TW202323054A - Gas barrier laminate - Google Patents

Abstract

This invention provides a gas barrier laminate having improved wet peel strength while maintaining good gas barrier properties. This invention discloses a laminate, which is a gas barrier laminate including a substrate, a first layer and a second layer in this order, wherein the first layer including an amino group-containing resin wherein the amount of amino groups in the first layer is 0.3 mmol/g or more, and the second layer includes a resin containing at least one functional group selected from the group consisting of hydroxy group, carboxyl group, amino group and sulfo group, and an inorganic layered compound.

Description

gas barrier laminate

This patent application claims the priority of Japanese Patent Application No. 2021-149873 (filing date: September 15, 2021) under the Paris Convention, which is hereby incorporated by reference in its entirety into this specification.

The present invention relates to a gas barrier laminate and a method for producing the gas barrier laminate.

For example, packaging materials for foods, cosmetics, and the like are required to have properties that inhibit the penetration of gases such as water vapor and oxygen, that is, gas barrier properties, in order to prevent their deterioration. A laminate having "a gas barrier layer formed by using polyvinyl alcohol or a derivative thereof" on a substrate is known as a packaging material having high gas barrier properties. Here, "gas barrier layer" refers to a layer used to suppress gas penetration.

Patent Document 1 describes a gas barrier layer comprising a polyvinylamine-polyvinyl alcohol copolymer. In addition, Patent Document 2 describes a laminate comprising a coating film and a base material formed from a coating solution containing a hydroxyl group-containing resin such as vinylamine-vinyl alcohol copolymer, an inorganic layer, and a substrate. Compounds, and liquid media.

[Prior Art Literature]

[Patent Document]

[Patent Document 1] Japanese Patent No. 5669738

[Patent Document 2] International Publication No. 2021/095755

Patent Document 1 describes that a gas barrier layer comprising the polyvinylamine-polyvinyl alcohol copolymer described in this document exhibits good oxygen barrier properties. However, according to the studies of the inventors of the present application, it has been found that the gas barrier layer described in Patent Document 1 is not sufficient in gas barrier properties. In addition, it was also found that although the laminate described in Patent Document 2 exhibited good gas barrier properties, the adhesion between the gas barrier layer and the substrate in the presence of water (hereinafter also referred to as "water-attached peel strength") ) still has room for improvement.

Therefore, the object of the present invention is to provide a gas barrier laminate, which can maintain good gas barrier properties and improve the water-attached peel strength.

The inventors of the present invention have completed the present invention as a result of earnest studies in order to solve the above-mentioned problems. That is, the present invention provides the following suitable aspects.

[1] A laminate, which is a gas barrier laminate comprising a substrate, a first layer, and a second layer in this order, wherein,

The first layer contains a resin containing amine groups, and the amount of amine groups in the first layer is 0.3 mmol/g or more,

The second layer includes: a resin containing at least one functional group selected from the group consisting of hydroxyl group, carboxyl group, amino group and sulfonic acid group, and an inorganic layered compound.

[2] The laminate according to [1], wherein the content of the layered inorganic compound in the second layer is 1 to 50% by mass relative to the total mass of the second layer.

[3] The laminate according to [1] or [2], wherein the resin contained in the second layer contains at least one functional group selected from the group consisting of hydroxyl groups and amino groups.

[4] The laminate according to any one of [1] to [3], wherein the resin contained in the second layer includes a hydroxyl group-containing resin.

[5] The laminate according to any one of [1] to [4], wherein the hydroxyl group-containing resin contained in the second layer is a vinyl alcohol-based resin.

[6] The laminate according to any one of [1] to [5], wherein the hydroxyl group-containing resin contained in the second layer includes a resin containing amino groups in addition to hydroxyl groups.

[7] The laminate according to any one of [1] to [6], wherein the amount of amine groups (mmol/g) in the first layer is greater than the amount of amine groups (mmol/g) in the second layer ).

[8] The laminate according to any one of [1] to [7], wherein the first layer contains "a resin containing a hydroxyl group but not containing an amino group" in addition to an amino group-containing resin.

[9] The laminate according to [8], wherein the "resin containing a hydroxyl group but not containing an amino group" contained in the first layer is a "vinyl alcohol-based resin not containing an amino group".

[10] The laminate according to any one of [1] to [9], wherein the "amino group-containing resin" contained in the first layer includes a resin containing hydroxyl groups in addition to amino groups.

[11] The laminate according to any one of [1] to [10], wherein the "amine group-containing resin" contained in the first layer includes an ethyleneamine-vinyl alcohol copolymer.

[12] The laminate according to any one of [1] to [11], wherein the content of the layered inorganic compound in the first layer is 50% by mass or less relative to the total mass of the first layer.

[13] The laminate according to any one of [1] to [12], wherein the first layer and/or the second layer further include: At least one additive in the group consisting of corrosion inhibitors and rust inhibitors.

[14] The laminate according to [13], wherein the additive includes a crosslinking agent.

[15] The laminate according to [14], wherein the crosslinking agent has an epoxy group.

[16] A method for manufacturing the laminate described in any one of [1] to [15], comprising the following steps:

The step of forming a first layer on the substrate, wherein the first layer comprises an amine group-containing resin; and

A step of forming a second layer on the first layer, wherein the second layer includes: a resin having at least one functional group selected from the group consisting of hydroxyl, carboxyl, amino and sulfonic acid groups, and an inorganic layer compound.

According to the present invention, it is possible to provide a gas barrier laminate capable of maintaining good gas barrier properties and improving the water-attached peel strength.

Fig. 1 is the schematic diagram of the measuring method of attached water peeling strength.

Embodiments of the present invention will be described in detail below. In addition, the scope of the present invention is not limited to the embodiments described here, and various changes can be made without departing from the gist of the present invention.

〔Gas barrier laminate〕

The gas barrier laminate of the present invention includes a substrate, a first layer, and a second layer in this order, wherein the first layer contains an amine group-containing resin, and the amount of amine groups in the first layer is 0.3 mmol/g or more. The inventors of the present invention found that if the first layer with a high concentration of amine groups is formed between the "substrate" and the "second layer functioning as a gas barrier layer", the gas of the obtained gas barrier laminate can be maintained. Barrier properties, and can improve the peeling strength of attached water. Xian believes that this is due to the high concentration of amine groups in the first layer, so the first layer not only functions as a gas barrier layer but also as a primer layer. In addition, in this specification, "gas barrier property" means the property of suppressing the permeation of gas such as oxygen or water vapor, and "gas barrier laminate" means a laminate including a gas barrier layer. In addition, in this specification, "water-attached peel strength" means the difference between "substrate" and "gas barrier layer including the first layer and the second layer" in the gas barrier laminate measured in the presence of water. Peel strength.

<layer 1>

The first layer contains "amino group-containing resin", and the amount of amino groups in the first layer is 0.3 mmol/g or more. Since the amount of amine groups in the first layer is 0.3 mmol/g or more, the gas barrier laminate of the present invention can maintain good gas barrier properties and improve the water-attached peel strength. On the other hand, when the amount of amine groups in the first layer is less than 0.3 mmol/g, the water-peeling strength tends to decrease.

The amount of amine groups in the first layer is preferably at least 0.5 mmol/g, more preferably at least 0.8 mmol/g, more preferably at least 1.0 mmol/g, still more preferably at least 1.5 mmol/g, most preferably at least 1.8 It is not less than mmol/g, more preferably not less than 2.0 mmol/g. When the amount of the above-mentioned amine groups is more than the above-mentioned lower limit, since the reaction between "the amine group in the first layer" and "functional groups such as carbonyl groups, aldehyde groups, carboxyl groups, and ester groups that may exist on the surface of the substrate" can be facilitated, and The adhesion or adhesiveness between the first layer and the base material is improved, so that the gas barrier property and the water-attached peel strength of the gas barrier laminate can be easily improved. In addition, the amount of amine groups in the first layer is preferably at most 10 mmol/g, more preferably at most 8.0 mmol/g, still more preferably at most 5.0 mmol/g, still more preferably at most 3.0 mmol/g.

The amount of amine groups in the first layer can be adjusted according to the amount (mmol/g) of amine groups in the amine group-containing resin contained in the first layer, the ratio of the amine group-containing resin contained in the first layer, and the like.

The amount of amine groups (mmol/g) in the first layer can be calculated by measuring the amount of amine groups (mmol/g) in the amine group-containing resin contained in the first layer by ¹ H NMR. For example, Calculated by the method described in the examples.

(resins containing amino groups)

As far as the amino group-containing resin is concerned, as long as it is a resin containing an amino group, there are no particular restrictions, for example: vinylamine-vinyl alcohol copolymer; polyethyleneimine (polyethyleneimine); vinylbenzenetrimethylammonium chloride , aminoethyl acrylate hydrochloride and other ethylenically unsaturated mono-, di-, or tri-alkylammonium salts, N-methylaminoethyl acrylate, N,N-dimethylaminoethyl methacrylate, Homopolymers such as N,N-dimethylaminomethyl-N-acrylamide, N,N-dimethylaminoethyl-N-acrylamide, and their copolymers. These amino group-containing resins can be used alone or in combination of two or more. In addition, the aforementioned amino group may be unsubstituted or substituted with an alkyl group or the like.

