JP2011131583A - Oxygen absorbing multilayered body - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an oxygen absorbing multilayered body excellent in resin processability and oxygen absorbing performance. <P>SOLUTION: The oxygen absorbing multilayered body is formed by laminating at least four layers of (A) a sealant layer containing a polyolefin resin, (B) an oxygen absorbing layer formed of an oxygen absorbing resin composition containing the polyolefin resin, a transition metal catalyst, and a polyamide resin, (C) an epoxy resin cured product layer obtained by curing an epoxy resin composition containing an epoxy resin and an epoxy resin curing agent, and (D) an outer layer in this order. The polyamide resin has a terminal amino group concentration smaller than or equal to 30 μeq/g, and is obtained by the polycondensation between an aromatic diamine and a dicarboxylic acid, and moreover, the total content of the transition metal catalyst and the polyamide resin in the oxygen absorbing layer is 15-60 wt.% relative to the total amount of the oxygen absorbing layer. Furthermore, the epoxy resin cured product layer contains ≥40 wt.% of a skeletal structure shown in formula (1) relative to the total amount of the epoxy resin cured product layer. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to an oxygen-absorbing multilayer body that exhibits excellent oxygen-absorbing performance and is free from strength reduction and odor generation due to oxidative degradation of resin.

  Conventionally, containers such as metal cans, glass bottles, and various plastic packages have been known as packaging containers, but quality deterioration due to oxygen in the packaging containers has been a problem. For this reason, 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 is provided. Development of packaging containers in which the gas barrier property is improved and the container itself is provided with an oxygen absorbing function has been performed. 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 for detecting foreign substances such as food, and the internal visibility is insufficient due to the problem of opacity. There was a problem that it cannot be used for beverages such as alcohol whose flavor is impaired. In addition, since the oxidation reaction of iron powder is used, the effect of oxygen absorption can be exhibited only when the material to be preserved is a high moisture type.

  On the other hand, in a composition composed of 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, and a resin composition having an oxygen scavenging function or There are also examples of oxygen absorbents 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.

  In recent years, an epoxy resin curing agent has been proposed as a laminating adhesive having a gas barrier function in a gas barrier laminate film (see Patent Document 7).

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 JP 2002-256208 A

  The objective of this invention is providing the oxygen absorption multilayer body excellent in oxygen absorption performance, resin strength, and resin processability which solved the said problem.

  The present inventors blend specific polyamides, transition metals and polyolefin resins in specific proportions, so that oxygen absorption performance is excellent, resin strength after storage is maintained, and oxygen absorption is excellent in processability. It has been found that a multilayer body is obtained.

  That is, the present invention includes A) a sealant layer containing a polyolefin resin, B) an oxygen absorbing layer comprising an oxygen absorbing resin composition containing a polyolefin resin, a transition metal catalyst and a polyamide resin, and C) an epoxy resin and an epoxy resin curing agent. A cured epoxy resin layer obtained by curing the contained epoxy resin composition, and D) an oxygen-absorbing multilayer body in which at least four outer layers are laminated in this order, wherein the polyamide resin is an aromatic diamine and a dicarboxylic acid A polyamide resin having a terminal amino group concentration of 30 μeq / g or less obtained by polycondensation with an acid, and the total content of the transition metal catalyst and the polyamide resin in the oxygen absorption layer is based on the total amount of the oxygen absorption layer 15-60% by weight, and the cured epoxy resin layer has a skeleton structure represented by the formula (1) as a cured epoxy resin product. An oxygen-absorbing multilayered body, characterized in that it contains 40 wt% or more relative to the total amount.

  According to the present invention, it is possible to provide an oxygen-absorbing multilayer body that has high oxygen absorption performance and hardly undergoes strength deterioration due to oxidation of polyamide resin.

  The oxygen-absorbing resin composition used in the oxygen-absorbing layer of the present invention is a polyamide resin having a terminal amino group concentration of 30 μeq / g or less obtained by polycondensation of an aromatic diamine and a dicarboxylic acid (hereinafter, the polyamide resin is referred to as “ Polyamide resin A "), transition metal catalyst and polyolefin resin. Hereinafter, details of each of these components will be described.

  The oxygen absorption performance of the oxygen-absorbing resin composition is considered to be better when there are more polyamide resins having oxygen-absorbing capacity. Surprisingly, the polyamide resin A, transition metal and polyolefin resin are mixed together at a certain ratio. It has been found that when blended, 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 proceed by melt polymerization for melting the aromatic diamine and dicarboxylic acid, solid phase polymerization for heating the polyamide resin pellets, or the like under reduced pressure.

  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, it is preferable to combine the methods 1), 3), 2) and 3) because a polyamide resin having better oxygen absorption performance and moldability during film production can be obtained. Hereinafter, these methods will be described.

  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. If 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 low crystallinity with a half-crystallization time of 150 seconds or more, or those having no melting point peak when measuring the melting point 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 the polyamide resin A and the polyolefin resin are mixed, considering the processability, the melt flow rate (hereinafter referred to as MFR) of the polyamide resin A is 200 ° C., 3 to 20 g / 10 minutes, 240 ° C., 4 Those having ˜25 g / 10 min are preferably used. 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. 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 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.

The polyolefin resin of the present invention includes high-density polyethylene, medium-density polyethylene, low-density polyethylene, linear low-density polyethylene, ultra-low-density polyethylene, various polyethylenes such as polyethylene using a metallocene catalyst, polystyrene, polymethylpentene, and propylene homopolymer. Polypropylenes such as polymers, propylene-ethylene block copolymers, and propylene-ethylene random copolymers can be used alone or in combination. Among these polyolefin resins, from the viewpoint of oxygen absorption performance, the oxygen permeability coefficient is preferably 80 to 200 cc · mm / (m ² · day · atm) (23 ° C. · 60% RH). When the polyolefin resin is used, good oxygen absorption performance can be obtained. Due to oxygen absorption performance and film processability, polyolefin resins include high-density polyethylene, medium-density polyethylene, low-density polyethylene, linear low-density polyethylene, various polyethylenes such as polyethylene using a metallocene catalyst, and propylene-ethylene block copolymers. Various polypropylenes such as propylene-ethylene random copolymer are particularly preferably used. 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.

  In consideration of the miscibility with the polyamide resin A, it is particularly preferable to add a maleic anhydride-modified polyolefin resin. The addition amount of the maleic anhydride-modified polyolefin resin is preferably 1 to 30 wt%, particularly preferably 3 to 15 wt% with respect to the polyolefin resin.

