JP2011162255A - Multilayer container - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a multilayer container which is excellent in gas barrier properties and oxygen absorbing properties, and can keep oxygen concentration in a low level under retort processing or after long-term preservation under bad conditions such as high-temperature and humidity or the like after the retort processing and restrain the contents over long periods from being deteriorated and changed in quality without causing its whitening and deformation through even the retort processing. <P>SOLUTION: In the multilayer container formed with a laminated body having an oxygen absorbing layer composed of a thermoplastic resin (G) including carbon-carbon double bonds and a resin composition including modified EVOH(C) and a gas barrier layer wherein its oxygen transmission rate is equal to or less than 10 ml/(m<SP>2</SP>*day*atm), the modified EVOH(C) is obtained by modifying EVOH(A) with an epoxy compound (B) having double bonds. At least part of the resin composition is cross-linked. The gas barrier layer is arranged outside the oxygen absorbing layer. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention has extremely excellent gas barrier properties, retort resistance, and oxygen absorption properties, even under retort processing conditions, or even after being stored for a long time under adverse conditions such as high temperature and humidity after retort processing. The present invention relates to a multilayer container that can keep the internal oxygen concentration at a low level and can suppress deterioration and alteration of contents for a long period of time, and a laminate that can be preferably used in the production of the multilayer container.

  In recent years, packaging materials used in packaging containers for packaging foods, non-food products such as pharmaceuticals, electronic components, etc. have suppressed the deterioration and alteration of the contents that are packaged, and their original functions and properties Therefore, it is necessary to prevent permeation of oxygen, water vapor, and other gases that deteriorate or alter the contents. In addition, the packaging material that aims to replace metal cans and glass bottles, which have a large environmental impact during disposal, has a gas barrier property that blocks these gases (gases) for a long period of time even during high-temperature and high-humidity atmospheres during and after retort processing. It is strongly demanded to have

  Conventionally, packaging materials that are required to have such gas barrier properties include metal foils made of metals such as aluminum, metal vapor-deposited films comprising metals or metal oxides, polyvinyl alcohol, ethylene- Gas barrier materials such as gas barrier plastic films made of vinyl alcohol copolymer, polyvinylidene chloride, polyacrylonitrile, etc., and gas barrier films made by coating these plastics on a film substrate have been used.

  Among these gas barrier materials, metal foils and metal vapor deposited films have very high gas barrier properties, but resistance to bending and pinholes is not sufficient depending on applications, and does not reach the gas barrier properties of metal cans and glass bottles. In addition, gas barrier plastics such as ethylene-vinyl alcohol copolymers [hereinafter sometimes abbreviated as “EVOH”] have sufficient gas barrier properties in normal applications, but still transmit a very small amount of oxygen. Therefore, when a very oxygen sensitive substance is stored for a long period of time, deterioration of the contents due to oxygen may progress little by little, and the metal can or glass bottle cannot be replaced. Furthermore, when packaging materials using EVOH are used for retort processing (usually 80 to 145 ° C., normal pressure to 0.2 MPa, in the presence of moisture), EVOH is whitened and deformed, and gas barrier properties are reduced. There was a problem.

  By the way, in order to improve the hot water resistance required at the time of retorting, several techniques for crosslinking EVOH have been proposed (see, for example, Patent Documents 1 to 8). By introducing a crosslink into EVOH, it is possible to prevent deterioration in performance and quality such as whitening, deformation, and reduction in barrier properties of EVOH during retort processing.

  Moreover, the gas permeation amount of EVOH is not zero, and permeates an amount of gas that cannot be ignored. In particular, EVOH is known to have a reduced gas barrier property under conditions such as during retorting and immediately after processing. In order to reduce such gas permeation, in particular oxygen permeation, which has a great influence on the contents of the package, in particular the quality of the food, and oxygen already present in the package at the time of packaging of the contents In order to absorb and remove oxygen, some techniques for mixing and using an oxygen absorbent in a packaging material have been proposed (see, for example, Patent Documents 9 to 13). The gas barrier property can be improved by mixing and using an oxygen absorbent in the packaging material.

Furthermore, a technique combining a technique for crosslinking EVOH and a technique for mixing and using an oxygen absorbent in a packaging material has been proposed (see Patent Document 14). According to the technique of Patent Document 14, a molded article having excellent oxygen absorption and hardly containing a harmful crosslinking agent and having excellent hot water resistance, heat resistance, impact resistance, flexibility and gas barrier properties is obtained. be able to.
However, in order to prevent deterioration and alteration of the contents over a long period of time during retort processing or under adverse conditions such as high temperature and humidity, it can be suitably used as an alternative to metal cans and glass bottles. There was room for further study.

JP 63-8448 A JP-A-5-271498 JP-A-9-157421 JP-A-9-234833 Japanese Patent Laid-Open No. 62-252409 JP 56-49734 A International Publication No. 02/092643 International Publication No. 03/072653 Japanese Patent Laid-Open No. 5-115776 JP 2001-106866 A JP 2001-106920 A JP 2002-146217 A Japanese Patent Laying-Open No. 2005-187808 International Publication No. 2009/051159

  The present invention has been made in order to solve the above-mentioned problems, and is excellent in gas barrier properties and oxygen absorption properties, and even under retort treatment or after retort treatment for a long time under adverse conditions such as high temperature and high humidity. To provide a multi-layer container that can maintain the internal oxygen concentration at a low level even after storage, can suppress deterioration and alteration of contents for a long period of time, and is not easily whitened or deformed even by retort processing. And it aims at providing the laminated body which can manufacture the said multilayer container easily.

  As a result of intensive studies to achieve the above object, the present inventors have found that an oxygen-absorbing resin is contained on the outside of the oxygen-absorbing resin-containing EVOH layer obtained by crosslinking the oxygen-absorbing resin in a specific modified EVOH. A multilayer container with a specific film that excels in the amount of oxygen that penetrates into the multilayer container during and after retorting, and even after being stored for a long time in a high-temperature, high-humidity atmosphere after retorting. The present invention has been completed through further investigation based on this finding, and found that it can be reduced and can be a multi-layer container comparable to metal cans and glass bottles.

That is, the present invention
[1] An oxygen absorption layer comprising a resin composition containing a thermoplastic resin (G) having a carbon-carbon double bond and a modified ethylene-vinyl alcohol copolymer (C), and an oxygen permeability of 10 ml / (m ² · day · atm) and a multilayer container formed from a laminate having a gas barrier layer of less than or equal to ² · day · atm), wherein the modified ethylene-vinyl alcohol copolymer (C) is an ethylene-vinyl alcohol copolymer (A ) Is modified with an epoxy compound (B) having a double bond, at least a part of the resin composition is crosslinked, and the gas barrier layer is disposed outside the oxygen absorbing layer. Multi-layer container,
[2] The amount of modification of the modified ethylene-vinyl alcohol copolymer (C) by the epoxy compound (B) having a double bond is the total amount of monomer units of the ethylene-vinyl alcohol copolymer (A). The multilayer container according to the above [1], which is 0.1 to 10 mol% based on the number of moles;
[3] In the gas barrier layer, at least a part of —COO— groups contained in the at least one functional group of the polymer having at least one functional group selected from a carboxyl group and a carboxylic anhydride group is 2 Laminated body (F1) having a layer containing a neutralized product neutralized with a metal ion having a valence or higher; Laminated body (F2) having a layer made of an inorganic material formed by vapor deposition; and polyvinylidene chloride polymer Or a multilayer container according to [1] or [2] above, which is at least one selected from the group consisting of: a layer (F3) of a composition containing the same;
[4] Any one of the above [1] to [3], wherein the thermoplastic resin (G) having a carbon-carbon double bond has a carbon-carbon double bond substantially only in the main chain. Two multi-layer container,
[5] The multilayer container of [4], wherein the thermoplastic resin (G) is polyoctenylene,
[6] Any one of the above [1] to [5], wherein the resin composition further comprises an ethylene-vinyl alcohol copolymer (D) not modified with an epoxy compound (B) having a double bond. Two multi-layer container,
[7] The multilayer container according to any one of the above [1] to [6], wherein the resin composition further contains a transition metal salt (H).
[8] The multilayer container according to [7], wherein the transition metal salt (H) is a cobalt salt,
[9] The multilayer container according to any one of the above [1] to [8], wherein the resin composition further comprises a compatibilizer (I),
[10] The multilayer container according to any one of the above [1] to [9], wherein the epoxy compound (B) having a double bond is allyl glycidyl ether,
[11] The multilayer container according to any one of [1] to [10], wherein the laminate further includes a seal layer, and the seal layer is an innermost layer.
[12] An oxygen absorption layer comprising a resin composition containing a thermoplastic resin (G) having a carbon-carbon double bond and a modified ethylene-vinyl alcohol copolymer (C), and an oxygen permeability of 10 ml / (m ² · day · atm) or lower gas barrier layer and a sealing layer, wherein the modified ethylene-vinyl alcohol copolymer (C) is an ethylene-vinyl alcohol copolymer (A). It is obtained by modifying with an epoxy compound (B) having a double bond, at least a part of the resin composition is cross-linked, and the oxygen absorbing layer is interposed between the gas barrier layer and the sealing layer. A laminate in which the seal layer is disposed on the outermost surface,
[13] The amount of modification of the modified ethylene-vinyl alcohol copolymer (C) by the epoxy compound (B) having a double bond is the total amount of monomer units of the ethylene-vinyl alcohol copolymer (A). The laminate of [12] above, which is 0.1 to 10 mol% with respect to the number of moles,
[14] In the gas barrier layer, at least a part of —COO— groups contained in the at least one functional group of the polymer having at least one functional group selected from a carboxyl group and a carboxylic anhydride group is 2 Laminated body (F1) having a layer containing a neutralized product neutralized with a metal ion having a valence or higher; Laminated body (F2) having a layer made of an inorganic material formed by vapor deposition; and polyvinylidene chloride polymer Or a layered product of the above [12] or [13], which is at least one selected from the group consisting of: a layer (F3) of a composition containing the same;
[15] Any one of the above [12] to [14], wherein the thermoplastic resin (G) having a carbon-carbon double bond has a carbon-carbon double bond substantially only in the main chain. One laminate,
[16] The laminate according to [15], wherein the thermoplastic resin (G) is polyoctenylene,
[17] Any one of the above [12] to [16], wherein the resin composition further comprises an ethylene-vinyl alcohol copolymer (D) not modified with an epoxy compound (B) having a double bond. One laminate,
[18] The laminate according to any one of the above [12] to [17], wherein the resin composition further contains a transition metal salt (H),
[19] The laminate according to [18], wherein the transition metal salt (H) is a cobalt salt,
[20] The laminate according to any one of the above [12] to [19], wherein the resin composition further comprises a compatibilizer (I),
[21] The laminate according to any one of [12] to [20] above, wherein the epoxy compound (B) having a double bond is allyl glycidyl ether,
[22] The laminate according to any one of [12] to [21], wherein the seal layer is a polyolefin layer,
About.

  In the multilayer container of the present invention, a specific oxygen absorption layer and a gas barrier layer are disposed at specific positions, and is excellent in gas barrier properties and oxygen absorption properties, and oxygen intrusion is highly suppressed even when retorting is performed. The internal oxygen concentration can be kept at a low level even after being stored for a long time under adverse conditions such as high temperature and humidity after retort treatment, and the deterioration and alteration of the contents due to oxygen etc. can be suppressed for a long time. Can do. Further, whitening and deformation are not easily caused by the retort processing. Moreover, according to the laminated body of this invention, the said multilayer container can be manufactured easily.

  The present invention will be described below. In the following description, specific materials may be exemplified as those that exhibit a specific function, but the present invention is not limited to this. Moreover, as long as there is no description in particular, the material illustrated may be used individually by 1 type, and may use 2 or more types together.

  The multilayer container of the present invention is formed from a laminate having an oxygen absorption layer and a gas barrier layer, and the gas barrier layer is disposed outside the oxygen absorption layer. And the said oxygen absorption layer consists of a resin composition containing the thermoplastic resin (G) which has a carbon-carbon double bond, and modified | denatured EVOH (C).

[Modified EVOH (C)]
The modified EVOH (C) used in the present invention is obtained by modifying EVOH (A) with an epoxy compound (B) having a double bond. What reacted with the epoxy compound (B) which has a heavy bond can be used.
As the EVOH (A), EVOH not modified with the epoxy compound (B) having a double bond can be used. As such EVOH (A), for example, a saponified ethylene-vinyl ester copolymer formed only from ethylene and a vinyl ester such as vinyl acetate; or a vinyl ester such as ethylene and vinyl acetate; Examples thereof include saponified ethylene-vinyl ester copolymers formed from other copolymerizable monomers. The ratio of the other copolymerizable monomer units to the total monomer units constituting the ethylene-vinyl ester copolymer is preferably 30 mol% or less, and more preferably 10 mol% or less. The ethylene content of EVOH (A) is preferably in the range of 5 to 60 mol%, more preferably in the range of 20 to 55 mol%, and more preferably in the range of 25 to 50 mol%. Further preferred. When the ethylene content of EVOH (A) is 5 mol% or more, a multilayer container having excellent water resistance can be obtained. Moreover, when the ethylene content of EVOH (A) is 60 mol% or less, a multilayer container having better gas barrier properties can be obtained. By modifying EVOH (A) having such an ethylene content with an epoxy compound (B) having a double bond, a modified EVOH having the same ethylene content as that of the EVOH (A) ( C) can be obtained.

  The saponification degree of EVOH (A) is preferably 90 mol% or more, more preferably 98 mol% or more, and further preferably 99 mol% or more. When the EVOH (A) has a saponification degree of 90 mol% or more, a multilayer container excellent in gas barrier properties and thermal stability can be obtained.

  The modified EVOH (C) used in the present invention can be obtained by reacting EVOH (A) with an epoxy compound (B) having a double bond in an extruder as described later. If EVOH (A) contains an excessive amount of alkali metal salt and / or alkaline earth metal salt, the resulting modified EVOH (C) may be colored. In addition, the viscosity of the modified EVOH (C) may be reduced, and the moldability may be reduced. In addition, as described later, when the above reaction is performed using a catalyst, an alkali metal salt and / or an alkaline earth metal salt may deactivate the catalyst. Therefore, the content of alkali metal salt and / or alkaline earth metal salt in EVOH (A) is preferably as low as possible. Specifically, the alkali metal salt contained in EVOH (A) is a metal element equivalent value. It is preferably 50 ppm or less, more preferably 30 ppm or less, and further preferably 20 ppm or less. Similarly, the alkaline earth metal salt contained in EVOH (A) is preferably 20 ppm or less, more preferably 10 ppm or less, further preferably 5 ppm or less in terms of metal element, and EVOH ( It is particularly preferred that A) is substantially free of alkaline earth metal salts.

EVOH (A) has a melt flow rate (MFR) at 190 ° C. under a load of 2160 g, preferably in the range of 0.1 to 100 g / 10 min, and in the range of 0.3 to 30 g / 10 min. More preferably, it is still more preferably in the range of 0.5 to 20 g / 10 minutes. When the melting point of EVOH (A) is around 190 ° C. or exceeds 190 ° C., MFR is measured at a plurality of temperatures above the melting point under a load of 2160 g, and the inverse of absolute temperature is plotted on the horizontal axis in a semi-logarithmic graph. The value obtained by plotting the logarithm of MFR and MFR on the vertical axis and extrapolating to 190 ° C. can be adopted as MFR under a load of 190 ° C. and 2160 g.
As EVOH (A), it is also possible to use a mixture prepared by mixing two or more types of EVOH (A) having different MFRs so that the MFR is within the above range as a whole.

  The epoxy compound (B) having a double bond used in the present invention is preferably a monovalent epoxy compound having one epoxy group in the molecule and a plurality of one double bond in the molecule. Can be used. Moreover, it is preferable that the molecular weight of the epoxy compound (B) which has a double bond is 500 or less. A divalent or higher valent epoxy compound having two or more epoxy groups in the molecule may cause cross-linking upon modification of EVOH (A). From the viewpoint of reactivity, the type of the double bond is preferably a vinyl group that is a monosubstituted olefin, a vinylene group or vinylidene group that is a disubstituted olefin, or a trisubstituted olefin, a vinyl group, a vinylene group, Or it is more preferable that it is a vinylidene group, and it is still more preferable that it is a vinyl group.

  Moreover, it is preferable that the epoxy compound (B) which has a double bond is a thing which can be easily removed from the modified EVOH (C) obtained from the excess used in the modification. As one of such removal methods, a method of volatilizing from the vent of the extruder is practical, and therefore, an epoxy compound (B) having a double bond preferably has a boiling point of 250 ° C. or less. What is 200 degrees C or less is more preferable. Moreover, it is preferable that the carbon number of the epoxy compound (B) which has a double bond exists in the range of 4-10. Specific examples of the epoxy compound (B) having such a double bond include 1,2-epoxy-3-butene, 1,2-epoxy-4-pentene, 1,2-epoxy-5-hexene, , 2-epoxy-4-vinylcyclohexane, allyl glycidyl ether, methallyl glycidyl ether, ethylene glycol allyl glycidyl ether and the like, and allyl glycidyl ether is preferable. Moreover, as another one of said removal methods, the method of washing and removing from the vent of an extruder is mentioned, In this case, it is preferable that the epoxy compound (B) which has a double bond is soluble in water. .

  Although the reaction conditions of EVOH (A) and the epoxy compound (B) having a double bond are not particularly limited, it is preferably carried out in an extruder as in the method described in Patent Document 7. At this time, it is preferable to add a catalyst. In this case, it is preferable to add a catalyst deactivator described later such as a carboxylate after the reaction. When an epoxy compound (B) having a double bond is added to EVOH (A) in a molten state in the extruder, volatilization of the epoxy compound (B) having the double bond can be prevented and the reaction amount It is preferable because it becomes easy to control. The epoxy compound (B) having an excessively added double bond can be removed from the vent of the extruder. Moreover, after pelletizing once after the said reaction, the epoxy compound (B) which has a remaining double bond can be removed by wash | cleaning the obtained pellet with warm water. In this case, the remaining catalyst can also be removed.

  The catalyst used in the above reaction preferably contains a metal ion belonging to Groups 3-12 of the periodic table. The most important thing as a metal ion contained in a catalyst is having moderate Lewis acidity. From this point, the catalyst preferably contains a metal ion belonging to Groups 3-12 of the periodic table. Among these, since it has moderate Lewis acidity, those containing ions of metals belonging to Group 3 or Group 12 of the periodic table are more preferable, and those containing ions of zinc, yttrium, or gadolinium. Further preferred. Among them, a catalyst containing zinc ions is optimal because it has extremely high catalytic activity and the thermal stability of the resulting modified EVOH (C) is more excellent.

  When the amount of the catalyst containing metal ions belonging to Groups 3 to 12 of the periodic table is too large, EVOH (A) tends to be gelled during melt-kneading, and when too small, the effect of the catalyst is high. Since there is a tendency not to be sufficiently achieved, the number of moles of metal ions with respect to the mass of EVOH (A) is preferably within a range of 0.1 to 20 μmol / g, and within a range of 0.5 to 10 μmol / g. It is more preferable that In addition, since the suitable usage-amount of the catalyst containing the ion of the metal which belongs to periodic table group 3-12 changes also with the kind of metal contained in it, the kind of anion mentioned later, etc., those points were also considered. Above, it can adjust suitably.