In one embodiment of the present invention, it is preferable that the amino group-containing resin contains "resin containing hydroxyl groups in addition to amino groups" from the viewpoint of easy improvement of gas barrier properties and water-peeling strength. , more preferably include "vinyl alcohol-based resins containing amino groups", and more preferably include vinylamine-vinyl alcohol copolymers. The ethyleneamine-vinyl alcohol copolymer may be a random copolymer or a block copolymer, but a random copolymer is preferable from the standpoint of manufacturability or cost.

In one embodiment of the present invention, the amount of amino groups in the "resin containing hydroxyl groups in addition to amino groups" is preferably at least 0.3 mmol/g, more preferably at least 0.5 mmol/g, and even more preferably at least 0.8 It is at least 1.0 mmol/g, more preferably at least 1.0 mmol/g, particularly preferably at least 1.5 mmol/g, even more preferably at least 1.8 mmol/g, especially preferably at least 2.0 mmol/g. When the amount of the amine groups is not less than the above lower limit, the amount of the amine groups in the first layer can be increased easily, and the gas barrier properties and the water-attached peel strength of the gas barrier laminate can be easily improved. In addition, the amount of amino groups in the "resin containing hydroxyl groups in addition to amino groups" is preferably at most 10 mmol/g, more preferably at most 8.0 mmol/g, still more preferably at most 5.0 mmol/g, still more preferably at most 3.0mmol/g or less. In addition, the amount of amine groups in the resin can be measured by performing ¹ H NMR measurement.

In one embodiment of the present invention, the amount of hydroxyl groups in the "resin containing hydroxyl groups in addition to amino groups" is preferably at least 1 mmol/g, more preferably at least 5 mmol/g, and more preferably at least 10 mmol/g , more preferably 15 mmol/g or more. If the amount of the said hydroxyl group is more than the said minimum, it will become easy to form a crystal structure by a hydrogen bond in a 1st layer, and it will become easy to improve gas barrier property. In addition, the amount of hydroxyl groups is preferably not more than 50 mmol/g, more preferably not more than 40 mmol/g, still more preferably not more than 30 mmol/g, still more preferably not more than 25 mmol/g. When the amount of hydroxyl groups is below the above upper limit, it is easy to suppress the decrease in interfacial activity of the "resin containing hydroxyl groups in addition to amino groups", and it is easy to improve compatibility with hydrophobic materials. In addition, the amount of hydroxyl groups in the resin can be measured by performing ¹ H NMR measurement.

In one embodiment of the present invention, the degree of saponification of the amino group-containing vinyl alcohol-based resin is preferable from the viewpoint of easily increasing the crystallinity of the amino-group-containing vinyl alcohol-based resin and improving the gas barrier properties. It is more than 80%, more preferably more than 90%, more preferably more than 95%, especially preferably more than 98%, and may be less than 100%.

In one embodiment of the present invention, when the amino group-containing resin includes "resin containing hydroxyl groups in addition to amino groups", from the viewpoint of easy improvement of gas barrier properties and water-attached peeling strength, relative to The total mass of the amino group-containing resin contained in the first layer, the content of the "resin containing a hydroxyl group in addition to the amino group" is preferably at least 60% by mass, more preferably at least 80% by mass, and more preferably at least 90% by mass. % by mass or more, more preferably at least 95% by mass, and most preferably at least 99% by mass. In addition, the aforementioned content may be preferably 100% by mass or less, more preferably 80% by mass or less, and more preferably 70% by mass or less.

In another embodiment of the present invention, the resin containing amino groups may include "resins containing amino groups but not containing hydroxyl groups" from the viewpoint of easily improving the peel strength (especially the water-attached peel strength). In terms of resins containing amine groups but not containing hydroxyl groups, for example, resins having at least one of primary amines, secondary amines or tertiary amines in the main chain, side chains or terminals and not having hydroxyl groups, such as poly Ethyleneimine, polyvinylamine, polyallylamine, polydiallylamine, polyvinylamidine, polylysine, etc. Among these resins, polyethyleneimine and polydiallylamine classified as main chain amines, and polyethyleneamine and polyallylamine classified as side-locked amines are preferred. Among these resins, polyethyleneimine, polyvinylamine, and polyallylamine are preferable from the viewpoint of availability.

In one embodiment of the present invention, the amount of amino groups in the "resin containing amino groups but no hydroxyl groups" is preferably at least 0.3 mmol/g, more preferably at least 0.5 mmol/g, and even more preferably at least 0.8 mmol /g or more, more preferably 1.0 mmol/g or more, particularly preferably 1.5 mmol/g or more, even more preferably 1.8 mmol/g or more, especially preferably 2.0 mmol/g or more. When the amount of the amine groups is not less than the above lower limit, the amount of the amine groups in the first layer can be increased easily, and the gas barrier properties and the water-attached peel strength of the gas barrier laminate can be easily improved. In addition, the amount of amino groups in the "resin containing amino groups but no hydroxyl groups" is preferably at most 10 mmol/g, more preferably at most 8.0 mmol/g, even more preferably at most 5.0 mmol/g, even more preferably at most 3.0 below mmol/g.

In one embodiment of the present invention, when the resin containing amino groups includes "resin containing amino groups but not containing hydroxyl groups", from the viewpoint of easy improvement of peel strength (especially water-attached peel strength), relative to the first The total mass of the amino group-containing resin contained in one layer, the content of the "amino group-containing but no hydroxyl group-containing resin" is preferably at least 5% by mass, more preferably at least 10% by mass, and more preferably at least 20% by mass or more, especially preferably 50% by mass or more. In addition, the aforementioned content is preferably at most 99% by mass, more preferably at most 80% by mass, and still more preferably at most 60% by mass.

In one embodiment of the present invention, the amino group-containing resin contained in the first layer may include both "a resin containing a hydroxyl group in addition to an amino group" and "a resin containing an amino group but not a hydroxyl group". , or just any of them. When the amino group-containing resin includes both "resins containing hydroxyl groups in addition to amino groups" and "resins containing amino groups but not containing hydroxyl groups", the content ratio [resins containing hydroxyl groups in addition to amino groups] ]: [Resin containing amino groups but not containing hydroxyl groups] (mass ratio) is preferably 99:1 to 1:99, more preferably 80:20 to 20:80, and more preferably 70:30 to 30:70.

In one embodiment of the present invention, the number average molecular weight of the amino group-containing resin is preferably above 5,000, more preferably above 10,000, more preferably above 12,000, still more preferably above 15,000, preferably below 100,000 , more preferably less than 50,000, more preferably less than 40,000, still more preferably less than 30,000. The number average molecular weight of the resin containing amino groups can be measured by gel permeation chromatography (GPC), for example, it can be measured according to the method described in the examples.

In one embodiment of the present invention, the amount of amine groups in the entire amine-group-containing resin contained in the first layer is preferably at least 0.3 mmol/g, more preferably at least 0.5 mmol/g, and even more preferably at least 0.8 It is at least 1.0 mmol/g, more preferably at least 1.0 mmol/g, particularly preferably at least 1.5 mmol/g, even more preferably at least 1.8 mmol/g, especially preferably at least 2.0 mmol/g. When the amount of the amine groups is not less than the above lower limit, it is easy to increase the amount of amine groups in the first layer, and it is easy to improve the gas barrier properties and the water-attached peel strength of the gas barrier laminate. In addition, the amount of amine groups in the amine group-containing resin contained in the first layer is preferably 10 mmol/g or less, more preferably 8.0 mmol/g or less, still more preferably 5.0 mmol/g or less, still more preferably 3.0 mmol/g or less. below mmol/g.

In one embodiment of the present invention, relative to the total mass of the first layer, the content of the amino group-containing resin in the first layer is preferably at least 20% by mass, more preferably at least 50% by mass, and even more preferably It is at least 65% by mass, more preferably at least 80% by mass, particularly preferably at least 90% by mass, more preferably at most 100% by mass.

(Amine-free resin)

In one embodiment of the present invention, the first layer may include "a resin not containing an amino group (also called a resin not containing an amino group)" in addition to the "resin containing an amino group". The "amino-group-free resin" that may be contained in the first layer includes, for example, polyvinyl alcohol, (meth)acrylic acid-vinyl alcohol copolymer, ethylene-vinyl alcohol copolymer, etc. Alcohol resin, etc. These resins may be used alone or in combination of two or more. Among these resins, the amino group-free resin is preferably "resin containing hydroxyl group but no amino group", more preferably vinyl alcohol-based resin without amino group, and more preferably vinyl alcohol.