  Further, the polyolefin resin of the present invention includes coloring pigments such as titanium oxide, additives such as antioxidants, slip agents, antistatic agents, stabilizers, fillers such as calcium carbonate, clay, mica, silica, and deodorants. An agent or 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 total content of the transition metal catalyst and the polyamide resin A in the oxygen-absorbing resin composition 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. Is 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.

  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.

  Moreover, the oxygen-absorbing resin composition of the present invention is in the form of a film or a sheet, (1) a sealant layer containing a polyolefin resin, (2) an oxygen-absorbing layer, (3) a cured epoxy resin layer, and (4) It is preferable to use as an oxygen-absorbing multilayer body formed by laminating at least four outer layers.

  In this case, the polyolefin resin used for the sealant layer is preferably the same as the polyolefin resin used for the oxygen-absorbing resin composition in consideration of compatibility.

  Although there is no restriction | limiting in particular in the thickness of an oxygen absorption layer, 5-100 micrometers is preferable and 10-50 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 composition can further improve the performance of absorbing oxygen and can prevent the workability and economy from being impaired. Further, the thickness of the sealant layer is preferably less because the sealant layer becomes an isolation layer from the oxygen absorbing layer, but is particularly preferably 2 to 50 μm, and particularly preferably 5 to 30 μm. In this case, compared with the case where the thickness is out of the above range, the oxygen absorbing rate of the oxygen absorbing resin composition can be further increased, and the workability can be prevented from being impaired. When processing into a film or sheet, considering the workability, the thickness ratio of the sealant layer and the oxygen absorbing layer is preferably 1: 0.5 to 1: 3, and 1: 1 to 1: 2.5. Particularly preferred.

In the oxygen-absorbing multilayer body of the present invention, the epoxy resin cured product layer is composed of an epoxy resin cured product obtained by curing an epoxy resin composition containing an epoxy resin and an epoxy resin curing agent, and the epoxy resin cured product The skeleton structure of the above formula (1) is contained in an amount of 40% by weight or more, preferably 45% by weight or more, more preferably 50% by weight or more. When the skeleton structure of the formula (1) is contained at a high level in the cured epoxy resin, a high gas barrier property is exhibited. According to the present invention, it is also possible to obtain an epoxy resin cured product having an oxygen barrier property of an oxygen permeability coefficient of 1.0 mL · mm / (m ² · day · MPa) (23 ° C. · 60% RH) or less. Below, an epoxy resin composition is demonstrated.

  The epoxy resin in the present invention may be any of an aliphatic compound, an alicyclic compound, an aromatic compound, or a heterocyclic compound. However, in consideration of the expression of high gas barrier properties, the aromatic moiety is located in the molecule. Is preferable, and an epoxy resin including the skeleton structure of the above formula (1) in the molecule is more preferable. Specific examples include an epoxy resin having a glycidylamino group derived from metaxylylenediamine, an epoxy resin having a glycidylamino group derived from 1,3-bis (aminomethyl) cyclohexane, and a glycidyl derived from diaminodiphenylmethane. Epoxy resin having amino group, epoxy resin having glycidylamino group and / or glycidyloxy group derived from paraaminophenol, epoxy resin having glycidyloxy group derived from bisphenol A, glycidyloxy group derived from bisphenol F Epoxy resin having a glycidyloxy group derived from phenol novolac, an epoxy resin having a glycidyloxy group derived from resorcinol, etc. It is. Among them, an epoxy resin having a glycidylamino group derived from metaxylylenediamine, an epoxy resin having a glycidylamino group derived from 1,3-bis (aminomethyl) cyclohexane, and a glycidyloxy group derived from bisphenol F Epoxy resins and epoxy resins having glycidyloxy groups derived from resorcinol are preferred.

  Furthermore, it is more preferable to use an epoxy resin having a glycidyloxy group derived from bisphenol F or an epoxy resin having a glycidylamino group derived from metaxylylenediamine, and a glycidylamino group derived from metaxylylenediamine It is particularly preferred to use an epoxy resin having

  Moreover, in order to improve various performances such as flexibility, impact resistance, and moist heat resistance, the above-mentioned various epoxy resins can be mixed and used at an appropriate ratio.

  The epoxy resin is obtained by reaction of alcohols, phenols or amines with epihalohydrin. For example, an epoxy resin having a glycidylamino group derived from metaxylylenediamine can be obtained by adding epichlorohydrin to metaxylylenediamine. Since metaxylylenediamine has four amino hydrogens, mono-, di-, tri- and tetraglycidyl compounds are formed. The number of glycidyl groups can be changed by changing the reaction ratio between metaxylylenediamine and epichlorohydrin. For example, an epoxy resin having mainly four glycidyl groups can be obtained by addition reaction of about 4 times mole of epichlorohydrin to metaxylylenediamine.

The epoxy resin is an excess of epihalohydrin with respect to various alcohols, phenols and amines in the presence of an alkali such as sodium hydroxide, 20 to 140 ° C., preferably 50 to 120 ° C. in the case of alcohols and phenols, amine In the case of a kind, it is synthesized by reacting at a temperature of 20 to 70 ° C. and separating the produced alkali halide.
The number average molecular weight of the produced epoxy resin varies depending on the molar ratio of epihalohydrin to various alcohols, phenols and amines, but is about 80 to 4000, preferably about 200 to 1000, preferably about 200 to 500. It is more preferable.

The epoxy resin curing agent in the present invention may be any of an aliphatic compound, an alicyclic compound, an aromatic compound, or a heterocyclic compound, such as polyamines, phenols, acid anhydrides, or carboxylic acids. Any commonly used epoxy resin curing agent can be used. These epoxy resin curing agents can be selected according to the use application of the laminate film and the required performance in the application.
Specifically, examples of polyamines include aliphatic amines such as ethylenediamine, diethylenetriamine, triethylenetetramine, and tetraethylenepentamine; aliphatic amines having an aromatic ring such as metaxylylenediamine and paraxylylenediamine; 1,3- Examples thereof include alicyclic amines such as bis (aminomethyl) cyclohexane, isophoronediamine and norbornanediamine; and aromatic amines such as diaminodiphenylmethane and metaphenylenediamine. Also, epoxy resins using these as raw materials, modified reaction products of polyamines and monoglycidyl compounds, modified reaction products of polyamines and epichlorohydrin, modified reaction products of polyamines and alkylene oxides having 2 to 4 carbon atoms, polyamines Amide oligomers, polyamines, polyfunctional compounds having at least one acyl group, and monovalent carboxylic acids and / or derivatives thereof, obtained by reaction of a group with a polyfunctional compound having at least one acyl group The amide oligomer obtained by this reaction can also be used as an epoxy resin curing agent.

