the measurement temperature, in the following description, among the half crystallization times at each temperature, the one with the shortest half crystallization time is referred to as “half crystallization time”. Described. In addition, a “polymer crystallization rate measuring apparatus MK-701 type” manufactured by Kotaki was used to measure the crystallization time and the semi-crystallization time.

(Synthesis conditions by melt polymerization of polyamide resin)
After heating and melting the dicarboxylic acid in a reaction can at 170 ° C., the aromatic diamine is gradually and continuously added so that the molar ratio of the dicarboxylic acid to the dicarboxylic acid is about 1: 1 while stirring the contents. And the temperature was raised to 240 ° C. After completion of the dropwise addition, the temperature was raised to 260 ° C. or higher and the reaction was continued. After completion of the reaction, the inside of the reaction can was slightly pressurized with nitrogen, the strand was extruded from a die head having holes, and pelletized with a pelletizer.

(Synthesis conditions by solid phase polymerization of polyamide resin)
The pellets obtained by melt polymerization by the above method were charged into a rotary tumbler equipped with a heating device, the pressure inside the tumbler was reduced to 1 torr or less while rotating, and the operation of bringing the pressure to normal pressure with nitrogen was performed three times. Thereafter, the inside of the apparatus was heated while rotating the tumbler to 30 torr or less, the inside of the apparatus was adjusted to 150 ° C. or more, and the reaction was performed at that temperature for a predetermined time. Then, it cooled to 60 degreeC and obtained the polyamide resin.

(Example 1)
Polyamide resin was synthesized by performing melt polymerization and solid phase polymerization under the above-mentioned synthesis conditions using metaxylylenediamine: sebacic acid: adipic acid in a molar ratio of 0.994: 0.4: 0.6. (Hereinafter, the polyamide resin is referred to as polyamide 1). The dropping time was 2 hours, the reaction time for melt polymerization was 1 hour, the pressure in the apparatus during solid phase polymerization was 1 torr or less, the polymerization temperature was 160 ° C., and the polymerization time was 4 hours. Polyamide 1 has a Tg of 73 ° C., a melting point of 184 ° C., a crystallization time of 2000 seconds or more, a terminal amino group concentration of 17.2 μeq / g, a terminal carboxyl group concentration of 65.5 μeq / g, a number average molecular weight of 24200, and an MFR of 240 ° C. It was 10.9 g / 10 minutes. Moreover, when the unstretched film was produced with the obtained polyamide 1 single-piece | unit and the oxygen permeability coefficient was calculated | required, it was 0.34cc * mm / (m < ² > * day * atm) (23 degreeC * 60% RH). . These results are shown in Table 1.

  Cobalt stearate was added to polyamide 1 as a transition metal catalyst by a side feed to molten polyamide 1 with a twin screw extruder so as to have a cobalt concentration of 300 ppm. Further, a mixture of the obtained polyamide and cobalt stearate (hereinafter referred to as cobalt stearate-containing polyamide 1) was added to a linear low density polyethylene (product name: “Kernel KF380” manufactured by Nippon Polyethylene Co., Ltd.), MFR4. 0 g / 10 min (measured according to JIS K7210), 240 ° C. MFR 8.7 g / 10 min, 250 ° C. MFR 10.0 g / 10 min, hereinafter referred to as LLDPE1), cobalt stearate-containing polyamide 1: LLDPE1 = 40: 60 weight ratio was melt-kneaded at 240 ° C. to obtain pellets composed of the oxygen-absorbing resin composition A.