In one embodiment of the present invention, the amount of hydroxyl groups in the "resin containing hydroxyl groups but not containing amino groups" is preferably at least 1 mmol/g, more preferably at least 5 mmol/g, and more preferably at least 10 mmol/g. Still more preferably, it is 15 mmol/g or more. When the amount of the said hydroxyl group is more than the said minimum, it will become easy to form a crystal structure by a hydrogen bond in a 1st layer, and it will become easy to improve gas barrier property. In addition, the amount of hydroxyl groups is preferably not more than 50 mmol/g, more preferably not more than 40 mmol/g, still more preferably not more than 30 mmol/g, still more preferably not more than 25 mmol/g. When the amount of the said hydroxyl group is below the said upper limit, it will become easy to suppress the fall of an interface activity, and it will become easy to improve the compatibility with a hydrophobic material.

In one embodiment of the present invention, the degree of saponification of the vinyl alcohol-based resin without amino groups is preferably above 80%, more preferably above 90%, even more preferably above 95%, and most preferably above 98%. , can also be 100% or less.

In one embodiment of the present invention, the number average molecular weight of the amino-free resin is preferably 10,000 or more, more preferably 30,000 or more, and more preferably 50,000 or more, more preferably 150,000 or less, more preferably It is less than 100,000, more preferably less than 70,000. The number average molecular weight of the amino-free resin can be measured by gel permeation chromatography (GPC), for example, it can be measured according to the method described in the examples.

In one embodiment of the present invention, relative to the total mass of the first layer, the total amount of the resins (amine group-containing resin and amino group-free resin) contained in the first layer is preferably 50% by mass or more , more preferably at least 60% by mass, more preferably at least 70% by mass, even more preferably at least 80% by mass, particularly preferably at least 90% by mass, and usually less than 100% by mass.

In one embodiment of the present invention, relative to the total mass of the resin contained in the first layer, the content of the resin containing amino groups in the resin contained in the first layer is preferably 20% by mass or more, more preferably 50 mass % or more, more preferably 70 mass % or more, still more preferably 80 mass % or more, especially preferably 90 mass % or more, usually 100 mass % or less.

In an embodiment of the present invention, the amount of amine groups in the resin contained in the first layer is preferably 0.5 mmol/g or more, preferably 0.8 mmol/g or more, more preferably 1.0 mmol/g or more, and More preferably, it is at least 1.5 mmol/g, more preferably at least 1.8 mmol/g, particularly preferably at least 2.0 mmol/g. When the amount of the amine groups is not less than the above lower limit, the amount of the amine groups in the first layer can be increased easily, and the gas barrier properties and the water-attached peel strength of the gas barrier laminate can be easily improved. In addition, the aforementioned amount of amine groups is preferably 10 mmol/g or less, more preferably 8.0 mmol/g or less, still more preferably 5.0 mmol/g or less, still more preferably 3.0 mmol/g or less.

(inorganic layered compound)

In one embodiment of the present invention, the first layer may further include an inorganic layered compound from the viewpoint of easy improvement of gas barrier properties. The layered inorganic compound that can be contained in the first layer is not particularly limited, and for example, it can be the same as the "layered inorganic compound contained in the second layer described later" and its preferred aspects are also included.

In one embodiment of the present invention, the content of the layered inorganic compound in the first layer is preferably 0.1% by mass or more relative to the total mass of the first layer from the viewpoint of easy improvement of gas barrier properties , more preferably at least 1% by mass, more preferably at least 5% by mass, even more preferably at least 10% by mass, and most preferably at least 15% by mass.

In addition, in an embodiment of the present invention, from the viewpoint of easily improving the water-attached peeling strength, the content of the inorganic layered compound in the first layer is preferably 50% by mass relative to the total mass of the first layer. It is less than or equal to 35% by mass, more preferably less than 20% by mass, more preferably less than 10% by mass, most preferably less than 5% by mass, and more preferably less than 1% by mass. The first layer may not substantially contain an inorganic stratiform compound.

(additive)

In an embodiment of the present invention, the first layer may further include at least one additive selected from the group consisting of a crosslinking agent, a UV absorber, an antioxidant, a surfactant, and an antirust agent. From the standpoint of improving gas barrier properties and water-attached peeling strength, the aforementioned additives are preferably cross-linking agents, surfactants and/or rust inhibitors, and more preferably at least contain cross-linking agents.

As far as the crosslinking agent is concerned, it may be an organic crosslinking agent or an inorganic crosslinking agent, but an organic crosslinking agent is preferred. As for the organic crosslinking agent, for example, a polyfunctional monomer having a functional group capable of reacting with "the amino group of the amino group-containing resin" and/or "the hydroxyl group optionally contained in the amino group-containing resin", such as A polyfunctional monomer having at least two functional groups selected from the group consisting of epoxy, vinyl, (meth)acryl, aldehyde, isocyanate and/or allyl. For the aforementioned multifunctional monomers, for example: ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, resorcinol diepoxy Propyl ether, 1,6-hexanediol diglycidyl ether, sorbitol polyglycidyl ether, glycerin polyglycidyl ether, diglycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether Compounds with epoxy groups such as glycidyl ether and neopentylthritol polyglycidyl ether; compounds with vinyl groups such as divinylbenzene; trimethylolpropane triacrylate, 1,6-hexanediol Diacrylate, 1,9-nonanediol diacrylate, 1,10-decanediol diacrylate, trimethylolpropane trimethacrylate, 1,6-hexanediol dimethacrylate, 1 ,9-nonanediol dimethacrylate, 1,10-decanediol dimethacrylate, triethylene glycol diacrylate, tetraethylene glycol dipropylene Compounds with (meth)acryl groups such as acrylate and cyanoethyl acrylate; compounds with allyl groups such as triallyl 1,2,4-benzenetricarboxylate and triallyl isocyanate compounds etc. These crosslinking agents can be used individually or in combination of 2 or more types. Among these cross-linking agents, the cross-linking agent is preferably a compound having an epoxy group, more preferably a 2-functional epoxy compound, a multifunctional (more than 3 functional) epoxy compound, and more preferably a 2-functional epoxy compound. Functional epoxy compounds are preferred.

In an embodiment of the present invention, the epoxy equivalent of the compound having an epoxy group is preferably 50 to 1000 g/equivalent, more preferably 100 to 500 g/equivalent, and more preferably 150 to 400 g/equivalent .

From the viewpoint of easy improvement of the water-attached peel strength, the content of the crosslinking agent in the first layer is preferably at least 0.5% by mass, more preferably at least 1% by mass, and still more preferably, relative to the total mass of the first layer. It is at least 3% by mass, more preferably at least 5% by mass, and most preferably at least 8% by mass. In addition, the aforementioned content is preferably at most 30% by mass, more preferably at most 20% by mass, and still more preferably at most 15% by mass.

系化合物所組成群組中之至少1種化合物。紫外線吸收劑可單獨使用或組合使用二種以上。本說明書中，「系化合物」係指記載有該「系化合物」的化合物之衍生物。例如，「二苯基酮系化合物」係指具有「作為母體骨架的二苯基酮」及「鍵結於二苯基酮的取代基」之化合物。 In terms of ultraviolet absorbers, for example, those selected from the group consisting of benzophenone-based compounds, salicylate-based compounds, benzotriazole-based compounds and three

It is at least one compound in the group consisting of compounds. The ultraviolet absorbent can be used alone or in combination of two or more. In this specification, a "series compound" refers to a derivative of a compound described with the "series compound". For example, a "benzophenone-based compound" refers to a compound having "benzophenone as a main skeleton" and a "substituent bonded to benzophenone".

Examples of antioxidants include phenolic antioxidants, sulfur-based antioxidants, and phosphorus-based antioxidants.

Rust inhibitors include, for example, azoles, inorganic acids, organic acids, and the like. Inorganic acids and organic acids may each be salts. Examples of azoles include imidazole, benzimidazole, 2-mercaptobenzimidazole, and benzotriazole.

Examples of inorganic acids include boric acid, nitrous acid, and phosphonic acid.

Surfactants include, for example, anionic surfactants, cationic surfactants, zwitterionic surfactants, and nonionic surfactants.

In an embodiment of the present invention, relative to the total mass of the first layer, the total amount of additives contained in the first layer is preferably 0.1 to 30% by mass, more preferably 1 to 20% by mass, and More preferably, it may be 5 to 15% by mass.

In an embodiment of the present invention, relative to the total mass of the first layer, the amount of sodium (Na) in the first layer is preferably 2500ppm or less, more preferably 1500ppm or less, and more preferably 1000ppm or less . When the amount of Na in the first layer is not more than the above upper limit, it is easy to obtain a gas barrier laminate excellent in gas barrier properties. The lower limit of the aforementioned amount of Na is not particularly limited, and may be 0 ppm or more. The amount of Na in the first layer can be adjusted according to the amount of Na in the first coating liquid forming the first layer. For example, the amount of Na in the first coating liquid can be reduced by cation exchange treatment or the like. In addition, the amount of Na in the first layer can be measured by inductively coupled plasma atomic emission spectrometry using an ICP emission analyzer.