Examples of phenols include polyphenols such as catechol, resorcinol and hydroquinone, and resole type phenol resins.
Acid anhydrides or carboxylic acids include aliphatic acid anhydrides such as dodecenyl succinic anhydride and polyadipic anhydride, and alicyclic acid anhydrides such as (methyl) tetrahydrophthalic anhydride and (methyl) hexahydrophthalic anhydride. Aromatic acid anhydrides such as phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and carboxylic acids thereof can be used.

In consideration of the expression of high gas barrier properties, an epoxy resin curing agent containing an aromatic moiety in the molecule is preferred, and an epoxy resin curing agent containing the skeleton structure of the above formula (1) in the molecule is more preferred.
Specifically, metaxylylenediamine or paraxylylenediamine, reaction products with epoxy resins or monoglycidyl compounds using these as raw materials, reaction products with alkylene oxides having 2 to 4 carbon atoms, epichlorohydrin Reaction products with these polyamines, reaction products with polyfunctional compounds having at least one acyl group, which can form amide group sites by reaction with these polyamines to form oligomers, reaction with these polyamines It is more preferable to use a reaction product of a polyfunctional compound having at least one acyl group and a monovalent carboxylic acid and / or a derivative thereof, which can form an amide group site to form an oligomer.

When considering high gas barrier properties and good adhesiveness, the following (X) and (Y) reaction products, or (X), (Y) and (Z) reaction products are used as epoxy resin curing agents. It is particularly preferable to use a product.
(X) a polyfunctional compound having at least one acyl group that can form an amide group site by reaction with metaxylylenediamine or paraxylylenediamine (Y) polyamine to form an oligomer (Z) having 1 to 1 carbon atoms 8 monovalent carboxylic acids and / or derivatives thereof

  Examples of the polyfunctional compound having at least one acyl group that can form an amide group site by reaction with the (Y) polyamine to form an oligomer include acrylic acid, methacrylic acid, maleic acid, fumaric acid, succinic acid, Carboxylic acids such as malic acid, tartaric acid, adipic acid, isophthalic acid, terephthalic acid, pyromellitic acid, trimellitic acid and their derivatives such as esters, amides, acid anhydrides, acid chlorides, etc., especially acrylic acid Methacrylic acid and derivatives thereof are preferred.

  In addition, monovalent carboxylic acids having 1 to 8 carbon atoms such as formic acid, acetic acid, propionic acid, butyric acid, lactic acid, glycolic acid, benzoic acid, and derivatives thereof such as esters, amides, acid anhydrides, acid chlorides, etc. The polyfunctional compound may be used in combination with the starting polyamine. The amide group site introduced by the reaction has a high cohesive force, and the presence of the amide group site in a high proportion in the epoxy resin curing agent provides higher oxygen barrier properties and better adhesive strength.

  The reaction molar ratio of (X) and (Y) or (X), (Y) and (Z) is the reactive functional group contained in (Y) with respect to the number of amino groups contained in (X). Or the ratio of the total number of reactive functional groups contained in (Y) and (Z) to the number of amino groups contained in (X) ranges from 0.3 to 0.97. preferable. When the ratio is less than 0.3, a sufficient amount of amide groups are not generated in the epoxy resin curing agent, and a high level of gas barrier properties and adhesiveness are not exhibited. Moreover, the ratio of the volatile molecule which remains in the epoxy resin curing agent is increased, which causes odor generation from the obtained cured product. Moreover, since the ratio of the hydroxyl group produced | generated by reaction of an epoxy group and an amino group in the hardening reaction material becomes high, it becomes a factor by which oxygen barrier property in a high humidity environment falls remarkably. On the other hand, in the range higher than 0.97, the amount of amino groups reacting with the epoxy resin is reduced, and excellent impact resistance and heat resistance are not exhibited, and the solubility in various organic solvents or water is lowered. When particularly considering the high gas barrier property, high adhesion, suppression of odor generation, and high oxygen barrier property in a high humidity environment of the obtained cured product, the molar ratio of the polyfunctional compound to the polyamine component is 0.6. A range of ˜0.97 is more preferable. In consideration of the expression of a higher level of adhesiveness, it is preferable that the epoxy resin curing agent in the present invention contains at least 6% by weight of an amide group based on the total weight of the curing agent.

In consideration of the development of high adhesion to the substrate, for example, an epoxy resin curing agent such as metaxylylenediamine or paraxylylenediamine can be reacted with the polyamine to form an amide group site to form an oligomer. The reaction ratio of the reaction product with the polyfunctional compound having at least one acyl group is 0.6 to 0.97, preferably 0.8 to 0.97 in terms of the molar ratio of the polyfunctional compound to the polyamine component. In particular, it is preferable to use an epoxy resin curing agent having a range of 0.85 to 0.97 and increasing the average molecular weight of the reaction product oligomer.
A more preferred epoxy resin curing agent is a reaction product of metaxylylenediamine and acrylic acid, methacrylic acid and / or derivatives thereof. Here, the reaction molar ratio of acrylic acid, methacrylic acid and / or derivatives thereof to metaxylylenediamine is preferably in the range of 0.8 to 0.97.

About the mixture ratio of the epoxy resin and epoxy resin hardening | curing agent in this invention, you may be a standard compounding range in the case of producing an epoxy resin hardened material by reaction of an epoxy resin and an epoxy resin hardening | curing agent generally. Specifically, the ratio of the number of active hydrogens in the epoxy resin curing agent to the number of epoxy groups in the epoxy resin is in the range of 0.5 to 5.0. If the range is less than 0.5, the remaining unreacted epoxy group causes the gas barrier property of the resulting cured product to decrease, and if it is greater than 5.0, the remaining unreacted amino group results in the resulting cured product. It becomes a cause of lowering the heat and heat resistance. In the case where gas barrier properties and wet heat resistance of the obtained cured product are particularly taken into consideration, the range of 0.8 to 3.0 is more preferable, and the range of 0.8 to 2.0 is particularly preferable.
In addition, when considering the expression of a high oxygen barrier property in a high humidity environment of the resulting cured product, the ratio of the number of active hydrogens in the epoxy resin curing agent to the number of epoxy groups in the epoxy resin is 0.8. A range of ~ 1.4 is preferred.
On the other hand, when thermoforming like a thermoforming container, the range of 1.6-5.0 is preferable and the range of 2.0-4.5 is more preferable.