The obtained composition A was used as an oxygen-absorbing resin layer, linear low-density polyethylene (product name; “ELITE 5220G” manufactured by Dow Chemical Company, MFR 3.5 g / 10 minutes (measured in accordance with JIS K7210), 240 ° C. Two-layer three-layer film (thickness; intermediate layer LLDPE2 layer 10 μm / oxygen) using MFR 8.4 g / 10 min, 250 ° C. MFR 9.1 g / 10 min, hereinafter referred to as LLDPE2) as an oxygen permeable layer and an intermediate layer Absorbing resin layer 20 μm / oxygen permeable layer LLDPE2 layer 10 μm) was subjected to corona discharge treatment at a width of 1000 mm and an intermediate layer surface at 80 m / min to produce a film roll. The film roll had no uneven thickness such as bumps, the appearance of the obtained film was good, and the HAZE was 15%. This film is laminated on the intermediate layer side by extrusion lamination with low-density polyethylene (product name: “Harmolex NH745N” manufactured by Nippon Polyethylene Co., Ltd.), and bleached kraft paper (basis weight 330 g / m ² ) / urethane-based dry Laminating adhesive (Product name: “AD817 / CAT-RT86L-60”, 3) manufactured by Toyo Morton Co., Ltd./Alumina-deposited PET film (Product name: “GL-AEC-F” manufactured by Toppan Printing Co., Ltd.), 12 ) / Urethane anchor coating agent (“EL-530A / B” manufactured by Toyo Morton Co., Ltd., 0.5) / Low density polyethylene (20) / LLDPE2 (10) / Oxygen absorbing resin composition (20) / LLDPE2 ( 10) The oxygen-absorbing paper base laminate was obtained. Using this laminate, a Gobeltop-type oxygen-absorbing paper container 1 having a bottom 7 cm square and a capacity of 1000 mL was obtained. The processability of the paper container could be made without any problem.

  This oxygen-absorbing paper container 1 was filled with 1000 mL of rice shochu so that the amount of air in the headspace was 20 cc, and stored at 40 ° C., and the headspace oxygen concentration on the seventh day and the wine flavor after one month were investigated. . In addition, the seal strength of the upper part of the gobeltop paper container after one month was measured.

(Example 2)
The oxygen-absorbing paper container was boxed in the same manner as in Example 1 except that the weight ratio at the time of melt kneading was changed to cobalt stearate-containing polyamide 1: LLDPE1 = 55: 45, and the flavor of the rice shochu and the headspace oxygen concentration And the heat-sealing strength of the upper part of the paper container was examined. These results are shown in Table 2.

(Example 3)
The oxygen-absorbing paper container was made in the same manner as in Example 1 except that the weight ratio at the time of melt kneading was changed to cobalt stearate-containing polyamide 1: LLDPE1 = 20: 80, and the flavor of rice shochu and the headspace oxygen concentration And the heat-sealing strength of the upper part of the paper container was examined. These results are shown in Table 2.

Example 4
The oxygen-absorbing paper container was boxed in the same manner as in Example 1 except that the weight ratio at the time of melt kneading was changed to cobalt stearate-containing polyamide 1: LLDPE1 = 17: 83, and the flavor of rice shochu and headspace oxygen concentration And the heat-sealing strength of the upper part of the paper container was examined. These results are shown in Table 2.

(Example 5)
Polyamide resin was synthesized by performing melt polymerization and solid phase polymerization under the above-mentioned synthesis conditions using metaxylylenediamine: sebacic acid: adipic acid in a molar ratio of 0.994: 0.3: 0.7. (Hereinafter, the polyamide resin is referred to as polyamide 2). The dropping time was 2 hours, the reaction time for melt polymerization was 1 hour, the pressure in the apparatus during solid phase polymerization was 1 torr or less, the polymerization temperature was 160 ° C., and the polymerization time was 4 hours. Polyamide 2 has a Tg of 78 ° C., a melting point of 194 ° C., a semicrystallization time of 2000 seconds or more, a terminal amino group concentration of 15.4 μeq / g, a terminal carboxyl group concentration of 67.1 μeq / g, a number average molecular weight of 24200, and an MFR of 240 ° C. It was 11.0 g / 10 minutes. In addition, an unstretched film was prepared from the obtained polyamide 2 alone, and its oxygen permeability coefficient was determined to be 0.21 cc · mm / (m ² · day · atm) (23 ° C. · 60% RH). . These results are shown in Table 1.

  Thereafter, in the same manner as in Example 1, cobalt stearate was added so as to have a cobalt concentration of 300 ppm, and the resulting polyamide 2 and cobalt stearate mixture (hereinafter referred to as cobalt stearate-containing polyamide 2) was added to LLDPE1. Was melt-kneaded at a weight ratio of cobalt stearate-containing polyamide 2: LLDPE1 = 40: 60 at 240 ° C. to obtain oxygen-absorbing resin pellets. Furthermore, after obtaining an oxygen-absorbing paper base laminate in the same manner as in Example 1, an oxygen-absorbing paper container was boxed, and the same storage test as in Example 1 was performed. These results are shown in Table 2.