<Layer 2>

The second layer includes: a resin containing at least one functional group selected from the group consisting of hydroxyl group, carboxyl group, amino group and sulfonic acid group (hereinafter also referred to as "resin A"), and an inorganic layered compound.

(Resin A)

Resin A is not particularly limited as long as it is a resin containing at least one functional group selected from the group consisting of hydroxyl, carboxyl, amino and sulfonic acid groups. The amino group may be unsubstituted or may be substituted with an alkyl group or the like. In addition, a carboxyl group, an amino group, and a sulfonic acid group may be in the form of a salt.

Resin A may be a homopolymer or a copolymer, and the copolymer may be any one of block copolymer, alternating copolymer, random copolymer, and combinations thereof. The resin A contained in the second layer has a At least one functional group in the group consisting of amino group, amine group and sulfonic acid group can maintain the gas barrier property of the gas barrier laminate and improve the water-attached peeling strength.

For resins having at least one functional group selected from the group consisting of hydroxyl, carboxyl and amine groups, examples include polyvinyl alcohol (PVA), vinylamine-vinyl alcohol copolymers, (meth)acrylic acid- Vinyl alcohol copolymer, ethylene-vinyl alcohol copolymer (EVOH), polyacrylic acid, polymethacrylic acid, polysaccharides and their derivatives, etc. Examples of the resin having a sulfonic acid group include derivatives obtained by substituting the hydroxyl group with a sulfonic acid group in a resin having a hydroxyl group such as polyvinyl alcohol. These resins can be used individually or in combination of 2 or more types. Among these resins, resin A preferably has at least one functional group selected from the group consisting of hydroxyl and amine groups from the viewpoint of improving gas barrier properties and film durability.

In one embodiment of the present invention, resin A is preferably composed of "hydroxyl-containing resin (also known as hydroxyl-containing resin)", and the aforementioned hydroxyl-containing resin is polyvinyl alcohol, (meth)acrylic acid Vinyl alcohol-based resins such as vinyl alcohol copolymers, ethylene-vinyl alcohol copolymers, and ethyleneamine-vinyl alcohol copolymers are preferred.

In one embodiment of the present invention, the resin containing hydroxyl groups may include "resins containing amino groups in addition to hydroxyl groups". The "resin containing an amino group in addition to a hydroxyl group" includes, for example, an amino group-containing vinyl alcohol-based resin, preferably an ethylene amine-vinyl alcohol copolymer. The ethyleneamine-vinyl alcohol copolymer may be a random copolymer or a block copolymer, but a random copolymer is preferable from the viewpoint of manufacturability and cost.

In one embodiment of the present invention, the aforementioned hydroxyl-containing resin may include only "resins containing amino groups in addition to hydroxyl groups" or "resins containing amino groups in addition to hydroxyl groups" and "resins that do not contain amine groups but contain hydroxyl groups".

In one embodiment of the present invention, the amount of amine groups in resin A is preferably above 0.3 mmol/g, more preferably above 0.5 mmol/g, even more preferably above 0.8 mmol/g, and even more preferably above 1.0 It is more than mmol/g, particularly preferably at least 1.5 mmol/g, more preferably at least 1.8 mmol/g, especially preferably at least 2.0 mmol/g. When the amount of the amine groups is more than the above lower limit, the amount of the amine groups in the second layer tends to be increased, and as a result, the gas barrier properties and the water-attached peel strength of the gas barrier laminate tend to be improved. In addition, the amount of amine groups in the resin A is preferably 10 mmol/g or less, more preferably 8.0 mmol/g or less, still more preferably 5.0 mmol/g or less, still more preferably 3.0 mmol/g or less.

In one embodiment of the present invention, the number average molecular weight of the resin A is preferably at least 500, more preferably at least 800, and still more preferably at least 1,000, from the viewpoint of easy improvement of the gas barrier properties and the durability of the film. Above, preferably less than 200,000, more preferably less than 100,000, more preferably less than 50,000. The number average molecular weight of resin A can be measured by gel permeation chromatography (GPC), for example, it can be measured according to the method described in the examples.

In an embodiment of the present invention, relative to the total mass of the second layer, the content of resin A in the second layer is preferably 30% by mass or more, more preferably 40% by mass or more, and more preferably 50% by mass % or more, more preferably at least 60% by mass, particularly preferably at least 65% by mass, more preferably at most 90% by mass, more preferably at most 85% by mass, and more preferably at most 80% by mass.

In one embodiment of the present invention, relative to the total mass of the resin A contained in the second layer, the content of the hydroxyl-containing resin in the resin A is preferably 60% by mass or more, more preferably 80% by mass or more, and More preferably, it is at least 90% by mass, and more preferably at least 95% by mass. The upper limit of the aforementioned content is not particularly limited, and may be, for example, 100% by mass or less.

In one embodiment of the present invention, with respect to the total mass of resin A contained in the second layer, the content of the "resin containing amino groups in addition to hydroxyl groups" in resin A is preferably 50% by mass or more, More preferably, it is at least 60% by mass, and more preferably at least 80% by mass. The upper limit of the aforementioned content is not particularly limited, and may be, for example, 100% by mass or less.

In one embodiment of the present invention, the amount of amine groups in the second layer is preferably above 0 mmol/g, more preferably above 0.3 mmol/g, still more preferably above 0.5 mmol/g, and even more preferably above 0.8 It is not less than mmol/g, particularly preferably not less than 1.0 mmol/g, particularly preferably not less than 1.2 mmol/g, particularly preferably not less than 1.5 mmol/g. If the amount of the amine groups is more than the above lower limit, the gas barrier property and the water-attached peeling strength of the gas barrier laminate will be easily improved. In addition, the amount of amine groups in the second layer is preferably at most 3.0 mmol/g, more preferably at most 2.5 mmol/g, still more preferably at most 2.0 mmol/g, still more preferably at most 1.8 mmol/g.

The amount of amine groups in the second layer can be determined according to "the amount of amine groups in the amine group-containing resin that can be included in the second layer (mmol/g)" and "the amount of amine group-containing resin that can be included in the second layer." Scale" and so on to adjust.

The amount (mmol/g) of amine groups in the second layer can be calculated by measuring the amount (mmol/g) of amine groups (mmol/g) in the amine-group-containing resin that can be included in the second layer by ¹ H NMR measurement, for example It can be calculated according to the method described in the examples.

(inorganic layered compound)

Since the second layer contains an inorganic layered compound, the gas barrier laminate of the present invention can maintain high gas barrier properties. The inorganic stratiform compound can be used individually or in combination of 2 or more types. In the present invention, the inorganic layered compound refers to an inorganic compound in which single crystal layers are stacked to form a layered structure. A layered structure refers to a structure in which "planes that are strongly bonded and closely arranged by atoms through covalent bonds" are stacked almost parallel by weak bonding forces such as van der Waals forces.

Clay minerals are mentioned as an inorganic layered compound, and clay minerals can be used individually or in combination of 2 or more types. In terms of clay minerals, examples include kaolinite, dickite, nacrite, halloysite, antigorite, and serpentine. Chrysotile, pyrophyllite, montmorillonite, beidellite, nontronite, saponite, sauconite, stevensite ( stevensite), lithium bentonite (hectorite), tetrasilicic mica, sodium taeniolite, muscovite, pearl mica (margarite), talc, vermiculite (vermiculite), phlogopite, green brittle mica (xanthophyllite), chlorite, diamond brucite (hydrotalcite) and the like. Clay minerals may also be treated with organic matter (for example, ion exchange, etc.) to improve dispersibility and the like.

In one embodiment of the present invention, the inorganic layered compound is preferably smectite clay mineral from the viewpoint of making the aspect ratio high and easily improving the gas barrier property and the viewpoint of availability. . The clay minerals of the bentonite group include, for example, montmorillonite, aluminum bentonite, iron bentonite, saponite, sauconite, stevensite, and hectorite, among which montmorillonite is more preferred.

In an embodiment of the present invention, the thickness of the single crystal layer of the inorganic layered compound is preferably 0.5 to 3.0 nm, more preferably 0.8 to 2.0 nm, and even more preferably 1.0 to 1.5 nm. The thickness of the single crystal layer can be measured by a powder X-ray diffraction method or the like.

In an embodiment of the present invention, the average particle size of the inorganic layered compound is preferably 0.1 to 20 μm , more preferably 0.2 to 10 μm , and more preferably 0.3 to 5 μm . When the average particle size of the inorganic layered compound is within the above range, it is easy to obtain a gas barrier layered product having good gas barrier properties and transparency. The average particle diameter of the inorganic layered compound is a volume-based median diameter (D50), which can be measured with a laser diffraction scattering particle size distribution measuring device.