  The counter anion of the metal ion in the catalyst containing metal ions belonging to Groups 3 to 12 of the periodic table is not particularly limited, but the conjugate acid is a monovalent anion that becomes a strong acid equivalent to or higher than sulfuric acid. Is preferred. This is because an anion in which the conjugate acid is a strong acid usually has a low nucleophilicity, so that it is difficult to react with the epoxy compound, and it can be prevented that the anion is consumed by the nucleophilic reaction and the catalytic activity is lost. In addition, by having such an anion as a counter ion, the Lewis acidity of the catalyst is improved and the catalytic activity is also improved.

Examples of monovalent anions in which the conjugate acid becomes a strong acid equivalent to or higher than sulfuric acid include sulfonate ions such as methanesulfonate ion, ethanesulfonate ion, trifluoromethanesulfonate ion, benzenesulfonate ion, and toluenesulfonate ion. Halogen ions such as chlorine ion, bromine ion and iodine ion; perchlorate ion; tetrafluoroborate ion (BF ₄ ⁻ ), hexafluorophosphate ion (PF ₆ ⁻ ), hexafluoroalcinate ion (AsF ₆ ⁻ ), Anions having four or more fluorine atoms such as hexafluoroantimonate ion; tetraphenylborate derivative ions such as tetrakis (pentafluorophenyl) borate ion; tetrakis (3,5-bis (trifluoromethyl) phenyl) borate; And carborane derivative ions such as cobalt (III) ion and bis (undecahydride-7,8-dicarboundecaborate) iron (III) ion. The Of these, sulfonic acid ions are preferable, and trifluoromethanesulfonic acid ions are most suitable.

  As described above, the catalyst used preferably contains a monovalent anion whose conjugate acid is a strong acid equivalent to or higher than sulfuric acid, but all anionic species in the catalyst must be the same anionic species. There is no. Rather, it is preferable that the conjugate acid has an anion that is a weak acid at the same time.

  Examples of anions in which the conjugate acid becomes a weak acid include alkyl anions, aryl anions, alkoxides, aryloxy anions, carboxylates, acetylacetonates, or derivatives thereof. Of these, alkoxide, carboxylate, acetylacetonate or derivatives thereof are preferably used.

  It is preferable that the number of moles of the anion in which the conjugate acid becomes a strong acid equivalent to or higher than that of sulfuric acid is 0.2 to 1.5 times the number of moles of metal ions in the catalyst. When the magnification is less than 0.2 times, the catalytic activity tends to be insufficient. Therefore, it is more preferably 0.3 times or more, and further preferably 0.4 times or more. On the other hand, when the magnification exceeds 1.5 times, the modified EVOH (C) tends to gel, and therefore, it is more preferably 1.2 times or less. The magnification is optimally 1 ×. In addition, when EVOH (A) as a raw material contains an alkali metal salt such as sodium acetate, the number of moles of anions in which the conjugate acid becomes a strong acid equivalent to or higher than sulfuric acid is increased by the amount that is neutralized and consumed. I can keep it.

  The method for preparing the catalyst is not particularly limited, but as a preferred method, a compound containing a metal belonging to Group 3 to 12 of the periodic table is dissolved or dispersed in a solvent, and sulfonic acid or the like is added to the resulting solution or suspension. And a method of adding a strong acid equivalent to or higher than sulfuric acid. Examples of the compound containing a metal belonging to Groups 3 to 12 of the periodic table used as a raw material include alkyl metals, aryl metals, metal alkoxides, metal aryloxides, metal carboxylates, and metal acetylacetonates. Here, when adding a strong acid to the solution or suspension of such a metal compound, it is preferable to add little by little. The solution containing the catalyst thus obtained can be introduced directly into the extruder.

  As the solvent for dissolving or dispersing the compound containing a metal belonging to Groups 3 to 12 of the periodic table, an organic solvent, particularly an ether solvent is preferable. This is because the reaction is difficult even at the temperature in the extruder and the solubility of the metal compound is good. Examples of ether solvents include dimethyl ether, diethyl ether, tetrahydrofuran, dioxane, 1,2-dimethoxyethane, diethoxyethane, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, and the like. The solvent used is preferably a solvent that is excellent in solubility of a compound containing a metal belonging to Groups 3 to 12 of the periodic table, has a relatively low boiling point, and can be almost completely removed by an extruder vent. In that respect, diethylene glycol dimethyl ether, 1,2-dimethoxyethane and tetrahydrofuran are particularly preferred.

  In the above-described catalyst preparation method, instead of the strong acid to be added, an ester of a strong acid such as a sulfonic acid ester may be used. Since esters of strong acids are usually less reactive than strong acids themselves, they may not react with metal compounds at room temperature. However, when injected into a high-temperature extruder maintained at about 200 ° C., the activity in the extruder is increased. The catalyst which has can be produced | generated.

As a method for preparing the catalyst, the method described below can also be employed. First, an aqueous catalyst solution is prepared by mixing a water-soluble compound containing a metal belonging to Groups 3 to 12 of the periodic table and a strong acid equivalent to or higher than sulfuric acid such as sulfonic acid in an aqueous solution. At this time, the aqueous solution may contain an appropriate amount of alcohol. Next, the obtained catalyst aqueous solution is brought into contact with EVOH (A) and then dried to obtain a target catalyst in a form blended with EVOH (A). As a specific method for bringing the catalyst aqueous solution into contact with EVOH (A), for example, a method of immersing pellets of EVOH (A), particularly porous hydrous pellets, in the catalyst aqueous solution is preferable. The pellets thus obtained are preferably dried to form dry pellets.
By introducing EVOH (A) containing the catalyst obtained as described above into an extruder, the subsequent reaction with the epoxy compound (B) having a double bond can be carried out.

  When a catalyst is used, it is preferable to add a catalyst deactivator after the reaction. As a catalyst deactivator used, what can reduce the function as a Lewis acid of a catalyst can be used, and the kind is not specifically limited. Alkali metal salts are preferably used. In order to deactivate a catalyst containing a monovalent anion whose conjugate acid is a strong acid equivalent to or higher than sulfuric acid, it is preferable to use an alkali metal salt of an anion of an acid weaker than the conjugate acid of the anion. By carrying out like this, the counter ion of the metal ion which belongs to the periodic table group 3-12 which comprises a catalyst is exchanged for the anion of a weak acid, As a result, the Lewis acidity of a catalyst can be reduced. The cation species of the alkali metal salt used for the catalyst deactivator are not particularly limited, and examples of the alkali metal salt include sodium salts, potassium salts, and lithium salts. Also, the anionic species is not particularly limited, and examples of the alkali metal salt include carboxylate, phosphate and phosphonate.

  Even if a salt such as sodium acetate or dipotassium monohydrogen phosphate is used as a catalyst deactivator, the thermal stability of the resulting modified EVOH (C) is considerably improved, but depending on the application, it still remains. It may be insufficient. This is because metal ions belonging to Groups 3 to 12 of the Periodic Table still have a function as a Lewis acid and thus act as a catalyst for decomposition and gelation of the modified EVOH (C). it is conceivable that. As a method for further improving this point, it is preferable to add a chelating agent that strongly coordinates to ions of metals belonging to Groups 3 to 12 of the periodic table as a catalyst deactivator. Such a chelating agent can be strongly coordinated to the ion of the metal, thereby making it possible to almost completely lose its Lewis acidity and to give a modified EVOH (C) excellent in thermal stability. Can do. Moreover, the strong acid which is the conjugate acid of the anion contained in a catalyst can also be neutralized as mentioned above by the said chelating agent being an alkali metal salt.

  Suitable chelating agents used as catalyst deactivators include oxycarboxylates, aminocarboxylates, aminophosphonates and the like. Specifically, examples of the oxycarboxylate include disodium citrate, disodium tartrate, and disodium malate. Aminocarboxylates include nitrilotriacetic acid trisodium, ethylenediaminetetraacetic acid disodium, ethylenediaminetetraacetic acid trisodium, ethylenediaminetetraacetic acid tripotassium, diethylenetriaminepentaacetic acid trisodium, 1,2-cyclohexanediamine tetraacetic acid trisodium, ethylenediamine diacetate. Illustrative examples include monosodium acetate and monosodium N- (hydroxyethyl) iminodiacetic acid. Examples of aminophosphonates include nitrilotrismethylenephosphonic acid hexasodium, ethylenediaminetetra (methylenephosphonic acid) octasodium, and the like. Among these, polyaminopolycarboxylic acid is preferable, and an alkali metal salt of ethylenediaminetetraacetic acid is optimal from the viewpoint of performance and cost.

  The addition amount of the catalyst deactivator is not particularly limited, and is appropriately adjusted depending on the type of metal ions contained in the catalyst, the number of coordination sites of the chelating agent, etc. If too small, the catalyst is not deactivated sufficiently. On the other hand, since the modified EVOH (C) obtained tends to be colored or the production cost tends to increase if it is too much, the mole of the catalyst deactivator with respect to the number of moles of metal ions contained in the catalyst. The ratio of the numbers is preferably 0.2 to 10, more preferably 0.5 to 5, and further preferably 1 to 3.

  The method for introducing the catalyst deactivator into the extruder is not particularly limited, but in order to uniformly disperse the catalyst deactivator, the catalyst deactivator is introduced as a solution containing the modified EVOH (C) in the molten state. It is preferable. Considering the solubility of the catalyst deactivator and the influence on the surrounding environment, the catalyst deactivator is preferably added as an aqueous solution.

  The catalyst deactivator may be added to the extruder after melt-kneading EVOH (A) and the epoxy compound (B) having a double bond in the presence of the catalyst. However, after the EVOH (A) and the epoxy compound (B) having a double bond are melt-kneaded in the presence of a catalyst and the epoxy compound (B) having an unreacted double bond is removed, the catalyst deactivator is removed. Is preferably added. As described above, when the catalyst deactivator is added as an aqueous solution, the catalyst deactivator is added before removing the epoxy compound (B) having an unreacted double bond. Thus, water is mixed into the epoxy compound (B) having a double bond to be recovered and used, and the separation operation takes time. In addition, after adding the aqueous solution of a catalyst deactivator, it is preferable to remove moisture by a vent or the like.

In the production method of the modified EVOH (C), as a suitable production process when a catalyst deactivator is used, for example,
(1) EVOH (A) melting step;
(2) Step of adding a mixture of an epoxy compound (B) having a double bond and a catalyst;
(3) Step of removing the epoxy compound (B) having an unreacted double bond;
(4) Step of adding an aqueous solution of a catalyst deactivator;
(5) a step of removing moisture under reduced pressure;
An example of sequentially passing through each of these steps is illustrated.

  From the viewpoint of carrying out the reaction smoothly, it is preferable to remove moisture and oxygen from the system. For this reason, you may remove a water | moisture content and oxygen using a vent etc. before adding the epoxy compound (B) which has a double bond in an extruder.

  The modification amount of the modified EVOH (C) by the epoxy compound (B) having a double bond is within the range of 0.1 to 10 mol% with respect to the total number of moles of monomer units of EVOH (A). Preferably, it is in the range of 0.3-5 mol%, more preferably in the range of 0.5-3 mol%. When the modification amount is 0.1 mol% or more, the modification effect can be sufficiently exhibited. Moreover, when the said modification | denaturation amount is 10 mol% or less, the gas barrier property and thermal stability of the multilayer container of this invention can be improved more.

  When the epoxy compound (B) having a double bond is reacted with EVOH (A), an epoxy compound (E) having no double bond may be added. Thereby, crystallinity can be reduced while minimizing the decrease in gas barrier properties of the obtained EVOH (C), and performance such as stretchability, thermoformability, and flexibility can be improved. As specific examples of such an epoxy compound (E) having no double bond, those described in Patent Document 7 can be used. Among these, from the viewpoint of performance, epoxy ethane (ethylene oxide), Monovalent epoxy compounds having a molecular weight of 500 or less, such as 1,2-epoxypropane (propylene oxide), 1,2-epoxybutane, and glycidol are preferred. It is preferable that carbon number of the epoxy compound (E) which does not have a double bond is 2-8.

  The method for adding the epoxy compound (E) having no double bond is not particularly limited. However, from the viewpoint of production efficiency, it is preferable to modify EVOH (A), an epoxy compound (B) having a double bond, and an epoxy compound (E) having no double bond at the same time. Specifically, a method of adding a mixture of an epoxy compound (B) having a double bond and an epoxy compound (E) having no double bond is exemplified as a suitable method. At this time, it is more preferable to add the catalyst at the same time.

  If the amount of the modified EVOH (C) modified by the epoxy compound (E) having no double bond is too large, the gas barrier property tends to be lowered, and stretchability, thermoformability, flexibility From the viewpoint of the improvement effect such as property, it is preferably in the range of 0.1 to 30 mol%, more preferably in the range of 0.5 to 20 mol% with respect to the total number of moles of monomer units of EVOH (A). More preferably, it is more preferably in the range of 1 to 15 mol%.

  The melt flow rate (MFR) of the modified EVOH (C) (190 ° C., under a load of 2160 g) is preferably within a range of 0.1 to 100 g / 10 minutes, and within a range of 0.3 to 30 g / 10 minutes. More preferably, it is more preferably within a range of 0.5 to 20 g / 10 minutes. When the melting point of the modified EVOH (C) is around 190 ° C. or exceeds 190 ° C., the MFR is measured at a plurality of temperatures above the melting point under a load of 2160 g, and the reciprocal absolute temperature is plotted on a horizontal axis in a semi-logarithmic graph. In addition, the value obtained by plotting the logarithm of MFR and the logarithm of MFR on the vertical axis and extrapolating to 190 ° C. can be adopted as MFR under a load of 190 ° C. and 2160 g.

[Thermoplastic resin having carbon-carbon double bond (G)]
The thermoplastic resin (G) having a carbon-carbon double bond used in the present invention (hereinafter sometimes simply referred to as “thermoplastic resin (G)”) is substantially carbon only in the main chain. -What has a carbon double bond can be used preferably. Here, the thermoplastic resin (G) "has a carbon-carbon double bond substantially only in the main chain" means that the carbon-carbon double bond existing in the main chain of the thermoplastic resin (G) is , 90% by mole or more of all carbon-carbon double bonds in the molecule of the thermoplastic resin (G), and the carbon-carbon double bonds present in the side chain are all in the molecule of the thermoplastic resin (G). It means 10 mol% or less of the carbon-carbon double bond. The ratio of the number of moles of carbon-carbon double bonds present in the main chain to the number of moles of all carbon-carbon double bonds in the molecule of the thermoplastic resin (G) is preferably 93 mol% or more. More preferably, it is 95 mol% or more. The ratio of the number of moles of carbon-carbon double bonds present in the side chain to the number of moles of all carbon-carbon double bonds in the molecule of the thermoplastic resin (G) is 7 mol% or less. Is preferable, and it is more preferable that it is 5 mol% or less.

Since the thermoplastic resin (G) has a carbon-carbon double bond in its molecule, it can react with oxygen efficiently, and as a result, it exhibits an oxygen absorbing function. In the present specification, the “carbon-carbon double bond” does not include the carbon-carbon double bond in the aromatic ring.
The amount of the carbon-carbon double bond of the thermoplastic resin (G) is preferably in the range of 0.001 to 0.020 mol / g, more preferably 0.005 to 0.018 mol / g. Within the range, more preferably within the range of 0.007 to 0.012 mol / g. When the amount of the carbon-carbon double bond is less than 0.001 mol / g, the oxygen absorption function of the obtained oxygen absorption layer tends to be insufficient, and when it exceeds 0.020 mol / g, the thermoplastic resin When (G) is molded together with other resins, coloring and foreign material defects tend to occur.

Examples of the thermoplastic resin (G) include polyoctenylene, polyheptenylene, polynorbornene, polycyclopentadiene, isoprene dimer hydrogenated ring-opened polymer, and the like. The isoprene dimer hydrogenated ring-opened polymer is represented by the following formula.
_{-CX = CX-CH 2 -CH 2} -CY 2 -CY 2 -CH 2 -CH 2 -
Here, one of the two Xs is a methyl group, the other is a hydrogen atom, and one of the four Ys is a methyl group, and the remaining three are hydrogen atoms. is there.

  The thermoplastic resin (G) may have various hydrophilic groups. Examples of the hydrophilic group include a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an amino group, an aldehyde group, a carboxyl group, an epoxy group, an ester group, a carboxylic acid anhydride group, and a boron-containing polar group (for example, boron Acid group, boronic acid ester group, boronic acid anhydride group, boronic acid base) and the like. These hydrophilic groups may exist in any part of the thermoplastic resin (G).

  The weight average molecular weight of the thermoplastic resin (G) is preferably in the range of 1,000 to 500,000, more preferably in the range of 10,000 to 250,000, and even more preferably. It is in the range of 60,000 to 200,000. When the weight average molecular weight of the thermoplastic resin (G) is less than 1,000 or more than 500,000, the moldability and handling properties of the resulting resin composition, strength and elongation when used as an oxygen absorbing layer are obtained. The mechanical properties such as degree tend to decrease.

  When a thermoplastic resin (G) having a carbon-carbon double bond substantially only in the main chain is used, the carbon-carbon double bond or its allylic position is partially oxidized or cut by oxygen absorption. Even when the carbon-carbon double bond in the side chain is cleaved, a low molecular weight fragment is hardly generated and an odorous substance is not easily generated.

  The thermoplastic resin (G) can be produced by a method of ring-opening metathesis polymerization of a cyclic olefin in an inert solvent in the presence of a polymerization catalyst and, if necessary, a chain transfer agent. This method has the advantage that there is no byproduct of ethylene and the manufacturing process is not complicated.

  The cyclic olefin is preferably a cyclic olefin having 7 or more carbon atoms, for example, cyclomonoene such as cycloheptene, cyclooctene, cyclononene, cyclodecene, norbornene; cyclodiene such as cyclooctadiene, cyclodecadiene, norbornadiene, dicyclopentadiene; cyclo And cyclotriene such as dodecatriene. These may have a substituent such as an alkoxy group, a carbonyl group, an alkoxycarbonyl group, or a halogen atom. Among these, cyclooctene is preferable in consideration of availability and economy.

  Examples of the polymerization catalyst for ring-opening metathesis polymerization include a catalyst (x-1) having a transition metal halide as a main component and a transition metal carbene complex catalyst (x-2). Examples of the catalyst (x-1) containing a transition metal halide as a main component include those containing a transition metal halide as a main component and an organometallic compound other than a transition metal as a promoter.

The transition metal halide is preferably a halide of Group 4 to Group 8 transition metal, such as MoBr ₂ , MoBr ₃ , MoBr ₄ , MoCl ₄ , MoCl ₅ , MoF ₄ , MoOCl ₄ , and MoOF ₄ . Molybdenum halides; WBr ₂ , WCl ₂ , WBr ₄ , WCl ₄ , WCl ₅ , WCl ₆ , WF ₄ , WI ₂ , WOBr ₄ , WOCl ₄ , WOF ₄ , WCl ₄ (OC ₆ H ₃ Cl ₂ ) ₂ Examples include tungsten halides; vanadium halides such as VOCl ₃ and VOBr ₃ ; titanium halides such as TiCl ₄ and TiBr _{4, and the} like.