  In the epoxy resin composition of the present invention, a thermosetting resin composition such as a polyurethane-based resin composition, a polyacrylic resin composition, a polyurea-based resin composition, or the like, if necessary, within a range not impairing the effects of the present invention. You may mix things.

  In the epoxy resin composition of the present invention, a wetting agent such as silicon or an acrylic compound may be added to various materials as needed in order to help wet the surface during application. Suitable wetting agents include BYK331, BYK333, BYK347, BYK348, BYK354, BYK380, BYK381, available from Big Chemie. When adding these, the range of 0.01 weight%-2.0 weight% is preferable on the basis of the total weight of an epoxy resin composition.

In addition, in order to improve various properties such as gas barrier properties, impact resistance, heat resistance, etc. of the cured epoxy resin layer in the present invention, silica, alumina, mica, talc, aluminum flakes, glass flakes are contained in the epoxy resin composition. An inorganic filler such as may be added.
In consideration of the transparency of the film, it is preferable that such an inorganic filler has a flat plate shape. When adding these, the range of 0.01 weight%-10.0 weight% is preferable on the basis of the total weight of an epoxy resin composition.

  Furthermore, in order to improve the adhesiveness with respect to the base material of the epoxy resin hardened material layer in this invention, you may add coupling agents, such as a silane coupling agent and a titanium coupling agent, in an epoxy resin composition. As the coupling agent, commercially available ones can be used. Among them, N- (2-aminoethyl) available from Chisso Corporation, Toray Dow Corning Corporation, Shin-Etsu Chemical Co., Ltd., etc. -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, N, N′-bis [[ 3-trimethoxysilyl] propyl] aminodiamine coupling agents such as ethylenediamine, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltri Epoxy such as methoxysilane and 3-glycidoxypropyltriethoxysilane Silane coupling agents, methacryloxy silane coupling agents such as 3-methacryloxypropyltrimethoxysilane, mercapto silane coupling agents such as 3-mercaptopropyltrimethoxysilane, and isocyanate silanes such as 3-isocyanatopropyltriethoxysilane What has an organic functional group which can react with the gas barrier resin composition of this invention, such as a coupling agent, is desirable. When adding these, the range of 0.01 weight%-5.0 weight% is preferable on the basis of the total weight of an epoxy resin composition. In the case where the substrate is a film on which various inorganic compounds such as silica and alumina are deposited, a silane coupling agent is more preferable.

  Examples of the outer layer in the present invention include polyester films such as polyethylene terephthalate and polybutylene terephthalate; polyamide films such as nylon 6, nylon 6,6, and metaxylene adipamide (N-MXD6); low density polyethylene, high density Polyolefin films such as polyethylene, linear low density polyethylene and polypropylene; polyacrylonitrile films; poly (meth) acrylic films; polystyrene films; polycarbonate films; ethylene-vinyl alcohol copolymer (EVOH) films; Examples include alcohol films; papers such as cartons; and metal foils such as aluminum and copper. Also, films obtained by coating various materials used as these substrates with various polymers such as polyvinylidene chloride (PVDC) resin, polyvinyl alcohol resin, ethylene-vinyl acetate copolymer saponified resin, acrylic resin; A film in which various inorganic compounds or metals such as silica, alumina, and aluminum are vapor-deposited; a film in which an inorganic filler is dispersed; a film having an oxygen scavenging function, and the like can be used.

  The cured epoxy resin in the present invention is characterized by having a high gas barrier property in addition to a suitable adhesion property to a substrate, and exhibits a high gas barrier property in a wide range from a low humidity condition to a high humidity condition. From this, the gas barrier film using the epoxy resin cured product in the present invention includes a PVDC coat layer, a polyvinyl alcohol (PVA) coat layer, an ethylene-vinyl alcohol copolymer (EVOH) film layer, a metaxylylene adipamide film. A gas barrier property at a very high level is exhibited without using a commonly used gas barrier material such as a layer, an inorganic vapor deposition film layer on which alumina, silica, or the like is deposited. Moreover, when an inorganic vapor deposition film is used as an outer layer, by using an epoxy resin cured product, it is possible to suppress a significant deterioration in gas barrier properties due to unexpected bending and maintain a high level of gas barrier properties.

  Gas barriers such as ethylene-vinyl alcohol copolymer (EVOH) film, polyvinyl alcohol film, polyvinyl alcohol coat film, polyvinyl alcohol coat film in which an inorganic filler is dispersed, metaxylene adipamide (N-MXD6) film, etc. The film has the disadvantage that its gas barrier property is lowered under high humidity conditions, but this drawback is eliminated by using the cured epoxy resin in the present invention as an outer layer. can do.

  Furthermore, since the cured epoxy resin in the present invention is excellent in toughness and heat-and-moisture resistance, a gas barrier film excellent in impact resistance, boiling resistance, retort resistance and the like can be obtained.

  In order to suppress foaming of the coating solution when preparing the coating solution of the epoxy resin composition in the present invention, an antifoaming agent such as silicon or an acrylic compound may be added to the coating solution. Suitable antifoaming agents include BYK019, BYK052, BYK065, BYK066N, BYK067N, BYK070, BYK080, and the like, which are available from Big Chemie, with BYK065 being particularly preferred. Moreover, when adding these antifoamers, the range of 0.01 weight%-3.0 weight% is preferable on the basis of the total weight of the epoxy resin composition in a coating liquid, 0.02 weight%-2 More preferred is 0.0% by weight.

  The thickness of the cured epoxy resin layer after applying and drying the epoxy resin composition of the present invention on various materials is 0.1 to 30 μm, preferably 0.2 to 10 μm. If it is less than 0.1 μm, sufficient gas barrier properties and adhesiveness are hardly exhibited. On the other hand, if it exceeds 50 μm, not only the drying property becomes poor, but also it becomes difficult to form a cured epoxy resin layer having a uniform thickness.