In an embodiment of the present invention, the aspect ratio of the inorganic layered compound (average particle size of the inorganic layered compound/thickness of the single crystal layer of the inorganic layered compound) is preferably 50 to 5000, more preferably 100 to 4000, and more preferably 200 to 3000. When the aspect ratio is more than the above lower limit, the gas barrier property will be easily improved. Moreover, if an aspect ratio is below the said upper limit, it will become easy to improve manufacturability and economical efficiency.

In one embodiment of the present invention, relative to the total mass of the second layer, the content of the layered inorganic compound in the second layer is preferably at least 1% by mass, more preferably at least 5% by mass, and more preferably at least 5% by mass. 10 mass % or more, still more preferably 15 mass % or more, especially preferably 20 mass % or more. In addition, the aforementioned content is preferably at most 50 mass %, more preferably at most 45 mass %, still more preferably at most 40 mass %, still more preferably at most 35 mass %. When the content of the layered inorganic compound in the second layer is more than the above-mentioned lower limit, the gas barrier property will be easily improved, and if it is below the above-mentioned upper limit, the water-attached peel strength will be easily improved.

(additive)

In an embodiment of the present invention, the second layer may further include at least one additive selected from the group consisting of a crosslinking agent, an ultraviolet absorber, an antioxidant, a surfactant, and an antirust agent. The aforementioned additives include, for example, the same ones as the "additives that may be contained in the first layer", and preferred embodiments are also the same as the "additives that may be contained in the first layer".

From the viewpoint of easy improvement of the water-attached peel strength, the content of the crosslinking agent in the second layer is preferably at least 0.5% by mass, more preferably at least 1% by mass, and even more preferably, relative to the total mass of the second layer. It is at least 3% by mass, more preferably at least 5% by mass, and most preferably at least 8% by mass. In addition, the aforementioned content is preferably at most 30% by mass, more preferably at most 20% by mass, and still more preferably at most 15% by mass.

In an embodiment of the present invention, relative to the total mass of the second layer, the total amount of additives contained in the second layer is preferably 0.1 to 30% by mass, more preferably 1 to 20% by mass, and More preferably, it may be 5 to 15% by mass.

In one embodiment of the present invention, relative to the total mass of the second layer, the amount of sodium (Na) in the second layer is preferably 2500ppm or less, more preferably 1500ppm or less, and more preferably 1000ppm or less . If the amount of Na in the second layer is not more than the above upper limit, a gas barrier laminate excellent in gas barrier properties will be easily obtained. The lower limit of the amount of Na is not particularly limited, and may be, for example, 0 ppm or more. The amount of Na in layer 2 can be It is adjusted according to the amount of Na in the second coating liquid forming the second layer. For example, the amount of Na in the second coating liquid can be reduced by cation exchange treatment or the like. In addition, the amount of Na in the second layer can be measured by inductively coupled plasma atomic emission spectrometry using an ICP emission analyzer.

<Substrate>

The gas barrier laminate of the present invention includes a substrate. As far as the base material is concerned, there is no particular limitation, and examples include polyesters such as polyethylene terephthalate and polyethylene naphthalate; polyolefins such as polyethylene and polypropylene; polystyrene, polyethylene Amide, polyvinyl chloride, polycarbonate, polyacrylonitrile, polyimide, etc. These base materials can be used individually or in combination of 2 or more types. In an embodiment of the present invention, the preferred substrate is polyolefin, more preferably polypropylene.

In one embodiment of the present invention, the surface of the substrate that is directly in contact with the first layer or indirectly in contact with other layers preferably has a functional group that can react with an amine group. When there is a functional group that can react with an amine group on the surface of the substrate, the "functional group that can react with an amine group on the surface of the substrate" and "the amine group in the first layer" will easily react to form a bond. The adhesion or adhesiveness between the first layer and the substrate is improved, so that the water-attached peel strength of the gas barrier laminate can be easily improved. As a functional group reactive with an amine group, a carbonyl group, an aldehyde group, a carboxyl group, an ester group etc. are mentioned, for example. In one embodiment of the present invention, the substrate can be treated with surface treatment such as corona treatment to impart functional groups that can react with amine groups to the surface of the substrate.

<Gas barrier laminate>

The gas barrier laminate of the present invention includes a substrate, a first layer, and a second layer in this order. In addition, the first layer of the gas barrier laminate contains "resin containing amino groups", the amount of amino groups in the first layer is 0.3 mmol/g or more, and the second layer contains "resin containing amino groups selected from hydroxyl, carboxyl, and amino groups". A resin with at least one functional group in the group consisting of a sulfonic acid group and a sulfonic acid group" and an "inorganic layered compound". Accordingly, the gas barrier laminate of the present invention can have both high gas barrier properties and high water-attached peel strength.

In one embodiment of the present invention, it is preferable that the amount of amine groups (mmol/g) in the first layer is greater than the amount (mmol/g) of amine groups in the second layer. If the amount of amine groups per 1g of the first layer is greater than the amount of amine groups per 1g of the second layer, the gas barrier properties and water-attached peeling strength can be easily improved.

In one embodiment of the present invention, the resin A contained in the second layer preferably includes: a resin having the same structure as "at least one of the structural units constituting the amino group-containing resin contained in the first layer" Constituent unit. For example, when the amine group-containing resin contained in the first layer is an ethyleneamine-vinyl alcohol copolymer and the resin A contained in the second layer is polyvinyl alcohol, since the polyvinyl alcohol contains One of the vinylamine unit and the vinyl alcohol unit of the copolymer” vinyl alcohol unit, so the polyvinyl alcohol contained in the second layer can be said to include: At least one of the constituent units of a thing" is a constituent unit of the same structure. When the resin A contained in the second layer contains a structural unit having the same structure as "at least one of the structural units constituting the amino group-containing resin contained in the first layer", the amino group-containing resin constituting the first layer and The compatibility of the resin A constituting the second layer is improved, and it is difficult to form an interface between the first layer and the second layer. As a result, the gas barrier property and the water-attached peel strength of the gas barrier laminate can be easily improved.

In one embodiment of the present invention, "the amino group-containing resin contained in the first layer" and "resin A contained in the second layer" are " is preferably containing at least "vinyl alcohol-based resin containing vinyl alcohol units as constituent units", and the amino-group-containing resin contained in the first layer and the resin A contained in the second layer are both vinyl alcohol-based Resin is more preferred.

In an embodiment of the present invention, the thickness of the first layer is preferably 0.001 to 10 μm , more preferably 0.01 to 1 μm , more preferably 0.05 to 0.5 μm , and even more preferably 0.08 to 0.2 μm .

In one embodiment of the present invention, the thickness of the second layer is preferably 0.001 to 10 μm , more preferably 0.01 to 5 μm , more preferably 0.05 to 1 μm , and even more preferably 0.1 to 0.5 μm μm .

In one embodiment of the present invention, it is preferable that the thickness of the first layer is thinner than that of the second layer.

In an embodiment of the present invention, the thickness of the substrate is preferably 5 to 50 μm , more preferably 10 to 40 μm , and more preferably 15 to 30 μm . In addition, when the gas barrier laminate includes two or more types of base materials, the thickness of the aforementioned base materials means the thickness of one base material.

In an embodiment of the present invention, the thickness of the gas barrier laminate of the present invention is preferably 5 to 60 μm , more preferably 10 to 40 μm , and more preferably 15 to 30 μm .

In one embodiment of the present invention, other layers such as an adhesive layer and a primer layer may exist between the base material, the first layer, and the second layer, but it is easy to improve the adhesion of the gas barrier laminate. From the viewpoint of water peeling strength, direct contact between the "substrate and the first layer" and "the first layer and the second layer" is preferable. That is, in one embodiment of the present invention, it is preferable that the gas barrier laminate of the present invention is composed only of the base material, the first layer, and the second layer, and is based on the base material, the first layer, and the second layer. The order of 2 layers is stacked.

The gas barrier laminate of the present invention has good gas barrier properties. In one embodiment of the present invention, according to JIS K7126-2-2006, the oxygen permeability of the gas barrier laminate of the present invention measured under the conditions of temperature 23°C and relative humidity 75%RH is preferably 100cc /(m ² .day.atm), more preferably 70 cc/(m ² .day.atm), more preferably 50 cc/(m ² .day.atm). Since the lower the oxygen permeability, the better the gas barrier properties of the gas barrier laminate, the lower limit is not particularly limited, for example, it may be 0 cc/(m ² .day.atm) or more.

The water-attached peel strength of the gas barrier laminate of the present invention is preferably at least 0.4N/15mm, more preferably at least 0.6N/15mm, more preferably at least 1N/15mm, and more preferably at least 1.5N/15mm. Especially preferably 2N/15mm or more. There is no particular limitation on the upper limit of the aforementioned moisture peeling strength, for example, it may be 10 N/15 mm or less. In addition, the water-attached peeling strength of the gas barrier laminate can be measured by applying water to the peeling surface so that water always exists on the peeling surface and performing a peeling test of the gas barrier laminate. determined by the method described.