  Examples of organometallic compounds other than transition metals that function as the promoter include, for example, trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, triphenylaluminum, tribenzylaluminum, diethylaluminum monochloride, Organo aluminum compounds such as di-n-butylaluminum monochloride, diethylaluminum monoiodide, diethylaluminum monohydride, ethylaluminum sesquichloride, ethylaluminum dichloride, methylaluminoxane, isobutylaluminoxane; tetramethyltin, diethyldimethyltin, tetraethyltin , Dibutyldiethyltin, tetrabutyltin, tetraoctyltin, trioctyltin Fluoride, trioctyltin chloride, trioctyltin bromide, trioctyltin iodide, dibutyltin difluoride, dibutyltin dichloride, dibutyltin dibromide, dibutyltin diiodide, butyltin trifluoride, butyltin trichloride, butyltin tribromide, dibutyltin tria Organotin compounds such as iodide; Organolithium compounds such as methyllithium, ethyllithium, n-butyllithium, sec-butyllithium and phenyllithium; Organic sodium compounds such as n-pentylsodium; Methylmagnesium iodide, ethylmagnesium bromide , Methylmagnesium bromide, n-propylmagnesium bromide, tert-butylmagnesium chloride, arylmagnesium chloride Organic magnesium compounds such as diethyl zinc; organic cadmium compounds such as diethyl cadmium; trimethylboron, triethylboron, tri-n-butylboron, triphenylboron, tris (perfluorophenyl) boron, N, N- And organic boron compounds such as dimethylanilinium tetrakis (perfluorophenyl) borate and trityltetrakis (perfluorophenyl) borate.

  As the transition metal carbene complex catalyst (x-2), carbene complex compounds of Group 4 to 8 transition metals in the periodic table can be used, for example, tungsten carbene complex catalyst, molybdenum carbene complex catalyst, rhenium carbene complex catalyst. And ruthenium carbene complex catalysts. Among these, a ruthenium carbene complex catalyst is preferable. Specific examples of the ruthenium carbene complex catalyst include, for example, benzylidene (1,3-dimesitylimidazolidine-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, (1,3-dimesitylimidazolidine-2-ylidene). ) (3-Methyl-2-buten-1-ylidene) (tricyclopentylphosphine) ruthenium dichloride, benzylidene (1,3-dimesityl-octahydrobenzimidazol-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, benzylidene [1 , 3-Di (1-phenylethyl) -4-imidazoline-2-ylidene] (tricyclohexylphosphine) ruthenium dichloride, benzylidene (1,3-dimesityl-2,3-dihydrobenzimidazol-2-ylidene) ( Licyclohexylphosphine) ruthenium dichloride, benzylidene (tricyclohexylphosphine) (1,3,4-triphenyl-2,3,4,5-tetrahydro-1H-1,2,4-triazol-5-ylidene) ruthenium dichloride, Heteroatoms such as (1,3-diisopropylhexahydropyrimidin-2-ylidene) (ethoxymethylene) (tricyclohexylphosphine) ruthenium dichloride, benzylidene (1,3-dimesitylimidazolidine-2-ylidene) pyridine ruthenium dichloride Examples include, but are not limited to, a ruthenium carbene complex in which a carbene compound and a neutral electron donating compound are bonded.

  These polymerization catalysts may be used individually by 1 type, or may use 2 or more types together. Among these, it is preferable to use a transition metal carbene complex catalyst (x-2) because it does not require a cocatalyst and is highly active.

  The amount of the polymerization catalyst used for the ring-opening metathesis polymerization is a molar ratio of the polymerization catalyst to the cyclic olefin to be subjected to the polymerization reaction, and is within the range of polymerization catalyst: cyclic olefin = 1: 100 to 1: 2,000,000. Is more preferable, and it is more preferably within a range of 1: 500 to 1: 1,000,000, and further preferably within a range of 1: 1,000 to 1: 700,000. If the amount of catalyst is too large, removal of the catalyst after the reaction tends to be difficult, and if it is too small, sufficient polymerization activity tends to be difficult to obtain.

  Examples of the chain transfer agent include α-olefins such as 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene; 2-butene, 2-pentene, 2-hexene, 3-hexene, Internal olefins such as 2-heptene, 3-heptene, 2-octene, 3-octene and 4-octene can be preferably used. These may be used alone or in combination of two or more.

  The amount of the chain transfer agent used is not particularly limited as long as it is an amount capable of producing a polymer having a sufficient molecular weight in the polymerization reaction. For example, the molar ratio of the chain transfer agent to the cyclic olefin is preferably in the range of cyclic olefin: chain transfer agent = 1,000: 1 to 20: 1, and in the range of 800: 1 to 50: 1. It is more preferable.

  Examples of the inert solvent include saturated aliphatic hydrocarbons (including saturated alicyclic hydrocarbons) such as hexane, heptane, octane, nonane, decane, dodecane, cyclohexane, cycloheptane, and cyclooctane; benzene, toluene, Aromatic hydrocarbons such as xylene and mesitylene; halogenated hydrocarbons such as methylene chloride, chloroform and carbon tetrachloride; ethers such as diethyl ether, tetrahydrofuran and 1,4-dioxane can be used. In view of easy solvent removal and operability, it is preferable to use saturated aliphatic hydrocarbons.

  Although the usage-amount of a solvent is not specifically limited, It is preferable to exist in the range of 1-1000 mass times with respect to the cyclic olefin used, and it is more preferable to exist in the range of 2-200 mass times. More preferably, it is in the range of -100 mass times.

  The temperature at which the ring-opening metathesis polymerization is carried out depends on the type of solvent used, the amount, etc., and is not necessarily constant, but is preferably in the range of −78 to 200 ° C., and in the range of 10 to 150 ° C. More preferably, it is within. The polymerization is preferably carried out in an inert gas atmosphere.

  An example of the production method when the thermoplastic resin (G) is polyoctenylene is as follows. First, polyoctenylene can be produced by performing ring-opening metathesis polymerization using cyclooctene as a raw material and using the above-described polymerization catalyst. Specifically, for example, ring-opening metathesis polymerization is carried out in the presence of the above-mentioned solvent using a polymerization catalyst such as benzylidene (1,3-dimesitylimidazolidine-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride. It is preferable to do this. The polymerization is preferably performed within 72 hours, although it varies depending on the melting point and boiling point of the solvent used.

  In the thermoplastic resin (G) obtained by the ring-opening metathesis polymerization, oligomers of about 2 to 10 mer of cyclic olefin as a raw material are easily generated, and it is difficult to suppress this generation, but odor From the above viewpoint, the content of the oligomer having a molecular weight of 1,000 or less in the thermoplastic polymer (G) is preferably 6% by mass or less. It is therefore recommended to remove such oligomers. There is no particular limitation on the method for removing the oligomer. For example, after the polymerization catalyst and solvent are removed after the polymerization is completed, an inert gas such as nitrogen is introduced under heating, a method of heating under high vacuum, water, etc. And azeotropic removal with an azeotropic solvent.

  Further, after the polymerization is completed, the polymerization catalyst and the solvent are removed, and the obtained thermoplastic resin (G) is processed into a strand, chip, or pellet by a method such as extrusion molding, and then a thermoplastic resin having a molecular weight exceeding 1,000 ( The oligomer can be removed by bringing G) into contact with an organic solvent that does not substantially dissolve and washing. Examples of such an organic solvent include alcohols such as methanol, ethanol, propanol and isopropanol; ketones such as acetone and methyl ethyl ketone; esters such as methyl acetate and ethyl acetate; ethers such as diethyl ether and tert-butyl methyl ether. Although the usage-amount of the said organic solvent is not specifically limited, It is preferable to exist in the range of 1 to 10,000 mass times with respect to a thermoplastic resin (G), and to be in the range of 10 to 1,000 mass times. Is more preferable, and from the viewpoint of operability, it is more preferably in the range of 20 to 800 times by mass. Although there is no restriction | limiting in particular in the temperature wash | cleaned with an organic solvent, it is preferable to exist in the range of -10-80 degreeC, and when considering operativity, it is more preferable to exist in the range of 0-60 degreeC. The washing method is not particularly limited, and a method of immersing the thermoplastic resin (G) processed into strands, chips, or pellets in an organic solvent; the thermoplastic resin (G) processed into strands, chips, or pellets as an organic solvent For example, a method in which the thermoplastic resin (G) processed into strands, chips, or pellets is fixed as in a fixed bed system, and an organic solvent is circulated. After washing, the organic solvent is separated, and the remaining organic solvent is removed by a method such as distilling off under reduced pressure or inert gas to obtain a thermoplastic resin (G) having a low oligomer content. Can do. The thermoplastic resin (G) having a molecular weight of 1,000 or less obtained in this manner has a molecular weight of 1,000 or less, and the oligomer is eluted from the thermoplastic resin (G) even when the retort treatment is performed. Very few transitions to other materials.

[Transition metal salt (H)]
The resin composition constituting the oxygen absorbing layer of the laminate forming the multilayer container of the present invention further contains a transition metal salt (H) in addition to the modified EVOH (C) and the thermoplastic resin (G). Is preferred. When the said resin composition contains transition metal salt (H), the oxygen absorption function of the oxygen absorption layer obtained can be improved more. Examples of the transition metal contained in the transition metal salt (H) include iron, nickel, copper, manganese, cobalt, rhodium, titanium, chromium, vanadium, and ruthenium. Among these, iron, nickel, copper, manganese, and cobalt are preferable, manganese and cobalt are more preferable, and cobalt is more preferable.

The counter ion of the transition metal contained in the transition metal salt (H) is preferably an anion derived from an organic acid. Examples of the organic acid include acetic acid, stearic acid, dimethyldithiocarbamic acid, palmitic acid, and 2-ethylhexane. Examples include acid, neodecanoic acid, linoleic acid, toluic acid, oleic acid, capric acid, and naphthenic acid.
As the transition metal salt (H), cobalt 2-ethylhexanoate, cobalt neodecanoate, and cobalt stearate are preferable.

  The content of the transition metal salt (H) is in the range of 1 to 50,000 ppm in terms of transition metal based on the mass of the resin composition constituting the oxygen absorption layer of the laminate forming the multilayer container of the present invention. Preferably, it is in the range of 5 to 10,000 ppm, more preferably in the range of 10 to 5,000 ppm. When the content of the transition metal salt (H) in the resin composition is 1 ppm or more in terms of transition metal, the oxygen absorption function of the obtained oxygen absorption layer is improved. On the other hand, when the content of the transition metal salt (H) in the resin composition is 50,000 ppm or less in terms of transition metal, the thermal stability of the obtained oxygen absorbing layer is further improved, and the gel and foreign matter defects are improved. Can be suppressed.

[EVOH (D)]
In addition to the thermoplastic resin (G) and the modified EVOH (C), the resin composition constituting the oxygen absorption layer of the laminate forming the multilayer container of the present invention is modified with an epoxy compound (B) having a double bond. EVOH (D) [which may be simply abbreviated as “EVOH (D)” hereinafter). When the resin composition contains EVOH (D), it is possible to obtain a multilayer container that is more excellent in gas barrier properties. As EVOH (D) that can be contained in the resin composition, those described above as EVOH (A) can be used.

[Compatibilizer (I)]
The resin composition constituting the oxygen absorbing layer of the laminate forming the multilayer container of the present invention can contain a compatibilizing agent (I). When the resin composition contains the compatibilizer (I), the compatibility between the resins used can be improved, and a more stable morphology can be given to the resulting oxygen-absorbing layer. In particular, this effect becomes remarkable when the resin composition contains the EVOH (D). The type of the compatibilizer (I) is not particularly limited and can be appropriately selected depending on the combination of the thermoplastic resin (G) and the modified EVOH (C) used.

  Since the modified EVOH (C) or EVOH (D) is a highly polar resin, the compatibilizer (I) is preferably a hydrocarbon polymer having a polar group. In the case where the compatibilizer (I) is a hydrocarbon polymer having a polar group, the compatibilizer (I) and the thermoplastic resin (G) are separated by a hydrocarbon polymer portion serving as a base of the polymer. Good affinity. Further, the compatibility between the compatibilizer (I) and the modified EVOH (C) or EVOH (D) is improved by the polar group of the compatibilizer (I). As a result, a stable morphology can be formed in the obtained oxygen absorption layer.

  Examples of the monomer capable of forming the hydrocarbon polymer portion serving as the base of the hydrocarbon polymer having the polar group include ethylene, propylene, 1-butene, isobutene, 3-methylpentene, and 1-hexene. , Α-olefins such as 1-octene; styrene, α-methylstyrene, 2-methylstyrene, 4-methylstyrene, 4-propylstyrene, 4-tert-butylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2 -Styrenic compounds such as ethyl-4-benzylstyrene, 4- (phenylbutyl) styrene, 2,4,6-trimethylstyrene, monofluorostyrene, difluorostyrene, monochlorostyrene, dichlorostyrene, methoxystyrene, tert-butoxystyrene ; 1-vinyl naphthalene, 2-vinyl naphth Examples thereof include vinyl naphthalene compounds such as thalene; conjugated dienes such as butadiene, isoprene, 2,3-dimethylbutadiene, 1,3-pentadiene, 1,3-hexadiene, and the like. One of these may contribute to the formation of the hydrocarbon polymer portion alone, or two or more may contribute to the formation of the hydrocarbon polymer portion.

The following hydrocarbon polymer can be formed from the monomer.
Olefin polymers such as polyethylene (ultra low density polyethylene, low density polyethylene, linear low density polyethylene, medium density polyethylene, high density polyethylene, etc.), polypropylene, ethylene-propylene copolymer; polystyrene, styrene-diene block Copolymers (styrene-isoprene diblock copolymer, styrene-butadiene diblock copolymer, styrene-butadiene-styrene triblock copolymer, styrene-isoprene-styrene triblock copolymer, etc.), hydrogenated products thereof Styrenic polymers such as
Among these, styrene-diene block copolymers (styrene-isoprene diblock copolymer, styrene-butadiene diblock copolymer, styrene-butadiene-styrene triblock copolymer, styrene-isoprene-styrene triblock copolymer). Polymers etc.) and styrene polymers such as hydrogenated products thereof are preferred.

  Examples of the polar group in the hydrocarbon polymer having the polar group include sulfur-containing groups such as a sulfonic acid group, a sulfenic acid group, and a sulfinic acid group; a hydroxyl group; an epoxy group; a ketone group, an ester group, an aldehyde group, and a carboxyl group. Group, carbonyl group-containing group such as acid anhydride group; nitrogen-containing group such as nitro group, amide group, urea group, isocyanate group; phosphorus-containing group such as phosphonic acid ester group, phosphinic acid ester group; boronic acid group, Examples thereof include boron-containing groups such as boronic acid ester groups, boronic acid anhydride groups, and boronic acid groups. Among these, the polar group is particularly preferably a carboxyl group or a boron-containing group. When the polar group is a carboxyl group, the obtained oxygen absorbing layer has high thermal stability. In particular, when the transition metal salt (H) is excessively contained in the resin composition, its thermal stability may be reduced, but the compatibilizer (I) having a carboxyl group together with the transition metal salt (H). If it is contained, thermal stability is maintained.

The manufacturing method of the hydrocarbon polymer having a polar group is not particularly limited, and for example, it can be manufactured by the following method.
1) A method of copolymerizing a monomer capable of forming the hydrocarbon polymer portion and a monomer having a polar group (or a group capable of forming the polar group);
2) A method of using an initiator or a chain transfer agent having a polar group (or a group capable of forming the polar group) when polymerizing the monomer capable of forming the hydrocarbon polymer portion;
3) A method in which a monomer capable of forming the hydrocarbon polymer portion is subjected to living polymerization, and a monomer having a polar group (or a group capable of forming the polar group) is used as a terminator (terminal treatment agent); And 4) after polymerizing a monomer capable of forming the hydrocarbon polymer portion to obtain a polymer, a reactive group in the polymer, for example, a carbon-carbon double bond portion, a polar group A method of introducing a monomer having (or a group capable of forming the polar group) by a reaction.
In the method 1), when copolymerization is performed, any polymerization method of random copolymerization, block copolymerization, and graft copolymerization may be employed.

  Specific examples of the compatibilizer (I) having such a polar group are disclosed in detail in, for example, Patent Document 12. Among the compatibilizers (I), hydrogenated products of styrene-diene block copolymers having a boronic ester group are preferred. The compatibilizer (I) may be used alone or in combination of two or more.

The content of the thermoplastic resin (G) in the resin composition is preferably in the range of 1 to 30% by mass, more preferably in the range of 2 to 20% by mass, and 3 to 15% by mass. More preferably, it is within the range. The total content of the modified EVOH (C), EVOH (D) and compatibilizer (I) in the resin composition is preferably in the range of 70 to 99% by mass, More preferably, it is within the range of 98% by mass, and even more preferably within the range of 85-97% by mass. In the said resin composition, when the content rate of a thermoplastic resin (G) is larger than 30 mass%, there exists a tendency for the gas barrier property with respect to oxygen gas, carbon dioxide gas, etc. of the obtained oxygen absorption layer to fall. On the other hand, when the content rate of a thermoplastic resin (G) is less than 1 mass%, the oxygen absorption function of the obtained oxygen absorption layer tends to be lowered.
Moreover, the ratio of the content rate of modified EVOH (C) in the total content of each of modified EVOH (C), EVOH (D) and compatibilizer (I) is in the range of 5 to 100% by mass. It is preferably within the range of 10 to 80% by mass, more preferably within the range of 20 to 60% by mass.
The resin composition is at least partially crosslinked as described later, but the content of each component in the resin composition is a ratio that does not consider the reaction of each component due to crosslinking. This corresponds to the content of each component in the resin composition before crosslinking.

  Various additives may be added to the above resin composition as necessary. Examples of such additives include sensitizers, curing agents, curing accelerators, antioxidants, plasticizers, ultraviolet absorbers, antistatic agents, colorants, fillers, and the like. It can mix | blend in the range which does not inhibit the effect of this invention. Specific examples of these additives include the following.

  Sensitizer: benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzyl diphenyl disulfide, tetramethyl thiuram monosulfide, azobisbutyronitrile, dibenzyl, diacetyl, acetophenone, 2,2-diethoxyacetophenone, benzophenone, 2-chlorothioxanthone, 2-methylthioxanthone and the like.

  Curing agents: methyl ethyl ketone peroxide, cyclohexane peroxide, cumene peroxide, benzoyl peroxide, dicumyl peroxide, t-butyl perbenzoate, and the like.

  Curing accelerator: amines such as methylaniline, dimethylaniline, diethylaniline, methyl-p-toluidine, dimethyl-p-toluidine, methyl-2-hydroxyethylaniline, di-2-hydroxyethyl-p-toluidine, or hydrochloric acid , Salts with acetic acid, sulfuric acid, phosphoric acid, etc.

  Antioxidant: 2,5-dibutyl-t-butylhydroquinone, 2,6-di-t-butyl-p-cresol, 4,4′-thiobis- (6-t-butylphenol), 2,2′-methylene -Bis- (4-methyl-6-butylphenol), octadecyl-3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate, 4,4'-thiobis- (6-t- Butylphenol).

  Plasticizer: Dimethyl phthalate, diethyl phthalate, dibutyl phthalate, wax, liquid paraffin, phosphate ester, etc.

  UV absorber: ethylene-2-cyano-3,3′-diphenyl acrylate, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3′-t-butyl-) 5'-methylphenyl) 5-chlorotriazole, 2-hydroxy-4-methoxybenzophenone, (2,2'-dihydroxy-4-methoxybenzophenone) and the like.

  Antistatic agents: pentaerythritol monostearate, sorbitan monopalmitate, sulfated oleic acid, polyethylene oxide, carbowax and the like.

  Colorant: Carbon black, phthalocyanine, quinacridone, azo pigment, titanium oxide, bengara, etc.

  Filler: Glass fiber, mica, celite, calcium silicate, aluminum silicate, calcium carbonate, silicon oxide, montmorillonite, etc.