  In considering the processability when forming the oxygen-absorbing multilayer body, it is preferable to interpose an intermediate layer containing a polyolefin resin between the cured epoxy resin layer and the oxygen-absorbing layer containing the oxygen-absorbing resin composition. The thickness of the intermediate layer is preferably substantially the same as the thickness of the sealant layer from the viewpoint of workability. In this case, considering variations due to processing, the thickness is the same if the thickness ratio is within ± 10%.

  The obtained oxygen-absorbing multilayer body can be used as an oxygen-absorbing paper container by laminating a paper substrate on the outside of the outer layer. The processability of the paper container laminated with the paper base material is preferably 60 μm or less, particularly preferably 50 μm or less, at the inner side of the gas barrier layer. 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.

  The obtained oxygen-absorbing multilayer body can be prepared as a film, processed into a bag shape and a lid material, and used. The obtained oxygen-absorbing multilayer body can be produced as a sheet and molded into a tray or a cup. Moreover, the obtained bag-shaped container and cup-shaped container can perform 80-100 degreeC boil sterilization process, 100-135 degreeC semi-retort sterilization process, retort sterilization process, and high retort sterilization process. Moreover, it is preferably used for a microwave cooking-compatible pouch that fills a bag-like container with contents such as food, provides an opening, and releases steam from the opening when cooking with a microwave oven. it can.

  Since this oxygen-absorbing resin composition can absorb oxygen regardless of the presence or absence of moisture in the preserved product, dry foods such as powder seasonings, powdered coffee, coffee beans, rice, tea, beans, rice crackers, rice crackers, etc. It can be suitably used for health foods such as pharmaceuticals and vitamins. In addition, the oxygen-absorbing resin composition obtained in the present invention can be suitably used for alcoholic beverages and carbonated beverages that cannot be stored due to the presence of iron, unlike conventional oxygen-absorbing resin compositions using iron powder. .

  In addition, liquid drinks such as juice and coffee, rice processed foods such as rice bran, polished rice, cooked rice, red rice, rice cake, cooked foods such as soup, stew, and curry, fruit, sheep gourd, pudding, red beans, rice cake, Sweets such as jelly, cakes, buns, fishery products such as tuna and fish shellfish, processed milk products such as cheese and butter, processed meat products such as meat, salami, sausage and ham, carrots, potatoes, asparagus, shiitake, radish And other vegetables and eggs.

  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 group 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 group 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 dropping, the temperature was raised to 260 ° C. 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.

(Epoxy resin curing agent)
A reaction vessel was charged with 1 mole of metaxylylenediamine. The temperature was raised to 60 ° C. under a nitrogen stream, and 0.93 mol of methyl acrylate was added dropwise over 1 hour. After completion of the dropwise addition, the mixture was stirred at 120 ° C. for 1 hour, and further heated to 160 ° C. in 3 hours while distilling off generated methanol. The mixture was cooled to 100 ° C., and a predetermined amount of methanol was added so that the solid content concentration became 70% by weight to obtain an epoxy resin curing agent a. The content of amide groups in the epoxy resin curing agent was 21% by weight.

(Seal strength measurement method)
It measured with the tension tester based on JISZ1526.

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 0.992: 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 semi-crystallization time of 2000 seconds or more, a terminal amino group concentration of 17.5 μeq / g, a terminal carboxyl group concentration of 91.6 μeq / g, a number average molecular weight of 23500, MFR of 240 ° C. Was 11.0 g / 10 min. 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 400 ppm. Furthermore, a linear low density polyethylene (product name: “Knel KF380” manufactured by Nippon Polyethylene Co., Ltd.) is used as a polyolefin resin in a mixture of the obtained polyamide and cobalt stearate (hereinafter referred to as cobalt stearate-containing polyamide 1). ”, MFR 4.0 g / 10 min (measured in accordance with JIS K7210), MFR 8.7 g / 10 min at 240 ° C., MFR 10.0 g / 10 min at 250 ° C., hereinafter referred to as LLDPE), and containing cobalt stearate Polyamide 1: LLDPE = 35: 65 In a weight ratio, it was melt-kneaded at 240 ° C. to obtain an oxygen-absorbing resin composition. Next, using this oxygen-absorbing resin composition, a two-layer / three-layer film 1 (thickness: 10 μm / 20 μm / 10 μm) having a skin layer of LLDPE, a width of 800 mm, 120 m / min, and one side subjected to corona discharge treatment And produced. The appearance of the obtained film was good, and HAZE was 14%.

  57 parts by weight of an epoxy resin having a glycidylamine moiety derived from metaxylylenediamine (product name: “TETRAD-X” manufactured by Mitsubishi Gas Chemical Co., Inc.), 182 parts by weight of an epoxy resin curing agent, and 253.6 parts by weight of methanol And 34.2 parts by weight of ethyl acetate were mixed to prepare a solution having a solid concentration of 35% by weight. 0.4 parts by weight of acrylic wetting agent (product name: “BYK381” manufactured by Big Chemie) and 0.1 part by weight of silicone antifoaming agent (product name: “BYK065” manufactured by BYK Chemie) In addition, the mixture was thoroughly stirred to obtain a coating solution (epoxy resin composition) having an equivalent ratio of active hydrogen in the epoxy resin curing agent to the epoxy group in the epoxy resin (active hydrogen / epoxy group) of 1.2. A stretched nylon film (product name: “N1201” manufactured by Toyobo Co., Ltd.) with a thickness of 15 μm was used as the outer layer, and the coating solution was applied to the corona-treated surface of the outer layer and dried at 90 ° C. for 5 seconds. Lamination was performed to obtain an oxygen-absorbing multilayer body 1 composed of LLDPE / oxygen absorbing layer / LLDPE / cured epoxy resin layer / outer layer. The content of the skeleton structure represented by the formula (1) in the cured epoxy resin layer was 62.0% by weight.

  A 13 cm x 18 cm three-sided bag is prepared from the obtained oxygen-absorbing multilayer body 1 and filled with 60 g of pineapple and 120 g of syrup liquid so that the headspace air volume is 20 cc, sealed, and heated at 85 ° C for 90 minutes. The headspace oxygen concentration immediately after the heat treatment was measured. Thereafter, the color tone of the pineapple when stored at 40 ° C. for 2 months and the seal strength of one side of the three-sided bag were measured. The results are shown in Table 2.

(Example 2)
An oxygen-absorbing multilayer body 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: LLDPE = 55: 45, filled with pineapple, and heat-treated. The oxygen concentration immediately after, the flavor after one month, and the seal strength of the bag were measured. These results are shown in Table 2.