[Manufacturing method of gas barrier laminate]

The gas barrier laminate of the present invention can be produced by a method including the following "first layer forming step" and "second layer forming step":

A step of forming a first layer on a substrate (first layer forming step), wherein the first layer contains an amine group-containing resin; and

A step of forming a second layer on the first layer (second layer forming step), wherein the second layer includes: having at least one function selected from the group consisting of hydroxyl, carboxyl, amino and sulfonic acid groups base resins, and inorganic layered compounds.

Therefore, the present invention also includes a method for producing a gas barrier laminate.

<1st layer formation step>

The first layer forming step is a step of forming the first layer on the base material by applying the first coating liquid on the base material and drying the coating film.

(1st coating solution)

The first coating liquid includes: an amine-group-containing resin and a liquid medium, and optionally an amine-free resin, an inorganic layered compound, and an additive. Since the first layer in the gas barrier laminate of the present invention is formed by drying and removing the liquid medium from the coating film of the first coating liquid, regarding the liquid that can be contained in the first coating liquid Components other than the matrix medium (such as resins containing amine groups, resins not containing amine groups, inorganic layered compounds, and additives) are similarly applicable to the description of each component in the item of <1st layer>. In addition, regarding the content of each component in the first coating liquid relative to the "solid content of the first coating liquid", the same applies to the "total mass of the first layer" of each component in the item of <1st layer> "Records of content. In addition, the solid fraction of the first coating liquid represents all components after excluding the liquid medium from the first coating liquid.

The liquid medium preferably includes: water and a liquid organic medium. In this specification, "liquid medium" means a medium that is liquid at 25°C and 1 atmosphere, and "liquid organic medium" means an organic compound that is liquid at 25°C and 1 atmosphere.

As a liquid organic medium, a monohydric alcohol, ethylene glycol, dimethylformamide, dimethylsulfoxide, acetone etc. are mentioned, for example. The liquid organic medium can be used individually or in combination of 2 or more types. Examples of monohydric alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol and the like.

When the liquid medium includes a liquid organic medium, the content of the liquid organic medium is preferably 1 to 70 parts by mass, more preferably 5 to 60 parts by mass, and more preferably 100 parts by mass of the liquid medium. 10 to 50 parts by mass.

In one embodiment of the present invention, the liquid medium is composed of "water" and "at least one selected from the group consisting of methanol, ethanol, 1-propanol, 2-propanol and 1-butanol." "Monohydric alcohol" is preferred, and it is more preferred to include water and ethanol. When the liquid medium contains water and monohydric alcohol, from the viewpoint of the stability of the coating liquid and the drying time of the coating film, the total amount of monohydric alcohol contained in the liquid medium per 100 parts by mass of the liquid medium Preferably it is 1-70 mass parts, More preferably, it is 5-60 mass parts, More preferably, it is 10-50 mass parts.

In an embodiment of the present invention, relative to the total mass of the first coating liquid, the content of the liquid medium is preferably 90 to 99.5% by mass, more preferably 91 to 99% by mass, and even more preferably 92 to 99.5% by mass. 98% by mass. Therefore, with respect to the total mass of the first coating liquid, the solid content of the first coating liquid is preferably 0.5 to 10% by mass, more preferably 1 to 9% by mass, and still more preferably 2 to 8% by mass. When the content of the liquid medium and the solid content of the first coating liquid are within the above-mentioned ranges, the gas barrier properties and film-forming properties can be easily improved.

The first coating liquid can be prepared by mixing and stirring the above-mentioned amine group-containing resin and liquid medium, and optionally an amine-free resin, inorganic layered compound, and additives. The mixing order and mixing method of each component are not particularly limited, for example, it can be prepared according to the following methods (1) to (3).

(1) A method of preparing a solution of an amino group-containing resin and an amino group-free resin by mixing an amino group-containing resin, a liquid medium, and an optional amino-group-free resin and stirring while heating . When the first coating liquid contains an inorganic stratiform compound and/or additive, the inorganic stratiform compound and/or additive are further added to the obtained aforementioned resin solution and stirred to disperse the inorganic stratiform compound and/or additive in the aforementioned resin solution method.

(2) When the first coating liquid contains an inorganic stratiform compound and/or an additive, by mixing and stirring the inorganic stratiform compound and/or additive with a liquid medium, the preparation containing the inorganic stratiform compound and/or A dispersion liquid of an additive, and a method of mixing and stirring the obtained dispersion liquid and a resin solution separately prepared in the same manner as the above-mentioned method (1).

(3) When the first coating liquid contains an inorganic stratiform compound and/or an additive, prepare a dispersion liquid comprising an inorganic stratiform compound and/or an additive in the same manner as the above-mentioned method (2), and in the obtained dispersion liquid A method of adding an amino group-containing resin and an optional amino group-free resin, stirring while heating, and dissolving the amino group-containing resin and the amino group-free resin in the liquid medium in the dispersion.

The temperature when dissolving the amino group-containing resin and the amino-free resin in the "liquid medium" or "the liquid medium in the dispersion liquid containing the inorganic layered compound and/or additive" is preferably 50 to 100 ℃, more preferably 60 to 100 ℃, the stirring speed is preferably 300 to 5,000rpm, more preferably 500 to 3,000rpm, the peripheral speed of stirring is preferably 1 to 8m/min, more preferably 2 to 6m/min , the stirring time is preferably 10 to 120 minutes, more preferably 20 to 110 minutes.

The temperature for dispersing the inorganic layered compound and/or additive in the "liquid medium" or "the solution of the resin containing amine group and the resin without amine group" is preferably from 20 to 100°C, more preferably from 30 to 80°C °C, the stirring speed is preferably 500 to 5,000rpm, more preferably 1,000 to 5,000rpm, and the stirring speed is preferably 1 to 20m/min, more preferably 2 to 15m/min, stirring time is preferably 10 to 150 minutes, more preferably 20 to 120 minutes.

When the first coating liquid contains an inorganic layered compound, in order to improve the dispersibility of the inorganic layered compound, it is preferable to perform high-pressure dispersion treatment of the dispersion liquid containing the inorganic layered compound using a high-pressure dispersing device. The high-pressure dispersion treatment includes, for example, an ultrahigh-pressure homogenizer manufactured by Microfluidics Corporation, a Nanomizer manufactured by Nanomizer Corporation, a Manton Gaulin type high-pressure dispersion device, and a homogenizer manufactured by Izumi Food Machinery. Here, the high-pressure dispersion treatment refers to a treatment of applying high shear and/or high pressure to the dispersion liquid by passing the dispersion liquid through a plurality of thin tubes at high speed.

The diameter of the thin tube of the high-pressure dispersing device is preferably 1 to 1,000 μm. The pressure of the high-pressure dispersion treatment is preferably from 500 to 2,000 kgf/cm ² , more preferably from 1,000 to 1,800 kgf/cm ² . The temperature during the high-pressure dispersion treatment is preferably from 10 to 50°C, more preferably from 15 to 45°C.

In one embodiment of the present invention, when preparing the first coating liquid, it is preferable to perform a cation exchange treatment to reduce the amount of Na in the first coating liquid. The cation exchange treatment can be performed with a cation exchange resin.

The cation exchange resin may, for example, be a resin introduced with a functional group having cation exchange capability. Cation exchange resins can be classified according to the acidic strength of the functional groups. Specifically, cation exchange resins can be classified into strongly acidic cation exchange resins having a sulfonic acid group or the like as a functional group, or weakly acidic cation exchange resins having a carboxyl group or the like as a functional group. Examples of the resin introduced with a functional group having cation exchange capability include styrene-based resins, acrylic resins, and methacrylic resins. In addition, cation exchange resins can be classified into gel type or macroporous type according to different resin structures such as crosslinking degree and porosity. In the preparation of the first coating liquid, the cation exchange resin that can be used is not particularly limited, and a commercially available one can also be used. Commercially available products include, for example, Rohm and Haas "Duolite C255LFH", "DIAION SK1B" manufactured by Mitsubishi Chemical Corporation, "Amberlite IR120B" manufactured by Dow Chemical Corporation, and the like. The amount of cation exchange resin used and the time of cation exchange treatment can be appropriately adjusted depending on the target Na amount.

(coating and drying)

The method of coating the first coating liquid on the base material is not particularly limited, and may be a batch method or a continuous method, such as direct gravure method, reverse gravure method, etc. Roller coating method, bottom feed three-roller reverse coating method, etc. Roller coating method, doctor blade method, die coating method, rod coating method, dipping method, spray coating method, curtain coating method, spin coating method, elastic coating method method, screen coating method, method using brush or brush, etc.