  The molding method for obtaining the oxygen-absorbing layer of the laminate forming the multilayer container of the present invention is not particularly limited, and for example, it may be carried out by melt molding the above resin composition or each component constituting it. Alternatively, the resin composition or a solution containing each component constituting the resin composition may be dried. In the case of melt molding, each component may be supplied to an extruder, melt-kneaded and molded as it is. Further, each component may be melt-kneaded and once pelletized to be molded, and a suitable means can be adopted as appropriate.

  The molding temperature in melt molding varies depending on the melting point of each component, etc., but the molten resin temperature is preferably in the range of 120 to 250 ° C.

  As the melt molding method, any molding method such as an extrusion molding method, a blow molding method, or an injection molding method can be employed. Examples of the extrusion molding method include a T-die method, a hollow molding method, and an inflation method. The shape of the obtained molded body is preferably a layered shape. Moreover, it is also possible to use secondary bodies, such as uniaxial or biaxial stretching or thermoforming, for molded objects, such as a film, a sheet | seat, and a tape obtained by the said shaping | molding method.

  At least a part of the resin composition constituting the oxygen absorption layer included in the laminate forming the multilayer container of the present invention is crosslinked. The crosslinking can be performed on a molded product obtained by molding the resin composition as described above. Specifically, for example, an electron beam, X-ray, Crosslinking can be performed by irradiating at least one selected from the group consisting of γ rays, ultraviolet rays and visible rays, or by heating.

  When using an electron beam, X-ray or γ-ray, the absorbed dose is preferably 1 kGy or more. The absorbed dose is more preferably in the range of 1 to 1,000 kGy, further preferably in the range of 5 to 500 kGy, and particularly preferably in the range of 10 to 200 kGy. When the absorbed dose is 1 kGy or more, the hot water resistance of the obtained oxygen absorbing layer can be further improved. Moreover, when the absorbed dose is 1,000 kGy or less, problems such as a significant decrease in the strength of the oxygen absorbing layer due to the decomposition of EVOH (C) and coloring can be suppressed.

  When the molded body is irradiated with an electron beam or the like to be crosslinked, the crosslinking reaction can proceed due to the contribution of the side chain double bond of the modified EVOH (C). At this time, there is a concern that a crosslinking reaction also occurs in the double bond of the thermoplastic resin (G), the double bond disappears, and the oxygen absorption performance of the oxygen absorption layer is lowered. However, when a thermoplastic resin (G) having a carbon-carbon double bond substantially only in the main chain as described above is used, a decrease in oxygen absorption performance is suppressed even after electron beam irradiation. The reason for this is not clear, but the carbon-carbon double bond present in the main chain is more reactive to radicals generated by irradiation with electron beams or the like than the carbon-carbon double bond present in the side chain. This is presumably because the absorbed dose as described above is not involved in the reaction.

  The thickness of the oxygen absorption layer (thickness of one layer) included in the laminate forming the multilayer container of the present invention is preferably in the range of 1 to 300 μm, and more preferably in the range of 3 to 150 μm. Preferably, it is in the range of 5-50 micrometers.

  The oxygen absorption layer of the laminate forming the multilayer container of the present invention is not particularly limited as long as it has the ability to absorb oxygen, but the oxygen absorption amount measured by the method described later in Examples ( (Integrated value) is preferably 5 ml / g or more, more preferably 10 ml / g or more, further preferably 30 ml / g or more, and particularly preferably 50 ml / g or more.

[Gas barrier layer]
The laminate forming the multilayer container of the present invention has a gas barrier layer having an oxygen permeability of 10 ml / (m ² · day · atm) or less.

When the oxygen permeability of a gas barrier layer exceeds 10 ml / (m < ² > * day * atm), the period which can suppress deterioration and alteration of the content packaged by the obtained multilayer container will become short. Therefore, the oxygen permeability of the gas barrier layer needs to be 10 ml / (m ² · day · atm) or less, preferably 3 ml / (m ² · day · atm) or less, preferably 1 ml / (m ² · Day · atm) or less, more preferably 0.8 ml / (m ² · day · atm) or less. The oxygen permeability (unit: ml / (m ² · day · atm)) of the gas barrier layer is measured using an oxygen permeability measuring device (for example, “MOCON OX-TRAN 10/50” manufactured by Modern Control Co., Ltd.) It is a value measured under the conditions of an oxygen pressure of 1 atm and a carrier gas pressure of 1 atm at 20 ° C. and 65% RH.

The gas barrier layer used in the present invention is not particularly limited as long as it has the above-described oxygen permeability, but is superior in oxygen barrier properties after retorting,
(1) A metal ion in which at least a part of the —COO— group contained in the at least one functional group of the polymer having at least one functional group selected from a carboxyl group and a carboxylic anhydride group is divalent or higher. A layered product (F1) having a layer containing a neutralized product neutralized in [hereinafter, sometimes simply referred to as “layer containing a neutralized product”];
(2) Laminate (F2) having an inorganic layer formed by a vapor deposition method; and (3) Polyvinylidene chloride polymer [hereinafter sometimes abbreviated as “PVDC”] or a composition containing the same Layer (F3);
At least one selected from the group consisting of can be preferably used. As is apparent from the above examples, the gas barrier layer used in the present invention may have a single layer structure or a laminate structure having two or more layers.

  Regarding the laminate (F1), laminate (F2), and layer (F3) described above, the laminate (F1) is superior in oxygen barrier properties after bending compared to the laminate (F2), and the layer (F3) Compared to retort treatment, oxygen barrier properties are excellent. Therefore, the gas barrier layer is preferably a laminate (F1).

[Laminate (F1)]
The laminate (F1) is a neutralized product of a polymer having at least one functional group selected from a carboxyl group and a carboxylic anhydride group [hereinafter sometimes simply referred to as “carboxylic acid-containing polymer”]. A layer comprising In the neutralized product, at least one functional group selected from a carboxyl group and a carboxylic anhydride group of the carboxylic acid-containing polymer [hereinafter sometimes abbreviated as “functional group (f)”] At least a part of —COO— group contained in is neutralized with a divalent or higher metal ion.

  The carboxylic acid-containing polymer has one or more carboxyl groups or one or more carboxylic anhydride groups in one molecule of the polymer. Specific examples of the carboxylic acid-containing polymer include one or more structural units having one or more carboxyl groups in one molecule of the polymer, such as acrylic acid units, methacrylic acid units, maleic acid units, and itaconic acid units. The thing which has. As another specific example, for example, one having at least one structural unit having a structure of carboxylic anhydride, such as a maleic anhydride unit or a phthalic anhydride unit, in one molecule of the polymer. A structural unit having one or more carboxyl groups and / or a structural unit having a carboxylic acid anhydride structure [hereinafter, both may be abbreviated as “carboxylic acid-containing units”] are included in the carboxylic acid-containing polymer. 1 type may be contained in 2 or more types may be contained.

  When the content of the carboxylic acid-containing unit in all the structural units of the carboxylic acid-containing polymer is 10 mol% or more, a laminate (F1) with improved gas barrier properties under high humidity is preferable. The content is more preferably 20 mol% or more, further preferably 40 mol% or more, and particularly preferably 70 mol% or more. In addition, when the carboxylic acid-containing polymer includes both a structural unit having one or more carboxyl groups and a structural unit having a carboxylic anhydride structure, the total content of both is within the above range. Is preferred.

  The carboxylic acid-containing polymer may consist only of carboxylic acid-containing units, but may further have other structural units other than the carboxylic acid-containing units. The structural unit other than the carboxylic acid-containing unit that the carboxylic acid-containing polymer may have is not particularly limited. For example, methyl acrylate unit, methyl methacrylate unit, ethyl acrylate unit, ethyl methacrylate Structural units derived from (meth) acrylic esters such as units, butyl acrylate units and butyl methacrylate units; structural units derived from vinyl esters such as vinyl formate units and vinyl acetate units; styrene units, p-styrene Examples include structural units derived from aromatic vinyl such as sulfonic acid units; structural units derived from olefins such as ethylene units, propylene units, and isobutylene units. The carboxylic acid-containing polymer may have only one type of these other structural units or may have two or more types.

  When the carboxylic acid-containing polymer has two or more kinds of structural units, the carboxylic acid-containing polymer is in the form of an alternating copolymer, a random copolymer, a block copolymer, or a tapered copolymer. Any of the form of a polymer may be sufficient.

  Preferable examples of the carboxylic acid-containing polymer include polyacrylic acid, polymethacrylic acid, and acrylic acid-methacrylic acid copolymer. The carboxylic acid-containing polymer may be one kind or a mixture of two or more kinds of polymers. For example, at least one polymer selected from polyacrylic acid and polymethacrylic acid may be used. Specific examples of the carboxylic acid-containing polymer having other structural units described above include, for example, ethylene-maleic anhydride copolymer, styrene-maleic anhydride copolymer, and isobutylene-maleic anhydride alternating copolymer. Saponified ethylene-acrylic acid copolymer, ethylene-ethyl acrylate copolymer, and the like.

  The molecular weight of the carboxylic acid-containing polymer is not particularly limited, but the number average molecular weight is 5,000 or more from the viewpoint of excellent gas barrier properties of the resulting laminate (F1) and excellent mechanical properties such as drop impact strength. Preferably, it is 10,000 or more, more preferably 20,000 or more. The upper limit of the molecular weight of the carboxylic acid-containing polymer is not particularly limited, but is generally 1,500,000 or less.

  The molecular weight distribution of the carboxylic acid-containing polymer is not particularly limited, but from the viewpoint of improving the surface appearance such as haze of the laminate (F1) and the storage stability of the solution (S) described later. The molecular weight distribution represented by the ratio of weight average molecular weight / number average molecular weight of the carboxylic acid-containing polymer is preferably in the range of 1 to 6, more preferably in the range of 1 to 5, More preferably, it is within the range of 4.

  In the neutralized product, at least a part of the —COO— group contained in at least one functional group selected from the carboxyl group and carboxylic anhydride group of the carboxylic acid-containing polymer is a divalent or higher-valent metal ion. Neutralized. In other words, the neutralized product of the carboxylic acid-containing polymer contains a carboxyl group neutralized with a divalent or higher valent metal ion.

  In the above neutralized product, the moles of carboxyl groups neutralized with divalent or higher metal ions relative to the total number of moles of —COO— groups contained in the functional group (f) of the carboxylic acid-containing polymer before neutralization. The ratio of the number is preferably 10 mol% or more, more preferably 20 mol% or more, further preferably 40 mol% or more, and particularly preferably 60 mol% or more. Although there is no restriction | limiting in particular in the upper limit of the said ratio, For example, it can be 99 mol% or less. Note that the carboxylic anhydride group is considered to contain two —COO— groups. That is, when the carboxylic acid-containing polymer has a moles of carboxyl groups and b moles of carboxylic anhydride groups, the total number of —COO— groups contained in the functional group (f) of the carboxylic acid-containing polymer. Is (a + 2b) moles. By laminating at least part of —COO— groups contained in the functional group (f) of the carboxylic acid-containing polymer with a metal ion having a valence of 2 or more, the laminate (F1) Good gas barrier properties can be exhibited under both wet conditions.

The neutralization degree (ionization degree) of the —COO— group contained in the functional group (f) of the carboxylic acid-containing polymer in the neutralized product is the ATR (the infrared absorption spectrum of the layer containing the neutralized product). It can be determined by measuring by the total reflection measurement method, or by scraping the neutralized product or a composition containing it from the laminate (F1) and measuring the infrared absorption spectrum by the KBr method. Before neutralization peak attributed to C = O stretching vibration of the carboxyl group or carboxylic anhydride group (ionization front) was observed in the range of ^{1600cm -1 ~1850cm} -1, after being neutralized (ionized) C = O stretching vibration of the carboxyl group is to be observed in a range of ^{1500cm -1 ~1600cm} -1, it can be evaluated by separating the two in the infrared absorption spectrum. Specifically, the ratio is determined from the maximum absorbance in each range, and -COO- contained in the functional group (f) of the carboxylic acid-containing polymer in the neutralized product using a calibration curve prepared in advance. The degree of neutralization (ionization degree) of the group can be calculated. A calibration curve can be created by measuring infrared absorption spectra for a plurality of standard samples having different degrees of neutralization.

  It is important that the metal ion that neutralizes the —COO— group contained in the functional group (f) is divalent or higher. When the functional group (f) is not neutralized or is neutralized only by monovalent ions described later, it is difficult to obtain good gas barrier properties. However, when the —COO— group contained in the functional group (f) is neutralized with a small amount of monovalent ions (cations) in addition to divalent or higher metal ions, the laminate (F1) Haze is reduced and the surface appearance is improved. As described above, the present invention includes a case where the functional group (f) of the carboxylic acid-containing polymer is neutralized with both a divalent or higher valent metal ion and a monovalent ion.

  Examples of the divalent or higher metal ion include calcium ion, magnesium ion, divalent iron ion, trivalent iron ion, zinc ion, divalent copper ion, lead ion, divalent mercury ion, barium ion, A nickel ion, a zirconium ion, an aluminum ion, a titanium ion, etc. can be mentioned. Among these, the divalent or higher metal ion is preferably at least one selected from calcium ion, magnesium ion and zinc ion.

In the neutralized product, the number of moles of carboxyl groups neutralized with monovalent ions with respect to the total number of moles of —COO— groups contained in the functional group (f) of the carboxylic acid-containing polymer before neutralization. The occupying ratio is preferably in the range of 0.1 to 10 mol%, more preferably in the range of 0.5 to 5 mol%, and in the range of 0.7 to 3 mol%. Further preferred. However, when the degree of neutralization with monovalent ions is high, the gas barrier property of the laminate (F1) tends to be reduced.
Examples of the monovalent ion include ammonium ion, pyridinium ion, sodium ion, potassium ion, lithium ion, and the like, and ammonium ion is preferable.

  The layer containing the neutralized product may be a layer made of only the neutralized product, or may be a layer made of a composition containing the neutralized product. The content of the neutralized product in the layer containing the neutralized product is preferably in the range of 25 to 100% by mass, because the gas barrier property of the resulting multilayer container becomes better, and 50 to 95% by mass. %, More preferably within a range of 55 to 90% by mass, and particularly preferably within a range of 60 to 85% by mass.

  The composition containing the neutralized product, in addition to the neutralized product of the carboxylic acid-containing polymer, contains at least one metal atom to which at least one characteristic group (atomic group) selected from a halogen atom and an alkoxy group is bonded. It preferably contains a hydrolysis condensate of the seed compound (L). By containing the hydrolysis condensate of compound (L), a gas barrier layer exhibiting extremely good gas barrier properties can be obtained. The hydrolysis condensate of the compound (L) may be reacted with other components (for example, a neutralized product of the carboxylic acid-containing polymer) contained in the composition.

  As the compound (L), at least one of the following compounds (α) and / or compounds (β) can be used. Hereinafter, the compound (α) and the compound (β) will be described.

The compound (α) is at least one compound represented by the following chemical formula (I).
^{_{M 1 X 1 n Y 1 k}} Z 1 m-n-k ··· (I)
In chemical formula (I), M ¹ is Si, Al, Ti, Zr, Cu, Ca, Sr, Ba, Zn, B, Ga, Y, Ge, Pb, P, Sb, V, Ta, W, La and Represents a metal atom selected from Nd. M ¹ is preferably Si, Al, Ti or Zr, and particularly preferably Si.
Further, in the chemical formula (I), ^{X 1} represents -OR ¹ or halogen atom. Here, R ¹ represents an alkyl group (preferably a methyl group or an ethyl group) such as a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, or a t-butyl group. The halogen atom X ¹ represents, for example, a chlorine atom, a bromine atom, an iodine atom, a chlorine atom is preferable.
In the chemical formula (I), Y ¹ represents a hydrogen atom or an alkyl group. Examples of the alkyl group include those described above as the alkyl group represented by R ¹ .
In Formula (I), Z ¹ represents an alkyl group substituted with a functional group having reactivity with a carboxyl group, an aralkyl group substituted with a functional group having reactivity with a carboxyl group, or a carboxyl group. An aryl group substituted with a functional group having reactivity, or an alkenyl group substituted with a functional group having reactivity with a carboxyl group (preferably an alkyl group substituted with a functional group having reactivity with a carboxyl group) ). Here, examples of the functional group having reactivity with a carboxyl group include an epoxy group, an amino group, a hydroxyl group, a halogen atom, a mercapto group, an isocyanate group, a ureido group, an oxazoline group, a carbodiimide group, and the like. Group, mercapto group, isocyanate group, ureido group and halogen atom are preferred. The alkyl group substituted with the functional group, can be exemplified those described above as the alkyl group represented by R ^1. Examples of the aralkyl group substituted with the functional group include a benzyl group, a phenethyl group, and a trityl group. Examples of the aryl group substituted with the functional group include a phenyl group, a naphthyl group, a tolyl group, a xylyl group, and a mesityl group. Examples of the alkenyl group substituted with the functional group include a vinyl group and an allyl group.
In the chemical formula (I), m is equal to the valence of the metal atom M ¹ . n represents an integer of 1 to (m−1). K represents an integer of 0 to (m−2). And it is 1 <= n + k <= (m-1).

  Specific examples of the compound (α) include, for example, γ-glycidoxypropyltrimethoxysilane, (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-aminopropyltrimethoxysilane, and γ-chloropropyltrimethoxysilane. , Γ-bromopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-ureidopropyltrimethoxysilane, chloromethylmethyldimethoxysilane, chloromethyldimethylmethoxysilane, 2-chloroethyl Methyldimethoxysilane, 2-chloroethyldimethylmethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyldimethylmethoxysilane, mercaptomethylmethyldimethoxysilane, mercaptomethy Dimethylmethoxysilane, 2-mercaptoethylmethyldimethoxysilane, 2-mercaptoethyldimethylmethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyldimethylmethoxysilane, isocyanatomethylmethyldimethoxysilane, isocyanatomethyldimethylmethoxysilane 2-isocyanatoethylmethyldimethoxysilane, 2-isocyanatoethyldimethylmethoxysilane, 3-isocyanatopropylmethyldimethoxysilane, 3-isocyanatopropyldimethylmethoxysilane, ureidomethylmethyldimethoxysilane, ureidomethyldimethylmethoxysilane, 2 -Ureidoethylmethyldimethoxysilane, 2-ureidoethyldimethylmethoxysilane, 3-ureidopropylmethyldi Toxisilane, 3-ureidopropyldimethylmethoxysilane, bis (chloromethyl) methylchlorosilane, chloromethyltrimethoxysilane, 2-chloroethyltrimethoxysilane, 2-chloropropyltrimethoxysilane, 4-chlorobutyltrimethoxysilane, 5- Chloropentyltrimethoxysilane, 6-chlorohexyltrimethoxysilane, bis (chloromethyl) dimethoxysilane, bis (chloroethyl) dimethoxysilane, bis (chloropropyl) dimethoxysilane, tris (chloromethyl) methoxysilane, tris (chloroethyl) methoxy Silane, tris (chloropropyl) methoxysilane, mercaptomethyltrimethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptopropyltrimethoxysilane 4-mercaptobutyltrimethoxysilane, 5-mercaptopentyltrimethoxysilane, 6-mercaptohexyltrimethoxysilane, bis (mercaptomethyl) dimethoxysilane, bis (mercaptoethyl) dimethoxysilane, bis (mercaptopropyl) dimethoxysilane, tris ( Mercaptomethyl) methoxysilane, tris (mercaptoethyl) methoxysilane, tris (mercaptopropyl) methoxysilane, fluoromethyltrimethoxysilane, 2-fluoroethyltrimethoxysilane, 3-fluoropropyltrimethoxysilane, bromomethyltrimethoxysilane, 2-bromoethyltrimethoxysilane, iodomethyltrimethoxysilane, 2-iodoethyltrimethoxysilane, 3-iodopropyltrimethoxysilane, (Chloromethyl) phenyltrimethoxysilane, (chloromethyl) phenylethyltrimethoxysilane, 1-chloroethyltrimethoxysilane, 2- (chloromethyl) allyltrimethoxysilane, (3-chlorocyclohexyl) trimethoxysilane, (4 -Chlorocyclohexyl) trimethoxysilane, (mercaptomethyl) phenyltrimethoxysilane, (mercaptomethyl) phenylethyltrimethoxysilane, 1-mercaptoethyltrimethoxysilane, 2- (mercaptomethyl) allyltrimethoxysilane, (3-mercapto (Cyclohexyl) trimethoxysilane, (4-mercaptocyclohexyl) trimethoxysilane, N- (3-triethoxysilylpropyl) gluconamide, N- (3-triethoxysilylpropyl) -4- Droxybutyramide, isocyanatomethyltrimethoxysilane, 2-isocyanatoethyltrimethoxysilane, 2-isocyanatopropyltrimethoxysilane, 4-isocyanatobutyltrimethoxysilane, 5-isocyanatopentyltrimethoxysilane, 6- Isocyanatohexyltrimethoxysilane, bis (isocyanatomethyl) dimethoxysilane, bis (isocyanatoethyl) dimethoxysilane, bis (isocyanatopropyl) dimethoxysilane, tris (isocyanatomethyl) methoxysilane, tris (isocyanatoethyl) methoxy Silane, tris (isocyanatopropyl) methoxysilane, ureidomethyltrimethoxysilane, 2-ureidoethyltrimethoxysilane, 2-ureidopropyltrimethoxysilane, 4-uree Dobutyltrimethoxysilane, 5-ureidopentyltrimethoxysilane, 6-ureidohexyltrimethoxysilane, bis (ureidomethyl) dimethoxysilane, bis (ureidoethyl) dimethoxysilane, bis (ureidopropyl) dimethoxysilane, tris (ureidomethyl) ) Methoxysilane, tris (ureidoethyl) methoxysilane, tris (ureidopropyl) methoxysilane and the like, and the methoxy group portion of these compounds is substituted with ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy. A compound in place of an alkoxy group such as a group or a t-butoxy group or a chlorine group may be used.