(Example 3)
An oxygen-absorbing multilayer body 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: LLDPE = 25: 75, filled with pineapple, and heat-treated. The oxygen concentration immediately after, the flavor after one month, and the seal strength of the bag were measured. These results are shown in Table 2.

Example 4
An oxygen-absorbing multilayer body 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: LLDPE = 17: 83, filled with pineapple, and heat-treated. The oxygen concentration immediately after, the flavor after one month, and the seal strength of the bag were measured. These results are shown in Table 2.

(Example 5)
A metaxylylenediamine and adipic acid were used in a molar ratio of 0.991: 1, and a polyamide resin was synthesized by performing melt polymerization and solid phase polymerization under the above synthesis conditions (hereinafter, the polyamide resin was 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 205 ° C., and the polymerization time was 4 hours. This polyamide 2 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 19.8 μeq / g, a terminal carboxyl group concentration of 68.6 μeq / g, and a number average molecular weight of 23,000. 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 14.4 g / 10min. An unstretched film was prepared from the obtained polyamide 2 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 1 except that the temperature at the time of melt kneading was set to 250 ° C., addition of cobalt stearate to polyamide 2, melt kneading with LLDPE, etc., to produce an oxygen-absorbing multilayer body, After filling with pineapple and heat treatment, the oxygen concentration immediately after the heat treatment, the flavor after one month, and the seal strength of the bag were measured. These results are shown in Table 2.

(Example 6)
Metaxylylenediamine and paraxylylenediamine are mixed at a ratio of 7: 3. 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, 0.2 wt% of phthalic anhydride was added and melt kneaded at 285 ° C. with a twin-screw extruder to seal the terminal amino group (hereinafter, the polyamide resin is referred to as polyamide 3). However, the dropping time was 2 hours, the polymerization temperature after completion of dropping of metaxylylenediamine in melt polymerization was 277 ° C., and the reaction time was 30 minutes. This polyamide 3 had a Tg of 87 ° C., a melting point of 259 ° C., a half crystallization time of 18 seconds, a terminal amino group concentration of 25.8 μeq / g, a terminal carboxyl group concentration of 65.6 μeq / g, and a number average molecular weight of 18,500. Moreover, since it was near melting | fusing point at 260 degreeC, MFR was not able to be measured, MFR of 260 degreeC was measured, and MFR in 270 degreeC was 29.8 g / 10min. An unstretched film was prepared from the obtained polyamide 3 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, in the same manner as in Example 1 except that the temperature at the time of melt kneading was changed to 270 ° C., addition of cobalt stearate to polyamide 3, melt kneading with LLDPE, etc., to produce an oxygen-absorbing multilayer body, After filling with pineapple and heat treatment, the oxygen concentration immediately after the heat treatment, the flavor after one month, and the seal strength of the bag were measured. These results are shown in Table 2.

(Example 7)
Metaxylylenediamine, adipic acid, and isophthalic acid were used in a molar ratio of 0.991: 0.8: 0.2, and a polyamide resin was obtained by performing melt polymerization and solid phase polymerization under the above synthesis conditions. Synthesized (hereinafter, the polyamide resin is referred to as polyamide 4). 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 215 ° C., and the polymerization time was 4 hours. Polyamide 4 had a Tg of 92 ° C., a melting point of 230 ° C., a half crystallization time of 250 seconds, a terminal amino group concentration of 14.8 μeq / g, a terminal carboxyl group concentration of 67.2 μeq / g, and a number average molecular weight of 23,000. 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 17.4 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 0.07 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 1 except that the temperature during melt-kneading was set to 250 ° C., addition of cobalt stearate to polyamide 4, melt-kneading with LLDPE, etc. were performed to produce an oxygen-absorbing multilayer body, After filling with pineapple and heat treatment, the oxygen concentration immediately after the heat treatment, the flavor after one month, and the seal strength of the bag were measured. These results are shown in Table 2.

(Example 8)
Metaxylylenediamine and sebacic acid were used in a molar ratio of 0.994: 1, and a polyamide resin was synthesized only by melt polymerization under the above synthesis conditions (hereinafter, the polyamide resin is referred to as polyamide 5). ). The dropping time was 2 hours, and the reaction time for melt polymerization was 1 hour. This polyamide 5 has a Tg of 61 ° C., a melting point of 190 ° C., a half crystallization time of 150 seconds, a terminal amino group concentration of 24.8 μeq / g, a terminal carboxyl group concentration of 57.2 μeq / g, a number average molecular weight of 17200, MFR of 240 ° C. Was 65.4 g / 10 min. An unstretched film was prepared with the obtained polyamide 5 alone, and the oxygen permeability coefficient was determined. The oxygen permeability coefficient was 1.58 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 1, addition of cobalt stearate to polyamide 5, melting and kneading with LLDPE, etc. were performed to produce an oxygen-absorbing multilayer body, filling with pineapple, and heat treatment. The oxygen concentration of 1 month, the flavor after one month, and the seal strength of the bag were measured. These results are shown in Table 2.

Example 9
Metaxylylenediamine, adipic acid, and isophthalic acid were used in a molar ratio of 0.998: 0.95: 0.05, and subjected to melt polymerization and solid phase polymerization under the above synthesis conditions to obtain a polyamide resin. Synthesized (hereinafter, the polyamide resin is referred to as polyamide 6). 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 215 ° C., and the polymerization time was 20 hours. This polyamide 6 has a Tg of 92 ° C., a melting point of 230 ° C., a half crystallization time of 250 seconds, a terminal amino group concentration of 28.8 μeq / g, a terminal carboxyl group concentration of 61.8 μeq / g, a number average molecular weight of 24200, MFR with 240 ° C. Was 10.1 g / 10 min. 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, in the same manner as in Example 1, addition of cobalt stearate to polyamide 6, melting and kneading with LLDPE, etc. were performed to produce an oxygen-absorbing multilayer body, filling with pineapple, and heat treatment, immediately after heat treatment The oxygen concentration of 1 month, the flavor after one month, and the seal strength of the bag were measured. These results are shown in Table 2.