The drying method of the coating film formed on the substrate by applying the first coating liquid is not particularly limited, but it is preferable to perform heating using a drying oven or a heater. The drying temperature is preferably from 50 to 150°C, more preferably from 60 to 150°C, and further from 70 to 140°C, and the drying time is preferably from 0.1 to 120 seconds, more preferably from 0.2 to 100 seconds, and more preferably from 0.5 to 100 seconds. 70 seconds. Drying is preferably carried out under atmospheric pressure.

<Second Layer Formation Step>

The second layer forming step is a step of forming a second layer on the first layer by applying the second coating liquid on the first layer formed in the first layer forming step and drying the coating film.

(2nd coating solution)

The 2nd coating liquid contains: resin A, an inorganic layered compound, a liquid medium, and additives as needed. Since the second layer in the gas barrier laminate of the present invention is formed by drying and removing the liquid medium from the coating film of the second coating liquid, regarding the liquid that may be contained in the second coating liquid Components other than the matrix medium (for example, resin A, inorganic layered compound, and additives) are similarly applicable to the description of each component in the item of <2nd layer>. In addition, regarding the content of each component in the second coating liquid relative to the "solid content of the second coating liquid", the same applies to the "total mass of the second layer" of each component in the item of <2nd layer> content of recorded. In addition, the solid fraction of the second coating liquid represents all components after excluding the liquid medium from the second coating liquid.

The liquid medium contained in the second coating liquid may be the same as the liquid medium contained in the first coating liquid, and the liquid medium contained in the first coating liquid is similarly applicable to the liquid medium contained in the second coating liquid. Relevant records of media.

In an embodiment of the present invention, relative to the total mass of the second coating liquid, the content of the liquid medium is preferably 90 to 99.5% by mass, more preferably 91 to 99% by mass, and even more preferably 92 to 99.5% by mass. 98% by mass. Therefore, with respect to the total mass of the second coating liquid, the solid content of the second coating liquid is preferably 0.5 to 10% by mass, more preferably 1 to 9% by mass, and still more preferably 2 to 8% by mass. When the content of the liquid medium and the solid content of the second coating liquid fall within the above-mentioned ranges, it is easy to improve the gas barrier properties and film-forming properties.

The second coating liquid can be prepared by mixing and stirring the above-mentioned resin A, the inorganic layered compound, the liquid medium, and additives as necessary. The mixing order and mixing method of each component are not particularly limited, for example, it can be prepared according to the following methods (1') to (3').

(1') A solution of resin A is prepared by mixing resin A and a liquid medium and stirring while heating, adding an inorganic laminar compound and optional additives to the obtained aforementioned resin solution, and stirring to make the inorganic A method for dispersing layered compounds and/or additives in the aforementioned resin solution.

(2') By mixing and stirring the inorganic layered compound and any additives with the liquid medium, a dispersion liquid containing the inorganic layered compound is prepared, and the obtained dispersion liquid is mixed in the same manner as the above-mentioned method (1'). A method of mixing and stirring the solution of resin A prepared separately.

(3') In the same manner as the above-mentioned method (2'), prepare a dispersion liquid containing an inorganic layered compound, add resin A to the obtained dispersion liquid, stir while heating, and dissolve resin A in the above-mentioned dispersion liquid liquid medium method.

The temperature at which the resin A is dissolved in the liquid medium or the dispersion containing the inorganic layered compound is preferably from 50 to 100°C, more preferably from 60 to 100°C, and the stirring speed is preferably from 300 to 5,000rpm, more preferably 500 to 3,000 rpm, the peripheral speed of stirring is preferably 1 to 8 m/min, more preferably 2 to 6 m/min, and the stirring time is preferably 10 to 120 minutes, more preferably 20 to 110 minutes.

The temperature for dispersing the layered inorganic compound and any additives in the liquid medium or the solution of resin A is preferably from 20 to 100°C, more preferably from 30 to 80°C, and the stirring speed is preferably from 500 to 5,000rpm, more preferably It is 1,000 to 5,000 rpm, the peripheral speed of stirring is preferably 1 to 20 m/min, more preferably 2 to 15 m/min, and the stirring time is preferably 10 to 150 minutes, more preferably 20 to 120 minutes.

In order to improve the dispersibility of the inorganic stratiform compound, it is preferable to perform high-pressure dispersion treatment of the dispersion liquid containing the inorganic stratiform compound using a high-pressure dispersing device. Regarding the high-pressure dispersion treatment, the same applies to the description of the high-pressure dispersion treatment in the item (first coating liquid).

In one embodiment of the present invention, in preparing the second coating liquid, it is preferable to perform a cation exchange treatment to reduce the amount of Na in the second coating liquid. Regarding the cation exchange treatment, the same applies to the description about the cation exchange treatment in the item (first coating solution).

(coating and drying)

The "method of coating the second coating liquid on the first layer" and the "method of drying the coating film formed on the first layer by applying the second coating liquid" are not particularly limited, and can be based on the "first coating liquid". The method of "coating the first coating liquid in the layer forming step" and the "method of drying the coating film formed from the first coating liquid" were carried out in the same manner.

Since the gas barrier laminate of the present invention has good gas barrier properties and high water-attached peel strength, it can be used as packaging materials for food, cosmetics, and the like.

[Example]

Hereinafter, the present invention will be more specifically described based on examples and comparative examples, but the present invention is not limited to the following examples.

[1. Raw material]

Raw materials used in Examples and Comparative Examples are listed below.

<resin>

NVF: ethylene amine-vinyl alcohol copolymer ("Ultiloc5003" manufactured by Sekisui Specialty Chemicals America, LLC, a random copolymer, the amount of amine groups in NVF: 2.3 mmol/g, the amount of hydroxyl groups in NVF: 20 mmol/g, Number average molecular weight: 20,000, degree of saponification: 99.0%)

PVA1: Polyvinyl alcohol ("RS2117" manufactured by Kuraray Co., Ltd., number average molecular weight: 190,000, degree of saponification: 99.6%)

PVA2: Polyvinyl alcohol ("PVA105" manufactured by Kuraray Co., Ltd., number average molecular weight: 65,000, degree of saponification: 98.5%)

<Inorganic layered compound>

High-purity montmorillonite ("Kunipia G" manufactured by Kunimine Industries, single crystal layer thickness a: 1.2156nm, average particle diameter: 560nm, aspect ratio: 460)

<liquid medium>

Ion-exchanged water (specific conductivity: below 0.7 μ s/cm)

ethanol

<additive>

Crosslinking agent: bifunctional epoxy compound ("Denacol EX-920" manufactured by Nagase ChemteX Corporation, epoxy equivalent: 176 g/equivalent)

〔2. Measurement method and evaluation method〕

The raw materials used in Examples and Comparative Examples and the properties of the obtained gas barrier laminates were measured and evaluated as follows.

<Amount of Hydroxyl Group and Amount of Amino Group in NVF>

(1) The monomer ratio of the vinyl acetate-N-vinylformamide copolymer of the precursor was measured by ¹ H NMR.

(2) A vinyl acetate-N-vinylformamide copolymer is hydrolyzed to produce a vinylamine-vinyl alcohol copolymer.

(3) The residual amounts of vinyl acetate and N-vinylformamide were measured by ¹ H NMR.

(4) Calculate the amount of hydroxyl groups (mmol/g) and the amount of amino groups (mmol/g) in each NVF by converting the residual amounts (mol) of the above-mentioned vinyl acetate and N-formaldehyde per 1 g of NVF.

(measurement device and conditions)

¹ H NMR apparatus (400 MHz): "Bruker Avance 400" manufactured by Bruker Corporation

Solvent: DMSO-d ₆

Sample concentration: 1% by mass

Measuring temperature: 25°C

Cumulative times: 16 times

D1 (delay between pulses): 0.1 seconds

<Number average molecular weight of resin>

The number average molecular weights of NVF and PVA were measured by gel permeation chromatography (GPC) with the following equipment and conditions. The result is as above.

(installation and conditions)

GPC device: "Viscotek TDA305" manufactured by Malvern

Column: "SB804X2+802.5" manufactured by SOLDEX

Sample solution: an aqueous solution containing a measurement sample (concentration 1% by mass), NaNO ₃ (pH adjuster, concentration 0.05M) and sodium azide (antifungal agent, concentration 0.00077M)

Detector temperature: 30°C

Column temperature: 30°C

<Oxygen Permeability of Gas Barrier Laminate>

The gas barrier properties of the gas barrier laminates obtained in Examples and Comparative Examples were evaluated by oxygen permeability. The oxygen permeability was measured in accordance with JIS K7126-2-2006 under the conditions of 23° C. and 75% RH, respectively, using an oxygen permeability measuring device (“OX-TRANML” manufactured by MOCON Corporation). The results are shown in Table 1.