  Among these, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ- Aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-ureidopropyltrimethoxysilane, γ- Ureidopropyltriethoxysilane is preferred.

The compound (β) is at least one compound represented by the following chemical formula (II).
M ² X ² _q Y ² _pq (II)
In chemical formula (II), M ² is Si, Al, Ti, Zr, Cu, Ca, Sr, Ba, Zn, B, Ga, Y, Ge, Pb, P, Sb, V, Ta, W, La and Represents a metal atom selected from Nd. M ² is preferably Si, Al, Ti or Zr, and particularly preferably Si, Al or Ti.
In the chemical formula (II), X ² represents —OR ² or a halogen atom. Here, R ² represents an alkyl group (preferably a methyl group or an ethyl group) such as a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, or a t-butyl group. The halogen atom X ² represents, for example, a chlorine atom, a bromine atom, an iodine atom, a chlorine atom is preferable.
In the chemical formula (II), Y ² represents an alkyl group, an aralkyl group, an aryl group or an alkenyl group. Examples of the alkyl group represented by Y ² include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, a t-butyl group, and an n-octyl group. Examples of the aralkyl group represented by Y ² include a benzyl group, a phenethyl group, and a trityl group. Examples of the aryl group represented by Y ² include a phenyl group, a naphthyl group, a tolyl group, a xylyl group, and a mesityl group. Moreover, examples of the alkenyl group represented by Y ² include a vinyl group and an allyl group.
Further, in the chemical formula (II), p is equal to the valence of the metal atom M ^2. q represents an integer of 1 to p.

In the chemical formulas (I) and (II), M ¹ and M ² may be the same or different. X ¹ and X ² may be the same or different.

  Specific examples of the compound (β) include, for example, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, octyltrimethoxysilane, phenyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, Silicon alkoxides such as chlorotrimethoxysilane, chlorotriethoxysilane, dichlorodimethoxysilane, dichlorodiethoxysilane, trichloromethoxysilane, and trichloroethoxysilane; halogenated silanes such as vinyltrichlorosilane, tetrachlorosilane, and tetrabromosilane; tetramethoxytitanium , Alkoxytitanium compounds such as tetraethoxytitanium, tetraisopropoxytitanium and methyltriisopropoxytitanium; halogens such as tetrachlorotitanium Titanium; alkoxyaluminum compounds such as trimethoxyaluminum, triethoxyaluminum, triisopropoxyaluminum, methyldiisopropoxyaluminum, tributoxyaluminum, diethoxyaluminum chloride; tetraethoxyzirconium, tetraisopropoxyzirconium, methyltriisopropoxyzirconium, etc. And the alkoxyzirconium compound.

  When the compound (L) is hydrolyzed, at least a part of the halogen and alkoxy groups of the compound (L) is substituted with a hydroxyl group. Furthermore, the hydrolyzate condenses to form a compound in which metal elements are bonded through oxygen. When this condensation is repeated, it becomes a compound that can be regarded as a metal oxide substantially.

  The hydrolysis condensate of compound (L) preferably has a degree of condensation (P) in the range of 65 to 99%, more preferably in the range of 70 to 99%, and in the range of 75 to 99%. More preferably, it is within. The degree of condensation (P) (%) of the hydrolysis condensate of compound (L) can be calculated as follows.

  A compound in which the total number of alkoxy groups and halogen atoms in one molecule of the compound (L) is a, and the total of condensed alkoxy groups and halogen atoms in the hydrolysis condensate of the compound (L) is i (pieces) When the ratio of (L) is yi (%) in all the compounds (L), i is an integer of 1 to a (including 1 and a) for each value {(i / a) × yi} And add them. That is, the degree of condensation (P) (%) can be obtained from the following formula.

  The value of yi in the hydrolysis condensate of the compound (L) in the layer containing the neutralized product can be measured by solid NMR (DD / MAS method) or the like.

  The hydrolyzed condensate of compound (L) includes compound (L), compound (L) partially hydrolyzed, compound (L) completely hydrolyzed, compound (L) partially hydrolyzed. Manufacture by a method adopted in, for example, a known sol-gel method, using a material obtained by decomposing and condensing, compound (L) completely hydrolyzed, partially condensing, or a combination thereof. Can do. These raw materials may be produced by a known method, or commercially available ones may be used. Although there is no particular limitation, for example, a condensate obtained by hydrolytic condensation of about 2 to 10 molecules can be used as a raw material. Specifically, for example, a material obtained by hydrolyzing and condensing tetramethoxysilane to form a dimer to 10-mer linear condensate can be used as a raw material.

  In the hydrolysis condensate of the compound (L) in the layer containing the neutralized product, the number of molecules to be condensed is the amount of water used in the hydrolysis condensation, the type and concentration of the catalyst, and the hydrolysis condensation. It can be controlled by temperature or the like.

  The specific production method of the hydrolyzed condensate of compound (L) is not particularly limited, but as a typical example of the sol-gel method, hydrolysis and condensation are performed by adding water, acid and alcohol to the above-mentioned raw materials. The method of performing is mentioned.

  Hereinafter, the compound (L) may be described as a metal alkoxide (a compound including a metal to which an alkoxy group is bonded), but a compound including a metal to which a halogen is bonded may be used instead of the metal alkoxide.

  As described above, the compound (L) can be at least one of the compound (α) and / or the compound (β). When the compound (L) includes only the compound (α) or includes both the compound (α) and the compound (β), it is preferable because the gas barrier property of the laminate (F1) can be improved. The compound (L) substantially consists of both the compound (α) and the compound (β), and the molar ratio of the compound (α) / the compound (β) is 0.5 / 99.5-40. More preferably within the range of / 60. When the compound (α) and the compound (β) are used in this proportion, the performance of the laminate (F1) such as gas barrier properties, mechanical properties such as tensile strength and elongation, appearance, and handling properties can be improved. The molar ratio of compound (α) / compound (β) is more preferably in the range of 3/97 to 40/60, and still more preferably in the range of 5/95 to 30/70.

  The content of the hydrolyzed condensate of compound (L) in the layer containing the neutralized product (provided that it is considered as the state before reacting when reacting with other components) is the multilayer obtained Since the gas barrier property of the container becomes better, it is preferably in the range of 5 to 50% by mass, more preferably in the range of 10 to 45% by mass, and in the range of 15 to 40% by mass. More preferably it is.

  The composition containing the neutralized product may further contain a compound having two or more hydroxyl groups, and the compound having two or more hydroxyl groups may contain other components (for example, the above carboxylic acid). And a neutralized product of an acid-containing polymer). In particular, when a compound having two or more hydroxyl groups reacts with a neutralized product of a carboxylic acid-containing polymer to form an ester bond, the gas barrier property after elongation of the resulting gas barrier layer is further improved.

  The compound having two or more hydroxyl groups includes a low molecular weight compound and a high molecular weight compound. Examples of the compound having two or more hydroxyl groups include polyvinyl alcohol, partially saponified polyvinyl acetate, ethylene-vinyl alcohol copolymer, polyethylene glycol, polyhydroxyethyl (meth) acrylate, polysaccharide (starch, etc.). And polysaccharide derivatives derived from polysaccharides (such as starch).

  The content of the compound having two or more hydroxyl groups in the layer containing the neutralized product (provided that it is considered as a state before reaction when reacting with other components) is 0.5 to It is preferably in the range of 50% by mass, more preferably in the range of 1 to 45% by mass, and still more preferably in the range of 2 to 40% by mass.

  The laminate (F1) is preferably a laminate in which the layer containing the neutralized product is laminated on at least one surface of the substrate. Here, the layer containing the neutralized product may be laminated on only one surface of the substrate, or may be laminated on both surfaces of the substrate. The laminate in which the layer containing the neutralized product is laminated on both surfaces of the substrate has an advantage that it is easy to perform post-processing such as bonding other resin layers (films and the like) described later.

  In the laminate (F1), the thickness of the layer containing the neutralized product is not particularly limited, but is preferably in the range of 0.1 to 100 μm. When the thickness is 0.1 μm or more, the gas barrier property of the laminate (F1) can be improved. In addition, when the thickness is 100 μm or less, the layer containing the neutralized product is hardly cracked during processing, transportation, and use of the laminate (F1). The thickness of the layer containing the neutralized product is more preferably in the range of 0.1 to 50 μm, and still more preferably in the range of 0.1 to 20 μm.

  As the substrate, a transparent thermoplastic resin film or a thermosetting resin film can be used. Among them, the thermoplastic resin film is particularly useful when the multilayer container of the present invention is used for food packaging. The base material may have a multilayer structure composed of a plurality of materials.

  Examples of the thermoplastic resin film include polyolefin resins such as polyethylene and polypropylene; polyester resins such as polyethylene terephthalate, polyethylene-2,6-naphthalate, polybutylene terephthalate, and copolymers thereof; nylon 6, nylon 66 Polyamide resin such as nylon 12; polystyrene; poly (meth) acrylate; polyacrylonitrile; polyvinyl acetate; polycarbonate; polyarylate; regenerated cellulose; polyimide; polyetherimide; polysulfone; A film obtained by molding an ionomer resin or the like. When the multilayer container of the present invention is used for food packaging, the substrate is preferably a film made of polyethylene, polypropylene, polyethylene terephthalate, nylon 6 or nylon 66, and polyethylene terephthalate, nylon 6 or nylon 66. More preferably, the film is made of The thermoplastic resin film may be either an unstretched film or a stretched film, but a stretched film is preferred from the viewpoint of moldability.

  Although it does not specifically limit as thickness of a thermoplastic resin film, It is preferable to exist in the range of 1-200 micrometers from a viewpoint of mechanical toughness, impact resistance, and a puncture resistance characteristic, and it is 5-100 micrometers. More preferably within range

  The base material may have an adhesive layer (T) on the side laminated with the layer containing the neutralized product. According to this structure, the adhesiveness of a base material and the layer containing the said neutralized material can be improved. The said adhesive layer (T) can be formed from a well-known adhesive, As a specific formation method, the surface of the above-mentioned thermoplastic resin film, a thermosetting resin film, etc. is mentioned with a well-known anchor coating agent, for example. The method of processing is mentioned.

  The total thickness of the laminate (F1) is not particularly limited, but is preferably in the range of 1 to 300 μm from the viewpoint of mechanical toughness, impact resistance, puncture resistance, More preferably, it is in the range of 5 to 150 μm.

  In the laminate (F1), for example, a layer made of a composition containing a hydrolysis condensate of the compound (L) and a carboxylic acid-containing polymer is formed on a substrate (first step), and then the group A layer made of the composition formed on a material is brought into contact with a solution containing metal ions having a valence of 2 or more (second step; hereinafter, this step may be referred to as an “ionization step”). be able to.

  In the first step, for example, compound (L), compound (L) partially hydrolyzed, compound (L) completely hydrolyzed, compound (L) partially hydrolyzed and condensed And at least one selected from those in which the compound (L) is completely hydrolyzed and partly condensed [hereinafter sometimes abbreviated as “compound (L) component”] and a carboxylic acid-containing compound A step of preparing a solution (S) containing a polymer, and a step of applying the solution (S) to at least one surface of a substrate and drying to form a layer containing a compound (L) component Can be implemented. The solution (S) can be dried by removing the solvent contained in the solution (S).

  In the carboxylic acid-containing polymer contained in the solution (S), as described above, a part of the —COO— group contained in the functional group (f) (for example, 0.1 to 10 mol%) is 1 It may be neutralized with a valent ion.

  Next, the layer formed on the base material in the first step is brought into contact with a solution containing divalent or higher metal ions (second step). In the second step, at least part of the —COO— group contained in the functional group (f) contained in the carboxylic acid-containing polymer in the layer is neutralized with a divalent or higher metal ion, and the carboxylic acid described above is obtained. It becomes a neutralized product of the containing polymer. At this time, the ratio of neutralizing with divalent or higher metal ions (the degree of ionization) can be achieved by changing conditions such as the temperature of the solution containing the metal ions, the concentration of the metal ions, and the immersion time in the solution containing the metal ions. Can be adjusted.

  In the second step, for example, a solution containing a divalent or higher metal ion is sprayed on the formed layer, or both the base material and the layer on the base material are immersed in a solution containing a divalent or higher metal ion. Can be done.

The solution (S) can be prepared using the compound (L) -based component, the carboxylic acid-containing polymer, and a solvent. Specifically, for example,
(1) A method in which a compound (L) -based component is added to and mixed with a solution in which a carboxylic acid-containing polymer is dissolved;
(2) A method in which the compound (α) that is the compound (L) component is added to the solution in which the carboxylic acid-containing polymer is dissolved, and then the compound (L) component is added and mixed;
(3) An oligomer (a kind of hydrolysis condensate) is prepared from the compound (L) component in the presence or absence of a solvent, and the oligomer and a solution in which the carboxylic acid-containing polymer is dissolved are mixed. Method;
Etc. In addition, a compound (L) type | system | group component and the oligomer prepared from it may be mixed with a solution independently, and may be mixed with a solution with the form of the solution which dissolved them.

  By adopting the above method (3) as the method for preparing the solution (S), a laminate (F1) having better gas barrier properties can be obtained. Hereinafter, the method (3) will be described more specifically.

  The method (3) includes a step (St1) of preparing a solution by dissolving a carboxylic acid-containing polymer in a solvent, and a step of preparing an oligomer by hydrolytic condensation of the compound (L) -based component under specific conditions. (St2) and the step (St3) of mixing the solution obtained in the step (St1) and the oligomer obtained in the step (St2).

  In the step (St1), the solvent used for dissolving the carboxylic acid-containing polymer may be selected according to the type of the carboxylic acid-containing polymer. For example, in the case of a water-soluble polymer such as polyacrylic acid or polymethacrylic acid, water is suitable. In the case of a polymer such as an isobutylene-maleic anhydride copolymer or a styrene-maleic anhydride copolymer, water containing an alkaline substance such as ammonia, sodium hydroxide, or potassium hydroxide is preferred. Further, in the step (St1), alcohols such as methanol and ethanol; ethers such as tetrahydrofuran, dioxane, trioxane and dimethoxyethane; ketones such as acetone and methyl ethyl ketone; ethylene glycol as long as the dissolution of the carboxylic acid-containing polymer is not hindered. Glycols such as propylene glycol; glycol derivatives such as methyl cellosolve, ethyl cellosolve, n-butyl cellosolve; glycerin; acetonitrile; dimethylformamide; dimethyl sulfoxide;

  In the step (St2), it is preferable to obtain an oligomer by hydrolyzing and condensing the compound (L) system component in a reaction system containing the compound (L) system component, an acid catalyst, water and, if necessary, an organic solvent. . Specifically, a technique employed in a known sol-gel method can be applied. When the compound (L) is used as the compound (L) component, a laminate (F1) having higher gas barrier properties can be obtained.

As the acid catalyst used in the step (St2), a known acid catalyst can be used. For example, hydrochloric acid, sulfuric acid, nitric acid, p-toluenesulfonic acid, benzoic acid, acetic acid, lactic acid, butyric acid, carbonic acid, oxalic acid, Maleic acid or the like can be used. Of these, hydrochloric acid, sulfuric acid, nitric acid, acetic acid, lactic acid and butyric acid are particularly preferred. Although the preferable usage-amount of an acid catalyst changes with kinds of catalyst to be used, it is a ratio which becomes in the range of 1 * 10 < ^-5 > -10 mol with respect to 1 mol of metal atoms of a compound (L) type | system | group component. The ratio is preferably in the range of 1 × 10 ^{−4 to} 5 mol, and more preferably in the range of 5 × 10 ⁻⁴ to 1 mol. When the usage-amount of an acid catalyst exists in this range, a laminated body (F1) with high gas barrier property is obtained.

  Moreover, although the preferable usage-amount of water in a process (St2) changes with kinds of compound (L) type | system | group component, the alkoxy group of a compound (L) type | system | group component or a halogen atom (when both are mixed together) 1 mol The ratio is preferably in the range of 0.05 to 10 mol, more preferably in the range of 0.1 to 4 mol, and in the range of 0.2 to 3 mol. More preferably, the ratio is as follows. When the usage-amount of water exists in this range, the gas barrier property of the laminated body (F1) obtained will become especially excellent. In the step (St2), when a component containing water such as hydrochloric acid is used, the amount of water used is preferably determined in consideration of the amount of water introduced by the component.

  Furthermore, in the reaction system of the step (St2), an organic solvent may be used as necessary. The organic solvent used will not be specifically limited if it is a solvent in which a compound (L) type component dissolves. For example, alcohols such as methanol, ethanol, isopropanol, and normal propanol are preferably used as the organic solvent, and alcohols having the same molecular structure (alkoxy component) as the alkoxy group of the compound (L) component are more preferably used. It is done. Specifically, methanol is preferred for tetramethoxysilane and ethanol is preferred for tetraethoxysilane. Although the usage-amount of an organic solvent is not specifically limited, It is preferable that it is the quantity which the density | concentration of a compound (L) type | system | group component exists in the range of 1-90 mass%, and is the quantity used in the range of 10-80 mass%. It is more preferable that the amount be in the range of 10 to 60% by mass.