(Example 6)
Polyamide resin was synthesized by performing melt polymerization and solid phase polymerization under the above-described synthesis conditions using metaxylylenediamine: adipic acid in a molar ratio of 0.994: 1 (hereinafter, the polyamide resin was referred to as polyamide 3). ). The dropping time was 2 hours, the reaction time for melt polymerization was 1 hour, the pressure in the apparatus during solid phase polymerization was 1 torr or less, the polymerization temperature was 205 ° C., and the polymerization time was 4 hours. This polyamide 3 had a Tg of 84 ° C., a melting point of 237 ° C., a half crystallization time of 25 seconds, a terminal amino group concentration of 16.0 μeq / g, a terminal carboxyl group concentration of 66.9 μeq / g, and a number average molecular weight of 24100. Moreover, since it was near melting | fusing point at 240 degreeC, MFR was not able to be measured, MFR of 250 degreeC was measured, and MFR in 250 degreeC was 14.5 g / 10min. An unstretched film was produced from the obtained polyamide 3 alone, and the oxygen permeability coefficient was determined. The oxygen permeability coefficient was 0.09 cc · mm / (m ² · day · atm) (23 ° C. · 60% RH). there were. These results are shown in Table 1.

  Thereafter, addition of cobalt stearate to polyamide 3 and melt-kneading with LLDPE 1 were carried out in the same manner as in Example 1 except that the temperature during melt-kneading was changed to 250 ° C. After obtaining the absorbent paper base laminate, an oxygen-absorbing paper container was boxed and the same storage test as in Example 1 was performed. These results are shown in Table 2.

(Example 7)
Metaxylylenediamine and paraxylylenediamine are mixed at a ratio of 8: 2, these diamines and adipic acid are used in a molar ratio of 1: 1, and only a melt polymerization is performed under the above synthesis conditions to obtain a polyamide resin. After the synthesis, 0.3 wt% of phthalic anhydride was added and melt kneaded at 270 ° C. with a twin-screw extruder to seal the terminal amino group (hereinafter, the polyamide resin is referred to as polyamide 4). However, the dropping time was 2 hours, the polymerization temperature after completion of dropping of the diamine mixture in melt polymerization was 270 ° C., and the reaction time was 30 minutes. Polyamide 4 had a Tg of 85 ° C., a melting point of 255 ° C., a half-crystallization time of 22 seconds, a terminal amino group concentration of 23.0 μeq / g, a terminal carboxyl group concentration of 65.5 μeq / g, and a number average molecular weight of 19,200. Moreover, since it was near melting | fusing point at 260 degreeC, MFR was not able to be measured, MFR of 270 degreeC was measured, and MFR in 270 degreeC was 32.8 g / 10min. An unstretched film was prepared from the obtained polyamide 4 alone, and the oxygen permeability coefficient was determined. The oxygen permeability coefficient was 0.13 cc · mm / (m ² · day · atm) (23 ° C. · 60% RH). there were. These results are shown in Table 1.

  Thereafter, addition of cobalt stearate to polyamide 4 and melt-kneading with LLDPE 1 were carried out in the same manner as in Example 1 except that the temperature at the time of melt-kneading was changed to 270 ° C. After obtaining the absorbent paper base laminate, an oxygen-absorbing paper container was boxed and the same storage test as in Example 1 was performed. These results are shown in Table 2.

(Example 8)
Polyamide resin was synthesized by using melt polymerization and solid phase polymerization under the above-mentioned synthesis conditions using metaxylylenediamine: adipic acid: isophthalic acid in a molar ratio of 0.994: 0.95: 0.05. (Hereinafter, the polyamide resin is referred to as polyamide 5). The dropping time was 2 hours, the reaction time for melt polymerization was 1 hour, the pressure in the apparatus during solid phase polymerization was 1 torr or less, the polymerization temperature was 205 ° C., and the polymerization time was 4 hours. This polyamide 4 had a Tg of 92 ° C., a melting point of 232 ° C., a half crystallization time of 220 seconds, a terminal amino group concentration of 16.7 μeq / g, a terminal carboxyl group concentration of 64.8 μeq / g, and a number average molecular weight of 24,500. Since it was near melting | fusing point in 240 degreeC, MFR was not measurable, MFR of 250 degreeC was measured, and MFR in 250 degreeC was 12.9 g / 10min. An unstretched film was prepared from the obtained polyamide 5 alone, and the oxygen permeability coefficient was determined. The oxygen permeability coefficient was 0.08 cc · mm / (m ² · day · atm) (23 ° C. · 60% RH). there were. These results are shown in Table 1.