(Example 10)
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 0.998: 0.6: 0.4. . 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 150 ° C., and the polymerization time was 8 hours. Thereafter, 0.2 wt% of phthalic anhydride was added and melt kneaded at 250 ° C. with a twin screw extruder to seal the terminal amino group (hereinafter, the polyamide resin is referred to as polyamide 7). This polyamide 7 has a Tg of 70 ° C., a melting point of 157 ° C., a half crystallization time of 18 seconds, a terminal amino group concentration of 15.8 μeq / g, a terminal carboxyl group concentration of 51.6 μeq / g, a number average molecular weight of 23,000 and an MFR of 240 ° C. Was 11.4 g / 10 min. An unstretched film was prepared from the obtained polyamide 5 alone, and the oxygen permeability coefficient was determined. The oxygen permeability coefficient was 0.74 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 1, addition of cobalt stearate to polyamide 7, melting and kneading with LLDPE, etc. were carried out to produce an oxygen-absorbing multilayer body, filling with pineapple, and heat treatment, immediately after heat treatment The oxygen concentration of 1 month, the flavor after one month, and the seal strength of the bag were measured. These results are shown in Table 2.

(Example 11)
Polyamide resin was synthesized by performing melt polymerization and solid phase polymerization under the above-described synthesis conditions using metaxylylenediamine: sebacic acid: adipic acid in a molar ratio of 0.992: 0.3: 0.7. (Hereinafter, the polyamide resin is referred to as polyamide 8). 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 8 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 19.5 μeq / g, a terminal carboxyl group concentration of 81.2 μeq / g, a number average molecular weight of 24500, MFR of 240 ° C. Was 10.5 g / 10 min. In addition, an unstretched film was prepared from the obtained polyamide 8 alone, and the 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, addition of cobalt stearate to polyamide 8, melting and kneading with LLDPE, etc. were carried out to produce an oxygen-absorbing multilayer body, filling with pineapple, and heat treatment, immediately after the heat treatment. The oxygen concentration of 1 month, the flavor after one month, and the seal strength of the bag were measured. These results are shown in Table 2.

(Example 12)
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 0.992: 0.7: 0.3. (Hereinafter, the polyamide resin is referred to as polyamide 9). 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 9 has a Tg of 65 ° C., a melting point of 170 ° C., a semicrystallization time of 2000 seconds or more, a terminal amino group concentration of 19.2 μeq / g, a terminal carboxyl group concentration of 80.0 μeq / g, a number average molecular weight of 25200, MFR with 240 ° C. Was 10.1 g / 10 min. Moreover, when the unstretched film was produced with the obtained polyamide 9 single-piece | unit and the oxygen permeability coefficient was calculated | required, it was 0.68cc * mm / (m < ² > * day * atm) (23 degreeC * 60% RH). . These results are shown in Table 1.

  Thereafter, in the same manner as in Example 1, addition of cobalt stearate to polyamide 9, melt kneading with LLDPE, etc. were carried out to produce an oxygen-absorbing multilayer, filling with pineapple, and heat treatment, immediately after the heat treatment The oxygen concentration of 1 month, the flavor after one month, and the seal strength of the bag were measured. These results are shown in Table 2.

(Example 13)
Cobalt stearate was added to LLDPE by side feed to the melted LLDPE with a twin screw extruder so that the cobalt concentration was 600 ppm. Furthermore, polyamide 1 was melt-kneaded at a weight ratio of polyamide 1: cobalt stearate-containing LLDPE = 35: 65 at 240 ° C. to the obtained mixture of LLDPE and cobalt stearate to obtain oxygen-absorbing resin pellets.

  Thereafter, in the same manner as in Example 1, an oxygen-absorbing multilayer body was produced, filled with pineapple and heat-treated, and the oxygen concentration immediately after the heat-treatment, the flavor after one month, and the seal strength of the bag were measured. These results are shown in Table 2.

(Comparative Example 1)
A film 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: LLDPE = 80: 20 to produce an oxygen-absorbing multilayer, filling with pineapple, and heating The oxygen concentration immediately after the heat treatment, the flavor after 1 month, and the seal strength of the bag were measured. These results are shown in Table 2.

(Comparative Example 2)
A film 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: LLDPE = 10: 90, an oxygen-absorbing multilayer body was produced, pineapple filling, and After heat treatment, the oxygen concentration immediately after the heat treatment, the flavor after one month and the seal strength of the bag were measured. These results are shown in Table 2.

(Comparative Example 3)
A polyamide resin was synthesized in the same manner as in Example 5 except that metaxylylenediamine and adipic acid were used in a molar ratio of 0.998: 1 and solid phase polymerization was not carried out (hereinafter, the polyamide is referred to as “polyamide resin”). The resin is denoted as polyamide 10). This polyamide 10 had a Tg of 78 ° C., a melting point of 237 ° C., a half crystallization time of 27 seconds, a terminal amino group concentration of 39.1 μeq / g, a terminal carboxyl group concentration of 70.2 μeq / g, and a number average molecular weight of 17,800. 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 51.0 g / 10min. Moreover, when the unstretched film was produced with the obtained polyamide 10 alone and the oxygen permeability coefficient was determined, it was 0.09 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 5, addition of cobalt stearate to polyamide 10, melt kneading with LLDPE, etc. were carried out to produce an oxygen-absorbing multilayer, filling with pineapple, and heat treatment, immediately after heat treatment The oxygen concentration of 1 month, the flavor after one month, and the seal strength of the bag were measured. These results are shown in Table 2.

(Comparative Example 4)
A polyamide resin was synthesized in the same manner as in Example 5 except that metaxylylenediamine and adipic acid were used in a molar ratio of 0.999: 1 and the polymerization time for solid phase polymerization was 2 hours (hereinafter referred to as “polyamide resin”). The polyamide resin is expressed as polyamide 11). Polyamide 11 had a Tg of 78 ° C., a melting point of 237 ° C., a half crystallization time of 25 seconds, a terminal amino group concentration of 34.8 μeq / g, a terminal carboxyl group concentration of 58.6 μeq / g, and a number average molecular weight of 21,800. 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 18.9 g / 10min. An unstretched film was prepared from the obtained polyamide 11 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 5, addition of cobalt stearate to polyamide 11, melt kneading with LLDPE, etc. were performed to produce an oxygen-absorbing multilayer body, filling with pineapple, and heat treatment, immediately after heat treatment The oxygen concentration of 1 month, the flavor after one month, and the seal strength of the bag were measured. These results are shown in Table 2.

  As is clear from Examples 1 to 13, the oxygen-absorbing multilayer body of the present invention has a good oxygen-absorbing performance, has a good food flavor, and has maintained the sealing strength of the film after oxygen absorption. It was an absorption multilayer.