  In the step (St2), the temperature of the reaction system is not necessarily limited when performing the hydrolytic condensation of the compound (L) component in the reaction system, but it is preferably in the range of 2 to 100 ° C. More preferably, it is in the range of 4 to 60 ° C, and further preferably in the range of 6 to 50 ° C. The reaction time varies depending on the reaction conditions such as the amount and type of the catalyst, but is preferably in the range of 0.01 to 60 hours, more preferably in the range of 0.1 to 12 hours, and still more preferably. Is in the range of 0.1 to 6 hours. The atmosphere of the reaction system is not necessarily limited, and an atmosphere such as an air atmosphere, a carbon dioxide atmosphere, a nitrogen stream, or an argon atmosphere can be employed.

  In the step (St2), the total amount of the compound (L) component may be added to the reaction system all at once, or may be added to the reaction system in several small portions. In any case, it is preferable that the total amount of the compound (L) component used satisfies the preferred range of the ratio with each of the above components. The oligomer prepared by the step (St2) preferably has a degree of condensation (P) of about 25 to 60% in terms of the degree of condensation (P).

  In the step (St3), a solution (S) is prepared by mixing an oligomer derived from the compound (L) component and a solution containing a carboxylic acid-containing polymer. From the viewpoint of the storage stability of the solution (S) and the gas barrier property of the resulting laminate (F1), the pH of the solution (S) is preferably in the range of 1.0 to 7.0. More preferably, it is in the range of ˜6.0, and further preferably in the range of 1.5 to 4.0.

  The pH of the solution (S) can be adjusted by a known method, for example, acidic compounds such as hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, acetic acid, butyric acid, ammonium sulfate, sodium hydroxide, potassium hydroxide, ammonia, It can be adjusted by adding a basic compound such as trimethylamine, pyridine, sodium carbonate or sodium acetate. At this time, when a basic compound that provides a monovalent cation is used in the solution, a part of the —COO— group contained in the functional group (f) of the carboxylic acid-containing polymer is neutralized with a monovalent ion. can do.

  In addition, the solution (S) may optionally be a compound having two or more hydroxyl groups, or a carbonate, hydrochloride, nitrate, hydrogencarbonate, sulfate, within the range not impairing the effects of the present invention. Metal salts of inorganic acids such as hydrogen sulfate, phosphate, borate and aluminate; Metal salts of organic acids such as oxalate, acetate, tartrate and stearate; Aluminum acetylacetonate Acetylacetonate metal complexes such as, cyclopentadienyl metal complexes such as titanocene, metal complexes such as cyano metal complexes; layered clay compounds; cross-linking agents; polymer compounds other than the above; plasticizers; antioxidants; An agent; a flame retardant may be included. The solution (S) is a fine powder of a metal oxide produced by hydrolyzing and polycondensing the metal alkoxide; a metal oxide prepared by hydrolyzing, polycondensing or burning the metal alkoxide dry. Fine powder; silica fine powder prepared from water glass may be included.

  The prepared solution (S) is applied to at least one surface of the substrate. The method for applying the solution (S) to the substrate is not particularly limited, and a known method can be employed. Preferred methods include, for example, casting method, dipping method, roll coating method, gravure coating method, screen printing method, reverse coating method, spray coating method, kit coating method, die coating method, metal ring bar coating method, chamber doctor combined coating Method, curtain coating method and the like.

  After applying the solution (S) onto the substrate, the solvent before the ionization step is obtained by removing the solvent contained in the solution (S). The method for removing the solvent is not particularly limited, and a known method can be applied. Specifically, methods such as a hot air drying method, a hot roll contact method, an infrared heating method, and a microwave heating method can be applied alone or in combination. A drying temperature will not be restrict | limited especially if it is 15-20 degreeC or more lower than the flow start temperature of a base material, and 15-20 degreeC or more lower than the thermal decomposition start temperature of a carboxylic acid containing polymer. The drying temperature is preferably within the range of 40 to 200 ° C, more preferably within the range of 60 to 180 ° C, and even more preferably within the range of 80 to 140 ° C. The removal of the solvent may be carried out under normal pressure or reduced pressure.

  By bringing the laminate before the ionization step obtained by the above steps into contact with a solution containing metal ions having a valence of 2 or more [hereinafter sometimes abbreviated as “solution (MI)”] (ionization step) The body (F1) can be obtained. The ionization process may be performed at any stage as long as the effects of the present invention are not impaired. For example, the ionization step may be performed when the single laminate (F1) is produced, or may be performed after the laminate is formed to form the multilayer container of the present invention, or the multilayer container of the present invention. It may be performed after making the form of, or may be performed after the contents are filled in the multilayer container and sealed.

  The solution (MI) can be prepared by dissolving, in a solvent, a compound that releases a divalent or higher valent metal ion (polyvalent metal compound) upon dissolution. The solvent used in preparing the solution (MI) is preferably water, but may be a mixture of an organic solvent miscible with water and water. Examples of such an organic solvent include lower alcohols such as methanol, ethanol, n-propanol, and isopropanol; ethers such as tetrahydrofuran, dioxane, trioxane, and dimethoxyethane; ketones such as acetone, methyl ethyl ketone, methyl vinyl ketone, and methyl isopropyl ketone. Glycols such as ethylene glycol and propylene glycol; glycol derivatives such as methyl cellosolve, ethyl cellosolve and n-butyl cellosolve; glycerin; acetonitrile; dimethylformamide; dimethylacetamide; dimethylsulfoxide;

As the polyvalent metal compound, a compound that releases the above metal ion as a divalent or higher metal ion that neutralizes the —COO— group contained in the functional group (f) of the carboxylic acid-containing polymer can be used. . Specifically, for example, calcium acetate, calcium hydroxide, calcium chloride, calcium nitrate, calcium carbonate, magnesium acetate, magnesium hydroxide, magnesium chloride, magnesium carbonate, iron (II) acetate, iron (II) chloride, iron acetate (III), iron chloride (III), zinc acetate, zinc chloride, copper acetate (II), copper acetate (III), lead acetate, mercury acetate (II), barium chloride, barium sulfate, nickel sulfate, lead sulfate, chloride Zirconium, zirconium nitrate, aluminum sulfate, potassium alum (KAl (SO ₄ ) ₂ ), titanium (IV) sulfate, or the like can be used. A polyvalent metal compound may be used individually by 1 type, or may use 2 or more types together. Preferred polyvalent metal compounds include calcium acetate, calcium hydroxide, magnesium acetate, and zinc acetate.

The concentration of the polyvalent metal compound in the solution (MI) is not particularly limited, but is preferably in the range of 5 × 10 ⁻⁴ to 50% by mass, more preferably in the range of 1 × 10 ⁻² to 30% by mass. More preferably, it is in the range of 1 to 20% by mass.

  When the laminate before the ionization step is brought into contact with the solution (MI), the temperature of the solution (MI) is not particularly limited, but the higher the temperature, the faster the ionization rate of the carboxylic acid-containing polymer. The temperature of the solution (MI) is preferably within the range of 30 to 140 ° C, more preferably within the range of 40 to 120 ° C, and even more preferably within the range of 50 to 100 ° C.

  It is desirable to remove the solvent remaining in the laminate after contacting the laminate before the ionization step with the solution (MI). The method for removing the solvent is not particularly limited, and a known method can be applied. Specifically, drying methods such as a hot air drying method, a hot roll contact method, an infrared heating method, and a microwave heating method can be applied alone or in combination of two or more. The temperature at which the solvent is removed is not particularly limited as long as it is 15 to 20 ° C. or more lower than the flow start temperature of the substrate and 15 to 20 ° C. or lower than the thermal decomposition start temperature of the carboxylic acid-containing polymer. The drying temperature is preferably within the range of 40 to 200 ° C, more preferably within the range of 60 to 150 ° C, and even more preferably within the range of 80 to 120 ° C. The removal of the solvent may be carried out under normal pressure or reduced pressure.

  In order not to impair the appearance of the surface of the laminate (F1), it is preferable to remove excess polyvalent metal compound adhering to the surface of the laminate before or after removing the solvent. As a method for removing the polyvalent metal compound, washing using a solvent in which the polyvalent metal compound dissolves is preferable. As the solvent in which the polyvalent metal compound dissolves, a solvent that can be used for the solution (MI) can be used, and the same solvent as the solvent for the solution (MI) is preferably used.

  In the method for manufacturing the laminate (F1), the layer formed in the first step is heat-treated at a temperature of 120 to 240 ° C. after the first step and before and / or after the second step. A process may be further included. That is, you may heat-process with respect to the laminated body before an ionization process, and / or the laminated body after an ionization process. The heat treatment may be performed at any stage as long as the removal of the solvent of the applied solution (S) is almost completed, but the surface appearance is good by heat-treating the laminate before the ionization process. A laminate (F1) is obtained. The temperature of the heat treatment is preferably in the range of 120 to 240 ° C, more preferably in the range of 130 to 230 ° C, and still more preferably in the range of 150 to 210 ° C. The heat treatment can be performed in air, under a nitrogen atmosphere, under an argon atmosphere, or the like.

[Laminate (F2)]
The laminate (F2) that can be used as a gas barrier layer has a layer made of an inorganic material such as an inorganic oxide formed by a vapor deposition method.

  The inorganic substance which comprises the layer which consists of the said inorganic substance should just have a gas barrier property with respect to oxygen, Preferably, it has transparency. Specific examples include inorganic oxides such as aluminum oxide, silicon oxide, silicon oxynitride, magnesium oxide, tin oxide, and mixtures thereof. Among these, aluminum oxide, silicon oxide, or magnesium oxide is preferable because of its excellent barrier properties against gases such as oxygen and water vapor.

  Although the preferable thickness of the layer which consists of inorganic substances changes with kinds of inorganic substances, such as an inorganic oxide which comprises the said layer, it is preferable to exist in the range of 2-500 nm. Within this range, a thickness at which the gas barrier properties and mechanical properties of the laminate (F2) are good may be selected. When the thickness of the layer made of an inorganic material is 2 nm or more, barrier properties against gases such as oxygen and water vapor can be expressed with good reproducibility. On the other hand, when the thickness of the layer made of an inorganic material is 500 nm or less, a decrease in gas barrier properties after the laminate (F2) is stretched and bent is suppressed. The thickness of the inorganic layer is more preferably in the range of 5 to 200 nm, and still more preferably in the range of 10 to 100 nm.

  The layer made of an inorganic substance can be formed by depositing an inorganic oxide on a substrate. Examples of the forming method include a vacuum deposition method, a sputtering method, an ion plating method, a chemical vapor deposition method (CVD), and the like. Among these, the vacuum vapor deposition method is preferable from the viewpoint of productivity. As a heating method in performing vacuum deposition, any of an electron beam heating method, a resistance heating method, and an induction heating method is preferable. Further, in order to improve the adhesion between the inorganic layer and the substrate and the denseness of the inorganic layer, vapor deposition may be performed using a plasma assist method or an ion beam assist method. Moreover, in order to improve the transparency of the layer made of an inorganic substance, a reactive vapor deposition method in which an oxygen gas or the like is blown to advance the reaction during vapor deposition may be employed.

  A transparent thermoplastic resin film or a thermosetting resin film can be used as the base material for forming the layer made of an inorganic substance. Among them, the thermoplastic resin film is particularly useful when the multilayer container of the present invention is used for food packaging. The base material may have a multilayer structure composed of a plurality of materials.

  Examples of the thermoplastic resin film include polyolefin resins such as polyethylene and polypropylene; polyester resins such as polyethylene terephthalate, polyethylene-2,6-naphthalate, polybutylene terephthalate, and copolymers thereof; nylon 6, nylon 66 Polyamide resin such as nylon 12; polystyrene; poly (meth) acrylate; polyacrylonitrile; polyvinyl acetate; polycarbonate; polyarylate; regenerated cellulose; polyimide; polyetherimide; polysulfone; A film obtained by molding an ionomer resin or the like. When the multilayer container of the present invention is used for food packaging, the substrate is preferably a film made of polyethylene, polypropylene, polyethylene terephthalate, nylon 6 or nylon 66, and polyethylene terephthalate, nylon 6 or nylon 66. More preferably, the film is made of The thermoplastic resin film may be either an unstretched film or a stretched film, but a stretched film is preferred from the viewpoint of moldability.

  Although it does not specifically limit as thickness of a thermoplastic resin film, It is preferable to exist in the range of 5-200 micrometers from a viewpoint of mechanical toughness, impact resistance, and a puncture resistance characteristic, and it is 5-100 micrometers. More preferably, it is within the range.

[Layer of PVDC or composition containing the same (F3)]
The layer (F3) that can be used as a gas barrier layer is a layer made of only PVDC or a layer made of a composition containing PVDC. The layer (F3) may have a single layer structure or a laminate structure having two or more layers. Examples of the layer (F3) include a PVDC (eg, vinylidene chloride-vinyl chloride copolymer) film, a film obtained by coating an emulsion mainly composed of PVDC on a thermoplastic resin film, and the like. As a film in which an emulsion mainly composed of PVDC is coated on a thermoplastic resin film, the coated surface is represented by “K”. For example, KNy (Ny: nylon), KPET (PET: polyethylene terephthalate), KPVA (PVA) : Polyvinyl alcohol), KOPP (OPP: biaxially stretched polypropylene), KPT (PT: cellophane), etc., and those having an oxygen permeability of 10 ml / (m ² · day · atm) or less are appropriately selected. Just choose.
As said thermoplastic resin film, what was mentioned above as a thermoplastic resin film which can be used as a base material in laminated body (F1) and (F2) can be used.

  When the layer (F3) is a layer made of a composition containing PVDC, the proportion of PVDC in the layer is preferably in the range of 20 to 100% by mass, and in the range of 50 to 100% by mass. More preferably.

  Although it does not specifically limit as thickness of a layer (F3), It is preferable to exist in the range of 1-200 micrometers from viewpoints, such as mechanical toughness, impact resistance, and a puncture resistance characteristic, and 5-100 micrometers. It is more preferable that it is in the range.

[Laminate]
As long as the laminate forming the multilayer container of the present invention has the oxygen absorbing layer and the gas barrier layer, the layer structure is not limited, and even if it has only the oxygen absorbing layer and the gas barrier layer, You may have further layers other than an oxygen absorption layer and a gas barrier layer. Examples of such other layers include resin layers other than the oxygen absorption layer and gas barrier layer (for example, polyolefin layer, nylon layer, polyester layer, polystyrene layer, polyurethane layer, polyvinyl chloride layer, polyacrylonitrile layer). , Polycarbonate layer, acrylic resin layer, ionomer layer, ethylene-acrylic acid copolymer layer, ethylene-methyl acrylate copolymer layer, ethylene-methacrylic acid copolymer layer, polyvinyl ester layer, ethylene-vinyl acetate copolymer For example, an elastomer layer), a paper layer, a fabric layer, and the like.
The laminated body forming the multilayer container of the present invention may have one oxygen absorbing layer and one gas barrier layer, or may have two or more of either or both of these layers. Moreover, when the said laminated body has said other layer, the said laminated body may have the other layer of 1 layer, or may have the other layer of 2 layers or more. When the laminate has two or more oxygen absorbing layers, these oxygen absorbing layers may have the same configuration or different configurations. When the laminate has two or more gas barrier layers, these gas barrier layers may have the same configuration or different configurations. When the laminate has two or more other layers, these other layers may have the same configuration or different configurations.

The specific layer structure of the above-mentioned laminate forming the multilayer container of the present invention is represented by “C” for the oxygen absorbing layer (provided that when a plurality of Cs need to be distinguished from each other, C ¹ , C ² ,. ..), And the gas barrier layer is expressed as “F” (however, when a plurality of F need to be distinguished from each other, expressed as F ¹ , F ² ,...), For example, C / F , C / F / C, F / C / F, F ¹ / F ² / C, F / C / F / C, C ² / C ¹ / F / C ¹ / C ² , F / C ¹ / C ² / F, F / C / polyolefin layer, F / C / nylon layer / polyolefin layer, F / nylon layer / C / polyolefin layer, nylon layer / F / C / polyolefin layer, paper layer / polyolefin layer / F / C / Polyolefin layer, paper layer / polyolefin layer / F / C / nylon layer / polyolefin layer, paper layer / poly Refin layer / F / nylon layer / C / polyolefin layer, paper layer / polyolefin layer / nylon layer / F / C / polyolefin layer, polyolefin layer / paper layer / polyolefin layer / F / C / polyolefin layer, polyolefin layer / paper layer / Polyolefin layer / F / nylon layer / C / polyolefin layer, polyolefin layer / paper layer / polyolefin layer / nylon layer / F / C / polyolefin layer, and the like. Note that an adhesive layer can be appropriately provided between the layers. The adhesive layer can be formed using an adhesive (for example, an anchor coat agent), an adhesive resin, or the like.
Hereinafter, the polyolefin layer, the nylon layer, and the paper layer will be described in detail.

  In the polyolefin layer, for example, low density polyethylene, medium density polyethylene, high density polyethylene, linear (linear) low density polyethylene, polypropylene, propylene copolymer (for example, alpha olefin of carbon 4-20, and the like) Copolymer), polybutene, polymethylpentene, ethylene-α-olefin (for example, α-olefin having 3 to 20 carbon atoms) copolymer, polyolefin such as ethylene-propylene copolymer, and unsaturated carboxylic acid. Alternatively, a film or sheet formed from one or two or more of those graft-modified with an acid anhydride or ester thereof can be used. These polyolefin layers may be stretched or unstretched. Among these, the polyolefin layer is preferably formed of low-density polyethylene, linear (linear) low-density polyethylene, or polypropylene, and is formed of linear (linear) low-density polyethylene or polypropylene. Those are more preferable. In addition, from the viewpoint of ease of molding, heat resistance, etc., any of the polyolefin layers constituting the laminate is an unstretched film or sheet formed from low-density polyethylene, linear (linear) low It is preferably composed of an unstretched film or sheet formed from high-density polyethylene, or an unstretched film or sheet formed from polypropylene, and unstretched formed from linear (linear) low-density polyethylene More preferably, the film or sheet is constituted by an unstretched film or sheet formed from polypropylene.

  When the laminate having a polyolefin layer is used as a multilayer container, the polyolefin layer is preferably the innermost layer. The innermost polyolefin layer is a non-stretched film or sheet formed from low-density polyethylene, a non-stretched film or sheet formed from linear (linear) low-density polyethylene, or a non-stretched film or sheet formed from polypropylene. It is preferable that the film is composed of a stretched film or sheet.

  The polyolefin layer serving as the innermost layer can function as a seal layer when the multilayer container of the present invention is produced. By using a laminate having a seal layer, the multilayer container of the present invention can be easily produced by a technique such as heat sealing. Therefore, the present invention is a laminate having the oxygen absorbing layer, the gas barrier layer, and the seal layer, the oxygen absorbing layer being disposed between the gas barrier layer and the seal layer, Includes a laminated body disposed on the outermost surface. From such a laminate, the multilayer container of the present invention in which the seal layer is the innermost layer can be obtained.

  The thickness of the polyolefin layer is not particularly limited, but is preferably in the range of 10 to 200 μm from the viewpoint of mechanical toughness, impact resistance, puncture resistance, and the like, in the range of 20 to 150 μm. More preferably, it is within.

  For the nylon layer, for example, a film or sheet formed of one or more of nylon 6, nylon 66, nylon 11, nylon 12, nylon 610, nylon 612, nylon MXD6, and the like can be used. These nylon layers may be stretched or unstretched. Among these, the nylon layer is preferably made of nylon 6 or nylon 66. The nylon layer is preferably a stretched film or sheet.

  The thickness of the nylon layer is not particularly limited, but from the viewpoint of mechanical toughness, impact resistance, puncture resistance, etc., it is preferably in the range of 1 to 200 μm, and in the range of 5 to 100 μm. More preferably, it is within.