  Thereafter, the addition of cobalt stearate to polyamide 5 and melt-kneading with LLDPE 1 were carried out in the same manner as in Example 1 except that the temperature during melt-kneading was 250 ° C. After obtaining the absorbent paper base laminate, an oxygen-absorbing paper container was boxed and the same storage test as in Example 1 was performed. These results are shown in Table 2.

Example 9
Cobalt stearate was added to LLDPE1 by a side feed to the melted LLDPE1 with a twin screw extruder so that the cobalt concentration became 800 ppm. Furthermore, polyamide 1 was melt-kneaded at 240 ° C. in a weight ratio of polyamide 1: cobalt stearate-containing LLDPE1 = 40: 60 to the obtained mixture of LLDPE1 and cobalt stearate to obtain oxygen-absorbing resin pellets.

  Thereafter, after obtaining an oxygen-absorbing paper base laminate in the same manner as in Example 1, the oxygen-absorbing paper container was boxed, and the same storage test as in Example 1 was performed. These results are shown in Table 2.

(Comparative Example 1)
The oxygen-absorbing paper base laminate was produced in the same manner as in Example 1 except that the weight ratio at the time of melt-kneading was changed to cobalt stearate-containing polyamide 1: LLDPE1 = 80: 20. Then, the same storage test as in Example 1 was performed. These results are shown in Table 2.

(Comparative Example 2)
An oxygen-absorbing paper base laminate was produced in the same manner as in Example 1 except that the weight ratio at the time of melt-kneading was changed to cobalt stearate-containing polyamide 1: LLDPE1 = 10: 90. Then, the same storage test as in Example 1 was performed. These results are shown in Table 2.

(Comparative Example 3)
A polyamide resin was synthesized in the same manner as in Example 6 except that metaxylylenediamine: adipic acid was used in a molar ratio of 1: 1 (hereinafter, the polyamide resin is referred to as polyamide 6). This polyamide 6 had a Tg of 84 ° C., a melting point of 237 ° C., a half crystallization time of 25 seconds, a terminal amino group concentration of 41.0 μeq / g, a terminal carboxyl group concentration of 42.5 μeq / g, and a number average molecular weight of 24,000. Moreover, since it was near melting | fusing point at 240 degreeC, MFR was not measurable, MFR of 250 degreeC was measured, and MFR in 250 degreeC was 13.9 g / 10min. An unstretched film was prepared from the obtained polyamide 6 alone, and the oxygen permeability coefficient was determined. The oxygen permeability coefficient was 0.09 cc · mm / (m ² · day · atm) (23 ° C. · 60% RH). there were. These results are shown in Table 1.

  Thereafter, in the same manner as in Example 6, addition of cobalt stearate to polyamide 6, melt kneading with LLDPE1, etc. were carried out to produce an oxygen-absorbing paper base laminate as in Example 1, and then oxygen absorption The paper container was boxed and the same storage test as in Example 1 was performed. These results are shown in Table 2.

(Comparative Example 4)
A polyamide resin was synthesized in the same manner as in Example 6 except that metaxylylenediamine: adipic acid was used in a molar ratio of 0.994: 1 and the polymerization time for solid phase polymerization was 1 hour (hereinafter referred to as “polyamide resin”). The polyamide resin is expressed as polyamide 7). This polyamide 7 had a Tg of 84 ° C., a melting point of 237 ° C., a half crystallization time of 25 seconds, a terminal amino group concentration of 35.9 μeq / g, a terminal carboxyl group concentration of 89.0 μeq / g, and a number average molecular weight of 16000. Moreover, since it was near melting | fusing point at 240 degreeC, MFR was not able to be measured, MFR of 250 degreeC was measured, and MFR in 250 degreeC was 45.2 g / 10min. An unstretched film was prepared from the obtained polyamide 7 alone, and the oxygen permeability coefficient was determined. The oxygen permeability coefficient was 0.09 cc · mm / (m ² · day · atm) (23 ° C. · 60% RH). there were. These results are shown in Table 1.

  Thereafter, in the same manner as in Example 6, cobalt stearate was added to polyamide 7 and melt kneading with LLDPE 1 was carried out to produce an oxygen-absorbing paper base laminate in the same manner as in Example 1. The paper container was boxed and the same storage test as in Example 1 was performed. These results are shown in Table 2.