  In contrast, in Comparative Example 1 in which the content of the polyamide resin A in the oxygen-absorbing resin composition exceeded 60% by weight, the sealing strength of the film was significantly deteriorated. In Comparative Example 2 in which the content of the polyamide resin A was less than 15% by weight, the oxygen absorption performance was insufficient. In particular, as is clear from the comparison between Comparative Examples 1 and 2 and Examples 1 to 4, if the content of the polyamide resin A in the oxygen-absorbing resin composition is large, good oxygen absorption performance is not necessarily obtained. It wasn't.

  On the other hand, as compared with Example 5, the molar ratio of metaxylylenediamine to adipic acid was increased, and the molar ratio of metaxylylenediamine to adipic acid was compared to Comparative Example 3 in which solid phase polymerization was not performed. At the same time, in Comparative Example 4 in which the solid-phase polymerization time was shortened, the terminal amino group concentration of the obtained polyamide resin exceeded 30 μeq / g, and good oxygen absorption performance could not be obtained. In Comparative Example 3, the appearance of the film was also deteriorated.

(Example 14)
4.75 parts by weight of a silane coupling agent (product name: “Silaace S330 (3-aminopropyltriethoxysilane)” manufactured by Chisso Corporation) was added to the coating liquid (epoxy resin composition) of Example 1 and stirred well. The coating solution (epoxy resin composition) was used, and a 12 μm thick silica-deposited PET film (product name; “Techbarrier L” manufactured by Mitsubishi Plastics, Inc.) was anchor-coated with 2 μm of the coating solution, dried at 85 ° C. for 1 second Using the two-type three-layer film 1 obtained in Example 1, the two-type three-layer film 1 was laminated by extrusion lamination with low-density polyethylene (product name: “Mirason 18SP” manufactured by Mitsui Chemicals, Inc.) Oxygen absorption of silica-deposited PET film / cured epoxy resin / low density polyethylene (20) / LLDPE (10) / oxygen absorbing resin composition (20) / LLDPE (10) A multilayer body was obtained. This oxygen-absorbing multilayered body was filled with radish pickles, stored at 23 ° C. after heat treatment at 80 ° C., and examined for flavor after 3 months. It was confirmed that the flavor of radish was well maintained.

(Example 15)
Instead of LLDPE, ethylene-propylene block copolymer (product name: “NOVATEC FG3DC” manufactured by Nippon Polypro Co., Ltd., MFR 9.5 g / 10 min at 230 ° C., MFR 10.6 g / 10 min at 240 ° C., hereinafter referred to as PP Oxygen-absorbing resin composition was obtained in the same manner as in Example 1 except that was used. Next, a two-kind three-layer film 2 (thickness: 15 μm / 30 μm / 15 μm) was produced in the same manner as in Example 1 except that the oxygen-absorbing resin composition was used as a core layer and the skin layer was replaced with PP instead of LLDPE. did. The obtained film had a HAZE of 24%.

  Next, 22 parts by weight of an epoxy resin having a glycidylamine moiety derived from metaxylylenediamine (product name: “TETRAD-X” manufactured by Mitsubishi Gas Chemical Co., Inc.), 236 parts by weight of an epoxy resin curing agent a, 242. 1 part by weight and 34.8 parts by weight of ethyl acetate were mixed to prepare a solution having a solid concentration of 35% by weight. 0.4 parts by weight of acrylic wetting agent (product name: “BYK381” manufactured by Big Chemie) and 0.1 part by weight of silicone antifoaming agent (product name: “BYK065” manufactured by BYK Chemie) In addition, the mixture was thoroughly stirred to obtain a coating solution (epoxy resin composition) having an equivalent ratio of active hydrogen in the epoxy resin curing agent to the epoxy group in the epoxy resin (active hydrogen / epoxy group) of 4.0. The content of the skeleton structure represented by the formula (1) in the cured epoxy resin was 63.5% by weight.

  An unstretched polypropylene sheet that has been subjected to corona treatment is coated with 8 μm of an epoxy resin composition on a corona-treated surface of 800 μm, dried at 90 ° C. for 10 seconds, and then laminated with two kinds of three-layer film 2 to obtain an oxygen-absorbing multilayer body. It was. The obtained multilayer body was thermoformed into a 70 cc cup (drawing ratio 2.7), filled with matcha pudding, and an alumina-deposited PET film (product name: “GL-AEH” manufactured by Toppan Printing Co., Ltd., 12) / A film of adhesive (3) / nylon (product name: “N1202”, 15 manufactured by Toyobo Co., Ltd.) / Adhesive (3) / PP (40) was heat-sealed as a lid material, and filled and sealed. The sealed container was heat-treated at 115 ° C. for 40 minutes, and the color tone of matcha pudding was observed when stored at 23 ° C. for 3 months. The color tone of the matcha pudding was well maintained.

  The present invention is superior in oxygen absorption performance by blending a specific polyamide resin, transition metal catalyst and polyolefin resin in a specific ratio in the oxygen absorption layer, and using a specific cured epoxy resin for lamination with the outer layer. It was an oxygen-absorbing multilayer body that retained the resin strength after storage, was excellent in processability, and could be applied to various containers and uses.

Claims (6)

A) Sealant layer containing polyolefin resin, B) Oxygen absorbing layer comprising an oxygen absorbing resin composition containing polyolefin resin, transition metal catalyst and polyamide resin, C) Epoxy resin composition containing epoxy resin and epoxy resin curing agent A cured epoxy resin layer obtained by curing the product, and D) an oxygen-absorbing multilayer body in which at least four outer layers are laminated in this order, and the polyamide resin is a polycondensation of an aromatic diamine and a dicarboxylic acid Is a polyamide resin having a terminal 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 absorption layer is 15 to 60% by weight based on the total amount of the oxygen absorption layer And the cured epoxy resin layer has a skeleton structure represented by the formula (1) with respect to the total amount of the cured epoxy resin layer. Oxygen absorbing multi-layer body, characterized in that it contains% by weight or more.
  The oxygen-absorbing multilayer body according to claim 1, wherein adipic acid, sebacic acid, isophthalic acid or a mixture thereof is used as the dicarboxylic acid.   3. The oxygen-absorbing multilayer body according to claim 1, wherein paraxylylenediamine, metaxylylenediamine, or a mixture thereof is used as the aromatic diamine.   The oxygen-absorbing multilayer body 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. 2. The oxygen-absorbing multilayer body according to 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. 2. The oxygen-absorbing multilayer body according to 1.