  Examples of the paper used for the paper layer include craft paper, fine paper, imitation paper, glassine paper, parchment paper, synthetic paper, white board paper, Manila ball, milk carton base paper, cup base paper, ivory paper, and the like.

The production method of the laminate for forming the multilayer container of the present invention is not particularly limited, and may be melt-molded, or each layer may be formed using an adhesive or the like, for example, a dry lamination method, a wet lamination method, or a hot melt lamination method. Etc., and may be coated with a solution. In the case of melt molding, a coextrusion molding method, a co-injection molding method, an extrusion coating method using a T die, or the like can be employed.
In producing the laminate, it may be practically advantageous to produce a gas barrier layer in advance and laminate it with the oxygen-absorbing layer or another resin layer.

[Multilayer container]
The multilayer container of the present invention is formed from the above laminate. And the gas barrier layer which the said laminated body has is arrange | positioned on the outer side of the oxygen absorption layer. In the multilayer container of the present invention, it is sufficient that at least one of the gas barrier layers included in the laminate is disposed outside at least one of the oxygen absorption layers. In the case of having a layer, some of them may be disposed inside the oxygen absorbing layer. However, in order for the oxygen absorption layer to efficiently absorb oxygen in the multilayer container, at least one of the oxygen absorption layers of the multilayer container must not have a gas barrier layer disposed inside thereof. Is preferred.

  The multilayer container of the present invention may be entirely formed of the laminate, but only a part of the multilayer container may be formed of the laminate. Specifically, when the multilayer container is composed of a cup and a lid, even if only the cup is formed of the laminate, only the lid is formed of the laminate, both of which are the laminate. May be formed. However, from the standpoint of maintaining the internal oxygen concentration at a low level for a long period of time, the multilayer container of the present invention is preferably in a form sealed only by the laminate.

  The shape of the multilayer container of the present invention is not particularly limited and can be appropriately designed according to the application. A paper container, a paper container with a window, etc. are mentioned.

  The method for producing the multilayer container of the present invention is not particularly limited. For example, the laminate can be produced in advance and heat-sealed, and more specifically, a plurality of methods can be used. The laminates can be heat-sealed, or one laminate can be bent and heat-sealed to have a desired shape. It can also be produced by thermoforming.

  The multilayer container of the present invention is highly suppressed in oxygen intrusion even after retorting, and the internal oxygen concentration is kept at a low level even after long-term storage under adverse conditions of high temperature and humidity after retorting. Can keep. Therefore, the multilayer container of the present invention can be preferably used for food packaging containing cooked rice, cup ramen, yogurt, fruit jelly, pudding, miso, space food, military food, and the like. In the multilayer container for food packaging, it is preferable that at least the lid material is formed of the laminate. Moreover, the multilayer container of this invention can be preferably used also for uses other than food packaging, such as a jacket material of a vacuum heat insulation board, a medical infusion bag, and an electronic member packaging container.

  Although there is no restriction | limiting in particular in the method of packaging a content with the multilayer container of this invention, For example, methods, such as vacuum packaging, skin pack, deep drawing packaging, and rocket packaging, are employable.

After filling the contents into the multilayer container of the present invention, a package having excellent long-term storage stability can be obtained by heat sterilization treatment, particularly retort treatment. For the retort treatment, various methods such as a recovery method, a replacement method, a steam method, a shower method, and a spray method can be adopted. After carrying out the retort treatment, it is preferable to dry within a range of 40 to 150 ° C. for 1 to 120 minutes in order to obtain a more transparent multilayer container.
In addition to the retort treatment, other heat sterilization methods such as a hot filling method can also be employed.

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.
The molecular structure, number average molecular weight and weight average molecular weight of the thermoplastic resin (G); ethylene content and saponification degree of EVOH (A) and (D); modification degree of modified EVOH (C); EVOH (A) And (D) and modified EVOH (C) melt flow rate (MFR); single-layer film retort suitability and oxygen absorption (integrated value); multi-layer container immediately after retort treatment, accumulated dissolved oxygen concentration, retort suitability, 1 year Each measurement or evaluation method of the accumulated dissolved oxygen concentration after the passage and the oxygen transmission rate (OTR) after the passage of one year is shown below.

The molecular structure of the thermoplastic resin (G) was determined by ¹ H-NMR (nuclear magnetic resonance) measurement using a CDCl ₃ solvent (using “JNM-GX-500 type” manufactured by JEOL Ltd.).

The number average molecular weight and weight average molecular weight of the thermoplastic resin (G) were measured by gel permeation chromatography (GPC), and expressed as polystyrene equivalent values. Detailed measurement conditions are as follows.
<Measurement conditions>
Apparatus: Showa Denko KK, gel permeation chromatography “SYSTEM-11”
Column: KF-806L (Shodex), column temperature: 40 ° C
Mobile phase: Tetrahydrofuran, Flow rate: 1.0 ml / min Detector: RI, Filtration: 0.45 μm filter, Concentration: 0.1% by mass

It was determined by ¹ H-NMR measurement (using “JNM-GX-500 type” manufactured by JEOL Ltd. ) using the ethylene content of EVOH (A) and (D) and the degree of saponification DMSO-d ₆ as a solvent.

A sample used for measuring the degree of modification of the modified EVOH (C) was pulverized, and low molecular weight components were extracted with acetone, and then dried at 120 ° C. for 12 hours. The sample after drying was subjected to ¹ H-NMR measurement (using “JNM-GX-500 type” manufactured by JEOL Ltd.) using DMSO-d ₆ as a solvent, and within the obtained spectrum, modified EVOH (C) The double bond methine proton peak (5.9 ppm) or double bond methylene proton peak (5.2 ppm) derived from the epoxy compound (B) having a double bond, and the EVOH skeleton (mainly Used to modify the molar ratio of the EVOH (A) monomer unit from the area ratio with the peak (1.4 ppm) derived from the methylene moiety forming the chain) and the ethylene content of the EVOH (A) used. The degree of modification was calculated as the number of moles of the epoxy compound (B) having a double bond.

EVOH (A) and (D) and modified EVOH (C) melt flow rate (MFR)
Using a melt indexer (“L260” manufactured by Techno Seven Co., Ltd.), the flow rate (g / 10 minutes) of the sample was measured and determined under the conditions of a load of 2.16 kg and a temperature of 190 ° C.

Retort suitability (evaluation with single layer film)
A retort apparatus (Nippon Co., Ltd.) obtained in the following examples or comparative examples was applied to a single-layer film after irradiation with an electron beam (single-layer films not irradiated with an electron beam for Comparative Examples 1, 4 and 5). Using a high-temperature high-pressure cooking sterilization tester “RCS-60 / 10RSPXG-FAM” manufactured by Osaka Seisakusho, the film was retorted at 120 ° C. for 30 minutes, and the state of the film immediately after that was visually observed and evaluated as follows. did.
○ ··· No film dissolution and good shape.
Δ: The film is slightly dissolved.
X: The film dissolves and does not leave a shape.

Oxygen absorption (cumulative amount)
About 0.2 g of a single-layer film (single-layer film not irradiated with an electron beam for Comparative Examples 1, 4 and 5) after irradiation with an electron beam obtained in the following Examples or Comparative Examples was precisely weighed, The bottle was placed in a standard bottle with an internal volume of 85 ml filled with air at 23 ° C. and 50% RH. The air in the standard bottle contained 21:79 oxygen and nitrogen in a volume ratio. In order to set the internal relative humidity to 100% RH, a filter paper containing water was enclosed, the mouth of the standard bottle was sealed with an epoxy resin using a multilayer sheet containing an aluminum layer, and then allowed to stand at 60 ° C. After sealing, the internal air was sampled with a syringe over time, and the oxygen concentration of this air was measured using gas chromatography. The holes vacated in the multilayer sheet at the time of sampling were sealed with epoxy resin each time. By calculating the amount of oxygen decrease from the volume ratio of oxygen and nitrogen obtained by measurement, the amount of oxygen absorbed (integrated amount) after 30 days in a 60 ° C., 100% RH atmosphere of the film was determined.

Two films having a size of 12 cm × 12 cm were cut out from the multilayer films obtained in Examples or Comparative Examples having a cumulative dissolved oxygen concentration or less immediately after the retort treatment , and these were stacked so that the CPP layers face each other. The sides were heat sealed to produce a bag. Next, for the purpose of measuring the cumulative dissolved oxygen concentration, the inner surface of the bag (the surface of the CPP layer) is a glass substrate type 5 mmφ oxygen for an optical oximeter (“Fibox 3” (product name) manufactured by PreSens). A sensor spot (“SP-PSt3-GSUP-YOP-D5” (product name) manufactured by PreSens) was attached with an epoxy adhesive. And after putting 50 ml of deaerated water having a dissolved oxygen concentration of 1.6 to 1.8 ppm (23 ° C.) obtained by bubbling the ion exchange water with nitrogen, the remaining one side is heat sealed and sealed. A multilayer container enclosing deaerated water was prepared.
This multilayer container is retorted using a retort apparatus (manufactured by Nisaka Manufacturing Co., Ltd., high temperature / high pressure cooking sterilization tester “RCS-60 / 10RSPXG-FAM”) at 120 ° C. for 30 minutes to obtain an optical oxygen concentration. The accumulated dissolved oxygen concentration in the multi-layer container immediately after the retort treatment was measured with a meter (“Fibox 3” (product name) manufactured by PreSens).

Retort suitability (evaluation with multilayer container)
The state of the multilayer container (multilayer film) immediately after the retort treatment obtained in the measurement of the cumulative dissolved oxygen concentration immediately after the retort treatment was visually observed and evaluated as follows.
○ ··· No separation of the intermediate layer and the inner and outer layers was confirmed, and the transparency of the intermediate layer was maintained.
X ··· Delamination or whitening of the intermediate layer is observed.

Accumulated dissolved oxygen concentration after 1 year A plurality of multilayer containers subjected to retort treatment were prepared by the same method as the measurement of the accumulated dissolved oxygen concentration immediately after the retort treatment. Next, they were stored in a constant temperature and humidity chamber at 20 ° C. and 90% RH or 40 ° C. and 90% RH for 1 year. The accumulated dissolved oxygen concentration in the multilayer container after storage for one year was measured and evaluated according to the following criteria.
○ ··· Cumulative dissolved oxygen concentration is 0.5 ppm or less.
X: The accumulated dissolved oxygen concentration exceeds 0.5 ppm.

Oxygen permeability after one year (OTR)
The multilayer container after storage for one year obtained in the evaluation of the cumulative dissolved oxygen concentration after the lapse of one year was disassembled, the multilayer film was taken out, and the oxygen permeability (OTR) was measured. The oxygen permeability (OTR) (unit: ml / (m ² · day · atm)) was measured at 20 ° C. using an oxygen permeability measuring device (“MOCON OX-TRAN 10/50” manufactured by Modern Control). The sample was mounted under the conditions of 65/100% RH so that the outermost layer side of the multilayer film was 65% RH and oxygen gas atmosphere, and the innermost layer (CPP) side was 100% RH and nitrogen atmosphere. Atmospheric pressure and carrier gas pressure were 1 atm.

[Production Example 1]
Production of thermoplastic resin (G) (polyoctenylene (G-1)) A 5-liter three-necked flask equipped with a stirrer and a thermometer was purged with nitrogen, and then 110 g (1.0 mol) of cyclooctene and cis- 624 g of a heptane solution in which 187 mg (1.7 mmol) of 4-octene was dissolved was charged. Next, a catalyst solution was prepared by dissolving 8.48 mg (10 μmol) of benzylidene (1,3-dimesitylimidazolidin-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride in 1 g of toluene, and this was added to the above heptane solution. In addition, ring-opening metathesis polymerization was performed at 70 ° C. After 5 minutes, analysis by gas chromatography (“GC-14B” manufactured by Shimadzu Corporation, column: “G-100” manufactured by Chemicals Inspection Association) confirmed the disappearance of cyclooctene. After adding 600 g of methanol to the obtained reaction liquid and stirring for 30 minutes at 40 ° C., the mixture was allowed to stand at 40 ° C. for 1 hour for liquid separation to remove the lower layer. After adding 600 g of methanol to the upper layer again and stirring at 40 ° C. for 30 minutes, the mixture was allowed to stand at 40 ° C. for 1 hour for liquid separation to remove the lower layer. Low boiling components such as heptane are distilled off from the upper layer under reduced pressure, and further dried at 50 Pa and 40 ° C. for 24 hours using a vacuum dryer, and contains an oligomer having a weight average molecular weight of 158,000 and a molecular weight of 1,000 or less. 101.2 g (yield 90%) of polyoctenylene having a rate of 8.5% by mass was obtained.
The ratio of the obtained polyoctenylene to the total carbon-carbon double bonds of the carbon-carbon double bonds in the side chain was 0%. In addition, the ratio with respect to this total carbon-carbon double bond is the amount of the carbon-carbon double bond in the main chain a (mol / g), and the amount of the carbon-carbon double bond in the side chain is b (mol). / G), 100 × b / (a + b).

  The total amount of the obtained polyoctenylene was crushed to about 1 mm square, put into a 500 ml separable flask equipped with a stirrer, a reflux tube and a thermometer, added with 300 g of acetone, and stirred at 40 ° C. for 3 hours. Acetone was removed by decantation, 300 g of acetone was added again, and the mixture was stirred at 40 ° C. for 3 hours. Acetone was removed by decantation, and then dried at 50 Pa and 100 ° C. for 6 hours using a vacuum dryer. The weight average molecular weight was 163,000, and the content of oligomers having a molecular weight of 1,000 or less was 3.1% by mass. 96.1 g of polyoctenylene (G-1) was obtained.

[Production Example 2]
Production weight average molecular weight of compatibilizer (I-1) 100,400, styrene / butadiene = 18/82 (mass ratio), 1,2-bond / 1,4-bond of butadiene unit = 47/53 (mol) Ratio), hydrogenation rate 97 mol%, carbon-carbon double bond amount 430 μmol / g, melt flow rate 5 g / 10 min (230 ° C., 2160 g load), styrene-butadiene-styrene having a density of 0.89 g / cm ³ Supply the hydrogenated triblock copolymer to the same direction twin screw extruder (“TEM-35B” manufactured by Toshiba Machine Co., Ltd.) at a rate of 7 kg / hr while replacing the inlet with nitrogen at 1 liter / min. did. The configuration and operating conditions of the twin screw extruder used for the reaction are as follows.
Screw diameter: 37mmφ, L / D: 52 (15 blocks)
Liquid feeder: C3 (liquid feeder 1) and C11 (liquid feeder 2)
Vent position: C6 (vent 1) and C14 (vent 2)
Screw configuration: Use seal rings between C5-C6, C10-C11, and C12 Temperature setting: C1 (water cooling), C2-C3 (200 ° C), C4-C15 (250 ° C), die (250 ° C)
Screw rotation speed: 400rpm
Next, a liquid mixture (TEAB / BBD = 29/71, mass ratio) of borane-triethylamine complex (TEAB) and boric acid 1,3-butanediol ester (BBD) is supplied from the liquid feeder 1 at a rate of 0.6 kg / hr. Then, 1,3-butanediol was supplied from the liquid feeder 2 at a rate of 0.4 kg / hr and continuously kneaded. During kneading, the pressure was adjusted so that the gauges of Vent 1 and Vent 2 showed about 2.7 kPa. As a result, a hydrogenated product of a modified styrene-butadiene-styrene triblock copolymer containing a boronic acid 1,3-butanediol ester group (BBDE) (compatibility agent (BB) at a rate of 7 kg / hr from the discharge port. I-1)) was obtained. The amount of boronic acid 1,3-butanediol ester group in the compatibilizer (I-1) was 210 μmol / g.

[Production Example 3]
Production of Modified EVOH (C-1) 28 parts by mass of zinc acetylacetonate monohydrate was mixed with 957 parts by mass of 1,2-dimethoxyethane to obtain a mixed solution. To this mixed liquid, 15 parts by mass of trifluoromethanesulfonic acid was added with stirring to obtain a catalyst solution.
Further, an extruder (“TEM-35BS” manufactured by Toshiba Machine Co., Ltd., 37 mmφ, L / D = 52.5) was used, and a screw, three vents, and three pressure inlets were installed. The resin feed port was cooled with water, the temperature of the screw rotation portion was set to 200 ° C., and the operation was performed at a screw rotation speed of 300 rpm. EVOH (ethylene content 32 mol%, MFR 6.0 g / 10 min, potassium content 8 ppm, phosphate group content 20 ppm, saponification degree 99 mol% or more) is charged at 20.0 kg / hr from the resin feed port. From the inlet, allyl glycidyl ether (AGE) was added at a rate of 1.76 kg / hr, and the catalyst solution was added at a rate of 0.2 kg / hr. Further, a 0.82 mass% aqueous solution of sodium acetate was added from the second pressure inlet at a rate of 0.3 kg / hr. Excess AGE was removed from the first vent under reduced pressure, water was added at a rate of 1 kg / hr from the third pressure inlet, and water and AGE were removed from the second and third vents under reduced pressure. As a result, a modified EVOH having an AGE modification amount of 1.0 mol%, an MFR of 2.0 g / 10 minutes, and a melting point of 171 ° C. [hereinafter referred to as modified EVOH (C-1)] was obtained. Table 1 summarizes the physical properties of the modified EVOH.

[Production Example 4]
Production of modified EVOH (C-2) In Production Example 3, the addition rate of allyl glycidyl ether (AGE) from the first pressure inlet and the addition rate of the catalyst solution were 2.93 kg / hr and 0.5 kg / hr, respectively. AGE modification amount 1.7 mol%, MFR 2.0 g / 10 min in the same manner as in Production Example 3, except that the addition rate of the 0.82 mass% sodium acetate aqueous solution from the second pressure inlet was 0.6 kg / hr. A modified EVOH having a melting point of 166 ° C. [hereinafter referred to as modified EVOH (C-2)] was obtained. Table 1 summarizes the physical properties of the modified EVOH (C-2).

[Production Example 5]
Production of gas barrier laminate (laminate (F-1)) Polyacrylic acid (PAA) having a number average molecular weight of 150,000 was dissolved in distilled water, and then ammonia water was added to add 1.5 of the carboxyl group of PAA. The mol% was neutralized to obtain a PAA aqueous solution having a solid content concentration of 10% by mass in the aqueous solution.

  Next, 68.4 parts by mass of tetramethoxysilane (TMOS) is dissolved in 82.0 parts by mass of methanol, and then 13.6 parts by mass of γ-glycidoxypropyltrimethoxysilane is dissolved. 13 parts by mass and 12.7 parts by mass of 0.1 N hydrochloric acid were added to prepare a sol, and this was stirred and subjected to hydrolysis and condensation reaction at 10 ° C. for 1 hour. The obtained sol was diluted with 185 parts by mass of distilled water, and then quickly added to 634 parts by mass of the 10% by mass PAA aqueous solution under stirring to obtain a solution (S1).

  On the other hand, a two-pack type anchor coating agent (AC; “Takelac A626” (trade name) and “Takenate A50” (trade name) manufactured by Mitsui Takeda Chemical Co., Ltd.) is applied to a stretched PET film (OPET; “Lumirror” manufactured by Toray Industries, Inc.). ”(Trade name), having a thickness of 12 μm) was coated with a bar coater and dried at 80 ° C. for 5 minutes to prepare a substrate (AC layer / OPET layer) having an AC layer. The solution (S1) was coated on the AC layer of the substrate using a bar coater so that the thickness after drying was 1 μm, and then dried at 80 ° C. for 5 minutes. Subsequently, the same operation as described above was performed on the other surface of the OPET. Then, it was formed from the layer (1 μm) / AC layer / OPET layer (12 μm) / AC layer / solution (S1) formed from the solution (S1) by performing a heat treatment in dry air at 200 ° C. for 5 minutes. A laminate having a layer configuration of a layer (1 μm) was obtained [hereinafter, this laminate may be referred to as a laminate (1)]. The layer formed from the solution (S1) of the laminate (1) was colorless and transparent and had a good surface appearance.