  As is clear from Examples 1 to 9, the oxygen-absorbing multilayer body of the present invention was excellent in oxygen-absorbing performance, satisfactorily maintained in the flavor of rice shochu, and suitable for storing rice shochu.

  On the other hand, the comparative example 1 in which the content of the polyamide resin A in the oxygen-absorbing resin layer exceeded 60% by weight and the comparison in which the content of the polyamide resin A in the oxygen-absorbing resin layer was less than 15% by weight In Example 2, the oxygen absorption function was insufficient, and the flavor of rice shochu decreased.

  On the other hand, compared with Example 6, in Comparative Example 3 in which the molar ratio of MXDA to adipic acid was increased and in Comparative Example 4 in which the solid phase polymerization time was shortened, the terminal amino group concentration exceeded 30 μeq / g, Absorption function was insufficient, and the flavor of rice shochu decreased.

(Comparative Example 5)
Iron powder having an average particle size of 25 μm and calcium chloride were mixed at a ratio of 100: 1 and kneaded at a weight ratio of LLDPE1 of 30:70 to obtain an iron powder-based oxygen-absorbing resin composition A. The iron powder-based oxygen-absorbing resin composition A was used as a core layer, and an attempt was made to produce a two-layer / three-layer film in the same manner as in Example 1. However, irregularities of the iron powder occurred on the film surface, and no film was obtained. Therefore, an iron powder-based oxygen-absorbing resin composition A was extruded and laminated at a thickness of 30 μm as an oxygen-absorbing resin layer onto a 40 μm-thick LLDPE2 film, and a laminate film was obtained in which the oxygen-absorbing resin layer surface was subjected to corona discharge treatment. This laminate film was laminated with bleached kraft paper and the like as in Example 1, and bleached kraft paper / urethane-based dry laminate adhesive (3) / alumina-deposited PET film (12) / urethane-based anchor coating agent (0.5). An attempt was made to produce a gobeltop oxygen-absorbing paper container comprising an oxygen-absorbing paper base laminate of low density polyethylene (20) / iron powder-based oxygen-absorbing resin composition A (30) / LLDPE2 (40). However, the thickness is large, and it is difficult to produce the corners of the paper container. The container production speed was reduced and defective products were finally removed to obtain a container. Thereafter, a preservation test of rice shochu was conducted in the same manner as in Example 1. However, an aldehyde odor was generated at the time of opening, and the flavor was significantly reduced.

  According to the present invention, an alcoholic beverage, in order from the inside, an oxygen permeable layer made of a thermoplastic resin, an oxygen absorbing resin layer containing a polyolefin resin, a transition metal catalyst, and a polyamide resin, and a gas barrier layer made of a gas barrier material. This is a method for storing an alcoholic beverage, which is stored in an oxygen-absorbing container using all or part of an oxygen-absorbing multilayer body in which layers are laminated.

Claims (6)

  Alcohol drinks are laminated in order from the inside, at least three layers: an oxygen permeable layer made of a thermoplastic resin, an oxygen absorbing resin layer containing a polyolefin resin, a transition metal catalyst, and a polyamide resin, and a gas barrier layer made of a gas barrier material. A method for storing alcoholic beverages, which is stored in an oxygen-absorbing container using all or part of the oxygen-absorbing multilayer body, wherein the polyamide resin is obtained by polycondensation of an aromatic diamine and a dicarboxylic acid. It is a polyamide resin having an amino group concentration of 30 μeq / g or less, and the total content of the transition metal catalyst and the polyamide resin in the oxygen-absorbing resin layer is 15 to 60% by weight with respect to the total amount of the oxygen-absorbing resin layer How to store alcoholic beverages.   The storage method according to claim 1, wherein adipic acid, sebacic acid, isophthalic acid or a mixture thereof is used as the dicarboxylic acid.   3. The preservation method according to claim 1, wherein paraxylylenediamine, metaxylylenediamine, or a mixture thereof is used as the aromatic diamine.   The storage method according to any one of claims 1 to 3, wherein the transition metal catalyst is cobalt stearate.   5. The molar ratio of the dicarboxylic acid in obtaining the polyamide resin is sebacic acid: adipic acid = 0.3 to 0.7: 0.7 to 0.3. 5. The storage method described in 1.   The molar ratio of the dicarboxylic acid when obtaining the polyamide resin is set to adipic acid: isophthalic acid = 0.7 to 0.97: 0.3 to 0.03. The storage method described in 1.