  Next, calcium acetate was dissolved in distilled water to a concentration of 5% by mass, and this aqueous solution was kept at 85 ° C. And the laminated body (1) obtained above was immersed in this aqueous solution (85 degreeC; MI-1) for about 300 seconds. After the immersion, the laminate is taken out, the surface thereof is washed with distilled water, and then dried at 80 ° C. for 5 minutes to obtain a gas barrier laminate [hereinafter sometimes referred to as laminate (F-1)]. Obtained. About this laminated body (F-1), the neutralization degree of the carboxyl group of the polyacrylic acid in the layer (layer containing the neutralized product) showing gas barrier properties (the neutralization degree of the —COO— group contained in the carboxyl group) Was measured by the following method. As a result, it was found that 97 mol% of the carboxyl groups were neutralized with calcium ions.

<Degree of neutralization of carboxyl groups by ions (ionization degree)>
About a laminated body (F-1), C = contained in the layer which shows gas barrier property in the mode of ATR (total reflection measurement) using a Fourier-transform infrared spectrophotometer ("8200PC" manufactured by Shimadzu Corporation). The peak of O stretching vibration was observed. Peak attributed to C = O stretching vibration of the carboxyl group of the ionization front of PAA was observed in the range of ^{1600cm -1 ~1850cm} -1, C = O stretching vibration of the carboxyl group after being ionized 1500 cm ^-1 ~ It was observed in the range of 1600 cm ⁻¹ . Then, the ratio was calculated from the maximum absorbance in each range, and the degree of ionization was determined using the ratio and a calibration curve prepared in advance by the following method.

Preparation of calibration curve Polyacrylic acid having a number average molecular weight of 150,000 was dissolved in distilled water, and the carboxyl group was neutralized with a predetermined amount of sodium hydroxide. The aqueous solution of the obtained neutralized product of polyacrylic acid was coated on the substrate so as to have the same thickness as the gas barrier property layer of the gas barrier laminate to be measured for ionization degree, and dried. . A stretched PET film (OPET; coated with a two-component anchor coating agent (AC; “Takelac A626” (trade name) and “Takenate A50” (trade name)) manufactured by Mitsui Takeda Chemical Co., Ltd.) is coated on the substrate. “Lumirror” (trade name) manufactured by Toray Industries, Inc., having a thickness of 12 μm) was used. In this way, eleven types of standard samples in which the degree of neutralization of carboxyl groups is different by 10 mol% between 0 and 100 mol% (laminate: layer made of neutralized polyacrylic acid / AC layer / PET layer) Was made. About these samples, the infrared absorption spectrum was measured in the mode of ATR (total reflection measurement) using the Fourier-transform infrared spectrophotometer ("8200PC" by Shimadzu Corporation). The two peaks corresponding to the C = O stretching vibration in the layer consisting of neutralized product of polyacrylic acid, ^i.e., a peak observed in the range of 1600cm ^-1 ~1850cm -1 and ^1500cm -1 ^{~1600cm -} The ratio of the maximum absorbance was calculated for the peak observed in the range of ¹ . Then, a calibration curve was created using the calculated ratio and the ionization degree of each standard sample.

[Example 1]
(1) 8 parts by mass of polyoctenylene (G-1) obtained in Production Example 1, 91 parts by mass of modified EVOH (C-1) obtained in Production Example 3, and a compatibilizer obtained in Production Example 2 ( I-1) 1 part by mass and 0.42 parts by mass of cobalt stearate (II) (400 ppm as cobalt atoms) were dry blended, and a 30 mmφ twin screw extruder (“TEX-30SS-30CRW-2V manufactured by Nippon Steel Works, Ltd.) )), The inside of the cylinder was melt-kneaded while purging with nitrogen, and pelletized using a pelletizer.

(2) The pellet obtained in the above (1) was melt-extruded from a coat hanger die using a 20 mmφ single screw extruder at 220 ° C. while purging the cylinder with nitrogen to obtain a single layer film having a thickness of 20 μm. . This single layer film was irradiated with an electron beam of 100 kGy (acceleration voltage 200 kV) in a nitrogen atmosphere to crosslink the modified EVOH (C-1) in the film.
The oxygen absorption amount and retort suitability of the single-layer film after irradiation with an electron beam were measured or evaluated by the method described above. The results are shown in Table 2.

(3) Adhesive for dry lamination (Dainippon) on one side of the single-layer film after irradiation with the electron beam obtained in (2) above (hereinafter, such a single-layer film may be referred to as C). “LX-500” (trade name) manufactured by Ink Chemical Industries, Ltd .: “KR-90S” (trade name) manufactured by Dainippon Ink and Chemicals, Inc .: ethyl acetate = 18: 1.2: 28.3 (mass ratio) The laminate (F-1) obtained in Production Example 5 to which the mixture prepared in Example 5 was applied (hereinafter sometimes simply referred to as “Ad”) was dry-laminated. Subsequently, unstretched polypropylene (“RXC-18 # 60” manufactured by Tosero Co., Ltd. (trade name), thickness 60 μm, coated with the same dry laminate adhesive (Ad) as described above on the other surface of C; (Simply abbreviated as “CPP”) was dry laminated. Thereafter, aging was performed at 23 ° C. for 5 days to obtain a multilayer film having a layer structure of F-1 / Ad / C / Ad / CPP.
Using the obtained multilayer film, by the above-described method, the accumulated dissolved oxygen concentration immediately after the retort treatment in the multilayer container made from the multilayer film, the suitability for retort, the accumulated dissolved oxygen concentration after 1 year, and after 1 year The oxygen transmission rate (OTR) was measured or evaluated. The results are shown in Table 2.

[Example 2]
(1) Polyoctenylene (G-1) 8 parts by mass obtained in Production Example 1, modified EVOH (C-2) 45.5 parts by mass obtained in Production Example 4, unmodified EVOH (D-1) ( Obtained in Production Example 2 of ethylene-vinyl alcohol copolymer, ethylene content 32 mol%, MFR 1.6 g / 10 min (190 ° C., 2160 g load), saponification degree 99 mol% or more) 45.5 parts by mass One part by weight of the compatibilizer (I-1) and 0.42 parts by weight of cobalt stearate (II) (400 ppm as cobalt atoms) were dry blended, and a 30 mmφ twin screw extruder (“TEX-” manufactured by Nippon Steel Co., Ltd.). 30SS-30CRW-2V "), and the inside of the cylinder was melt-kneaded while purging with nitrogen, and pelletized using a pelletizer.

(2) The pellet obtained in the above (1) was melt-extruded from a coat hanger die using a 20 mmφ single screw extruder at 220 ° C. while purging the cylinder with nitrogen to obtain a single layer film having a thickness of 20 μm. . This single layer film was irradiated with an electron beam of 100 kGy (acceleration voltage 200 kV) under a nitrogen atmosphere to crosslink the modified EVOH (C-2) in the film.
The oxygen absorption amount and retort suitability of the single-layer film after irradiation with an electron beam were measured or evaluated by the method described above. The results are shown in Table 2.

(3) As C in Example 1 (3), except that the single-layer film after irradiation with the electron beam obtained in (2) above was used, in the same manner as (3) in Example 1, A multilayer film having a layer structure of F-1 / Ad / C / Ad / CPP was obtained.
Using the obtained multilayer film, by the above-described method, the accumulated dissolved oxygen concentration immediately after the retort treatment in the multilayer container made from the multilayer film, the suitability for retort, the accumulated dissolved oxygen concentration after 1 year, and after 1 year The oxygen transmission rate (OTR) was measured or evaluated. The results are shown in Table 2.

[Examples 3 to 11]
In Example 2 (1), in place of unmodified EVOH (D-1), unmodified EVOH (D-2) (ethylene-vinyl alcohol copolymer, ethylene content 27 mol%, MFR 4.1 g / 10 minutes (210 ° C., 2160 g load), saponification degree 99 mol% or more) was used, and the pellets were prepared in the same manner as in Example 2 (1) except that each component was blended in the proportions shown in Table 2. Produced.
In the same manner as in (2) of Example 2 except that the obtained pellets were used and the amount of electron beam irradiation in (2) of Example 2 was set to the values shown in Table 2, A single layer film was obtained. The oxygen absorption and retort suitability were measured or evaluated by the methods described above.
Moreover, the multilayer film which has the layer structure of F-1 / Ad / C / Ad / CPP was used like (3) of Example 2 using each single layer film after irradiation with the obtained electron beam. I got each.
Using each of the obtained multilayer films, the accumulated dissolved oxygen concentration immediately after the retort treatment, suitability for retort in the multilayer container made from the multilayer film by the above-described method, the accumulated dissolved oxygen concentration after 1 year, and 1 year elapsed Later oxygen permeability (OTR) was measured or evaluated. The results are shown in Table 2.

[Examples 12 and 13]
In Example 3, instead of using the laminate (F-1), an alumina-deposited polyethylene terephthalate (PET) film (“BARRIALOX” (trade name), 12 μm in thickness, manufactured by Toray Film Processing Co., Ltd.), or polyvinylidene chloride ( PVDC) film (“Saran UB” manufactured by Asahi Kasei Co., Ltd. (trade name), thickness 15 μm) was used in the same manner as in Example 3 except that alumina-deposited PET (however, the alumina-deposited layer was compared with the PET layer). Multilayer films having a layer configuration of (inside) / Ad / C / Ad / CPP (Example 12) or a layer configuration of PVDC / Ad / C / Ad / CPP (Example 13) were obtained.
Using each of the obtained multilayer films, the accumulated dissolved oxygen concentration immediately after the retort treatment, suitability for retort in the multilayer container made from the multilayer film by the above-described method, the accumulated dissolved oxygen concentration after 1 year, and 1 year elapsed Later oxygen permeability (OTR) was measured or evaluated. The results are shown in Table 2.

[Comparative Examples 1-5]
In Example 2 (1), in place of unmodified EVOH (D-1), unmodified EVOH (D-2) (ethylene-vinyl alcohol copolymer, ethylene content 27 mol%, MFR 4.1 g / 10 minutes (210 ° C., 2160 g load) and a saponification degree of 99 mol% or more), and the pellets were prepared in the same manner as (1) of Example 2 except that each component was blended in the proportions shown in Table 3. Produced.
Other than using the obtained pellet and setting the amount of electron beam irradiation in Example 2 (2) to the value shown in Table 3 (Comparative Examples 1, 4 and 5 were not irradiated with an electron beam) In the same manner as in (2) of Example 2, a single-layer film after irradiation with an electron beam (Comparative Examples 1, 4 and 5 were single-layer films not irradiated with an electron beam) was obtained. The oxygen absorption and retort suitability were measured or evaluated by the methods described above.
In addition, using each obtained single-layer film after irradiation with an electron beam (single-layer films not irradiated with an electron beam for Comparative Examples 1, 4 and 5), the same as (3) of Example 2 was performed. Thus, multilayer films having a layer structure of F-1 / Ad / C / Ad / CPP were obtained.
Using each of the obtained multilayer films, the accumulated dissolved oxygen concentration immediately after the retort treatment, suitability for retort in the multilayer container made from the multilayer film by the above-described method, the accumulated dissolved oxygen concentration after 1 year, and 1 year elapsed Later oxygen permeability (OTR) was measured or evaluated. The results are shown in Table 3.

[Comparative Examples 6-8]
In Example 3, instead of using the laminate (F-1), a stretched PET film (“Lumirror” (trade name) manufactured by Toray Industries, Inc., thickness: 12 μm; hereinafter, sometimes simply referred to as “OPET”) , Stretched polyamide film ("EMBLEM ON-BC" (trade name) manufactured by Unitika Ltd., thickness: 15 [mu] m; hereinafter may be simply abbreviated as "ON"), or stretched polypropylene film ("Pyrene manufactured by Toyobo Co., Ltd.") Layer structure of OPET / Ad / C / Ad / CPP in the same manner as in Example 3 except that “P2161” (trade name), thickness 20 μm; hereinafter simply referred to as “OPP” may be used. (Comparative Example 6), multilayer film having a layer configuration of ON / Ad / C / Ad / CPP (Comparative Example 7) or a layer configuration of OPP / Ad / C / Ad / CPP (Comparative Example 8) It was obtained, respectively.
Using each of the obtained multilayer films, the accumulated dissolved oxygen concentration immediately after the retort treatment, suitability for retort in the multilayer container made from the multilayer film by the above-described method, the accumulated dissolved oxygen concentration after 1 year, and 1 year elapsed Later oxygen permeability (OTR) was measured or evaluated. The results are shown in Table 3.

[Comparative Example 9]
In Example 3, C / Ad / F-1 / Ad was performed in the same manner as in Example 3, except that the position of the single layer film used as C and the position of the laminate (F-1) used as the outer layer were changed. A multilayer film having a layer structure of / CPP was obtained.
Using the obtained multilayer film, by the above-described method, the accumulated dissolved oxygen concentration immediately after the retort treatment in the multilayer container made from the multilayer film, the suitability for retort, the accumulated dissolved oxygen concentration after 1 year, and after 1 year The oxygen transmission rate (OTR) was measured or evaluated. The results are shown in Table 3.

In addition, about each of the laminated body (F-1), alumina vapor deposition PET film, PVDC film, stretched PET film, stretched polyamide film, and stretched polypropylene film which were used by each said Example or comparative example, 20 degreeC and 65% RH. The oxygen permeability (OTR) under the following conditions was measured by the following method, and the results are shown in Table 4 below.
Oxygen permeability (OTR)
Using an oxygen permeability measuring apparatus ("MOCON OX-TRAN 10/50" manufactured by Modern Control Co., Ltd.), the measurement was performed under the conditions of 20 at 65 ° C and 65% RH under conditions of an oxygen pressure of 1 atm and a carrier gas pressure of 1 atm.

  From the above results, it can be seen that the multilayer container satisfying the configuration of the present invention not only has a high oxygen barrier property immediately after the retort treatment but also can maintain a high oxygen barrier property for one year or more.

  The multilayer container of the present invention is excellent in gas barrier properties and oxygen absorption, and oxygen intrusion is highly suppressed even after retort treatment, and even after being stored under bad conditions such as high temperature and high humidity after retort treatment, For example, the environment at the time of disposal can be maintained because the oxygen concentration of the content can be kept at a low level, deterioration and alteration due to oxygen etc. of the contents can be suppressed over a long period of time, and the retort treatment hardly causes whitening or deformation. As an alternative to heavy metal cans and glass bottles, food packaging applications such as cooked rice, cup ramen, yogurt, fruit jelly, pudding, miso, space food, military food, etc. It can be preferably used for applications other than food packaging, such as medical infusion bags and electronic member packaging containers.

Claims (22)

An oxygen-absorbing layer comprising a resin composition comprising a thermoplastic resin (G) having a carbon-carbon double bond and a modified ethylene-vinyl alcohol copolymer (C); and an oxygen permeability of 10 ml / (m ² · day) Atm) A multilayer container formed of a laminate having the following gas barrier layer, wherein the modified ethylene-vinyl alcohol copolymer (C) is obtained by converting the ethylene-vinyl alcohol copolymer (A) into two It is obtained by modifying with an epoxy compound (B) having a heavy bond, at least a part of the resin composition is crosslinked, and the gas barrier layer is disposed outside the oxygen absorbing layer. Multi-layer container.   The modified amount of the modified ethylene-vinyl alcohol copolymer (C) by the epoxy compound (B) having a double bond is the total number of moles of monomer units of the ethylene-vinyl alcohol copolymer (A). The multilayer container according to claim 1, wherein the content is 0.1 to 10 mol%.   In the gas barrier layer, at least a part of —COO— group contained in the at least one functional group of the polymer having at least one functional group selected from a carboxyl group and a carboxylic anhydride group is divalent or more. A laminate (F1) having a layer containing a neutralized product neutralized with metal ions; a laminate (F2) having a layer made of an inorganic material formed by vapor deposition; and a polyvinylidene chloride polymer or The multilayer container according to claim 1 or 2, which is at least one selected from the group consisting of: a layer (F3) of a composition comprising:   The multilayer container according to any one of claims 1 to 3, wherein the thermoplastic resin (G) having a carbon-carbon double bond has a carbon-carbon double bond substantially only in the main chain. .   The multilayer container according to claim 4, wherein the thermoplastic resin (G) is polyoctenylene.   The multilayer container according to any one of claims 1 to 5, wherein the resin composition further comprises an ethylene-vinyl alcohol copolymer (D) not modified with an epoxy compound (B) having a double bond. .   The multilayer container according to claim 1, wherein the resin composition further contains a transition metal salt (H).   The multilayer container according to claim 7, wherein the transition metal salt (H) is a cobalt salt.   The multilayer container according to any one of claims 1 to 8, wherein the resin composition further comprises a compatibilizer (I).   The multilayer container according to any one of claims 1 to 9, wherein the epoxy compound (B) having a double bond is allyl glycidyl ether.   The multilayer container according to claim 1, wherein the laminate further has a seal layer, and the seal layer is an innermost layer. An oxygen-absorbing layer comprising a resin composition comprising a thermoplastic resin (G) having a carbon-carbon double bond and a modified ethylene-vinyl alcohol copolymer (C); and an oxygen permeability of 10 ml / (m ² · day) Atm) A laminate having the following gas barrier layer and a seal layer, wherein the modified ethylene-vinyl alcohol copolymer (C) is a double bond of the ethylene-vinyl alcohol copolymer (A). The resin composition is obtained by modification with an epoxy compound (B), wherein at least a part of the resin composition is crosslinked, and the oxygen absorption layer is disposed between the gas barrier layer and the seal layer. A laminate in which the seal layer is disposed on the outermost surface.   The modified amount of the modified ethylene-vinyl alcohol copolymer (C) by the epoxy compound (B) having a double bond is the total number of moles of monomer units of the ethylene-vinyl alcohol copolymer (A). It is 0.1-10 mol% with respect to the laminated body of Claim 12.   In the gas barrier layer, at least a part of —COO— group contained in the at least one functional group of the polymer having at least one functional group selected from a carboxyl group and a carboxylic anhydride group is divalent or more. A laminate (F1) having a layer containing a neutralized product neutralized with metal ions; a laminate (F2) having a layer made of an inorganic material formed by vapor deposition; and a polyvinylidene chloride polymer or The laminate according to claim 12 or 13, which is at least one selected from the group consisting of: a layer (F3) of a composition comprising:   The laminate according to any one of claims 12 to 14, wherein the thermoplastic resin (G) having a carbon-carbon double bond has a carbon-carbon double bond substantially only in the main chain. .   The laminate according to claim 15, wherein the thermoplastic resin (G) is polyoctenylene.   The laminate according to any one of claims 12 to 16, wherein the resin composition further comprises an ethylene-vinyl alcohol copolymer (D) not modified with an epoxy compound (B) having a double bond. .   The laminate according to any one of claims 12 to 17, wherein the resin composition further comprises a transition metal salt (H).   The laminate according to claim 18, wherein the transition metal salt (H) is a cobalt salt.   The laminate according to any one of claims 12 to 19, wherein the resin composition further comprises a compatibilizer (I).   The laminate according to any one of claims 12 to 20, wherein the epoxy compound (B) having a double bond is allyl glycidyl ether.   The laminate according to any one of claims 12 to 21, wherein the seal layer is a polyolefin layer.