<Measurement of water-attached peel strength>

On the coating film of the uppermost layer of the gas barrier laminates obtained in Examples and Comparative Examples, a urethane-based adhesive (manufactured by Toyo Morton Co., Ltd.) was applied, and dried at 80° C. for 20 minutes in a hot air oven to form an adhesive. Agent layer (thickness of the adhesive layer: 16 μm ). For this adhesive layer, a non-stretched polypropylene film ("P1111" manufactured by Toyobo Co., Ltd.) with a thickness of 50 μm was attached as a sealing layer by dry lamination, and aged at 40°C for 1 day to obtain a "base material /1st layer/2nd layer/adhesive layer/sealing layer)”, “substrate/1st layer/adhesive layer/sealing layer)” or “substrate/2nd layer/adhesive layer/sealing layer) Laminated body for evaluation of peel strength of laminated structure.

The obtained laminate for peel strength evaluation was cut into strips with a width of 15 mm so that the substrate or sealant layer was not broken, and a part of the obtained strip-shaped laminate for peel strength evaluation was peeled off by hand for 5 mm or more . At the peeled interface, use a dropper or a syringe to drop a few drops of water, and close the substrate and sealing layer for 2 seconds to allow water to penetrate. Then, the previously peeled base material side was set as the lower side, and the sealant layer side was set as the upper side, and the sealant layer and the base material of the laminate for peel strength evaluation were sandwiched by the chucks of the testing machine. In addition, when When the adhesion is strong and the pre-peeling cannot be performed as mentioned above, then the pre-peeling is not performed, and after the water is penetrated into the interface between the sealing layer and the substrate in the same manner as above, the sealing layer and the substrate are respectively clamped by the chucks of the testing machine. Substrate. According to the test method stipulated in JIS-K6854-3:1999 "Adhesives - Peel Adhesive Strength Test Method - Part 3: T-peel" of Japanese Industrial Regulations, at 23°C, 50%RH and a tensile speed of 300mm/min Under these conditions, the peel strength between the base material and the sealing layer was measured using a small tabletop tester (“EZ-LX” manufactured by Shimadzu Corporation). The aforementioned measurement was carried out while dripping water on the peeling surface using a dropper or a syringe so that water always existed on the peeling surface (so that water accumulated on the interface existed). A schematic diagram of the aforementioned measurement is shown in FIG. 1 .

The results are shown in Table 1. In addition, when the base material or the sealing layer was broken and the peel strength could not be measured, it was described as "crack".

<Example 1>

1. Preparation of the first coating solution

110 g of ion-exchanged water and 30 g of NVF were placed in a polypropylene container, and the mixture of ion-exchanged water and NVF was heated up to 90° C. while stirring at 1,000 rpm. After the temperature was raised, the NVF was dissolved in water by stirring at 90° C. and 1,000 rpm for 60 minutes. The resulting resin solution was cooled to below 60°C. After cooling, 77 g of ethanol was added to the resin solution over 5 minutes while stirring at 60° C. or less at 1,000 rpm, and further stirred at 1,000 rpm for 10 minutes to obtain a solution (A). This solution (A) was diluted with a diluent (water/ethanol=2/1 (mass ratio) to a solid content of 1.3% by mass to obtain a first coating liquid.

The content of NVF in the first coating liquid (100% by mass) was 1.3% by mass, and the content of the liquid medium (water and ethanol) was 98.7% by mass. In addition, the amount of ethanol was 33.3 parts by mass with respect to 100 parts by mass of the liquid medium.

2. Preparation of the second coating solution

A solution (A) was obtained in the same manner as the first coating solution.

Next, 15 g of montmorillonite was added to 360 g of ion-exchange water, and it stirred at room temperature and 3,500 rpm for 30 minutes, and obtained the dispersion liquid (B).

Add the solution (A) and the dispersion (B) to a polypropylene container so that the ratio of the resin in the solution (A) to the inorganic layered compound in the dispersion (B) becomes resin/inorganic layered compound=60/ 40 (mass ratio). The mixture of solution (A) and dispersion (B) was stirred at room temperature and 3,500 rpm for 60 minutes. Then, 5 g of ion-exchanged water and 153 g of ethanol were further added to the mixture over 15 minutes, and stirred at room temperature for 10 minutes to obtain a dispersion (C).

Under the conditions of 30°C and 1250kgf/cm ² , the resulting dispersion (C) was subjected to a high-pressure dispersion device ("Ultra-high pressure homogenizer M110-E/H" manufactured by Microfluidics Corporation, diameter of thin tube: 100 μm ) High-pressure dispersion treatment to obtain dispersion (D).

With respect to 100 parts by mass of the obtained dispersion (D), 3.0 parts by mass of a cation exchange resin (Duolite C255LFH (manufactured by Rohm and Haas JAPAN)) was added to the dispersion (D) to perform cation exchange. Then, by Filtration removed the cation exchange resin from the dispersion (D) to obtain a dispersion (E). The content of NVF in the dispersion (E) (100% by mass) was 4.0% by mass, and the content of montmorillonite was 2.0% by mass , the content of the liquid medium (water and ethanol) is 94.0% by mass. In addition, the amount of ethanol is 33.3 parts by mass relative to 100 parts by mass of the liquid medium. Use diluent (water/ethanol=2/1 (mass ratio) ), and dilute this dispersion liquid (E) to a solid content of 4.0% by mass to obtain a second coating liquid.

The NVF content in the second coating liquid (100 mass %) was 2.7 mass %, the smectite content was 1.3 mass %, and the liquid medium (water and ethanol) content was 96.0 mass %. In addition, the amount of ethanol was 33.3 parts by mass with respect to 100 parts by mass of the liquid medium.

3. Fabrication of gas barrier laminates

On the corona-treated surface of a biaxially stretched polypropylene film (hereinafter referred to as "OPP") ("FOA" manufactured by Futamura Chemical Co., Ltd.) with a thickness of 20 μm , the first coating liquid was coated with a bar coater , dried at 100° C. for 1 minute in a hot air oven to form a first layer on the substrate to obtain a laminate of the substrate/first layer (thickness of the first layer: 0.1 μm ). Next, on the first layer, apply and dry the second coating liquid in the same way as the first coating liquid, and produce a substrate/first layer/second layer (thickness of the second layer: 0.2 μm ) Gas barrier laminate. In addition, drying is performed in the atmospheric environment of normal pressure.

<Example 2>

In the preparation of the dispersion (C) in the second coating liquid, in addition to mixing the solution (A) and the dispersion (B) so that NVF/inorganic layered compound = 67/33 (mass ratio), and A gas barrier laminate was fabricated in the same manner as in Example 1.

<Example 3>

A gas barrier laminate was produced in the same manner as in Example 2 except that the thickness of the second layer was set to 0.4 μm .

<Example 4>

A gas barrier laminate was produced in the same manner as in Example 2, except that PVA1 was used instead of NVF in the second coating liquid and ion exchange of the dispersion (D) was not performed.

<Example 5>

A gas barrier laminate was fabricated in the same manner as in Example 2 except that PVA1 was used instead of NVF in the second coating solution.

<Example 6>

In the preparation of the first coating liquid, for the solution (A), in addition to mixing the dispersion liquid (B) so that NVF/inorganic layered compound = 70/30 (mass ratio), for the obtained solution (A) and the dispersion The mixture of liquid (B) with A gas barrier laminate was fabricated in the same manner as in Example 2, except that high-pressure dispersion treatment and cation exchange were performed in the same manner as in the preparation of the dispersion liquid (D) and dispersion liquid (E).

<Example 7>

In the preparation of the first coating liquid, for the solution (A), in addition to mixing the dispersion liquid (B) such that NVF/inorganic layered compound = 67/33 (mass ratio), the obtained solution (A) and the dispersion liquid The mixture of (B) is subjected to high-pressure dispersion treatment and cation exchange in the same manner as the preparation of the dispersion liquid (D) and the dispersion liquid (E), and when preparing the dispersion liquid (C) in the second coating liquid so that A gas barrier laminate was produced in the same manner as in Example 1, except that the solution (A) and the dispersion (B) were mixed so that NVF/inorganic layered compound=70/30 (mass ratio).

<Embodiment 8>

In the preparation of the first coating liquid, for the solution (A), in addition to mixing the dispersion liquid (B) such that NVF/inorganic layered compound = 60/40 (mass ratio), the obtained solution (A) and the dispersion liquid A gas barrier laminate was produced in the same manner as in Example 2, except that the mixture of (B) was subjected to high-pressure dispersion treatment and cation exchange in the same manner as the preparation of the dispersion liquid (D) and dispersion liquid (E).

<Example 9>

In the preparation of the first coating liquid, for the solution (A), in addition to mixing the dispersion liquid (B) such that NVF/inorganic layered compound = 50/50 (mass ratio), the obtained solution (A) and the dispersion liquid A gas barrier laminate was produced in the same manner as in Example 2, except that the mixture of (B) was subjected to high-pressure dispersion treatment and cation exchange in the same manner as the preparation of the dispersion liquid (D) and dispersion liquid (E).

<Example 10>

In preparation of the solution (A) in the first coating liquid, a gas barrier laminate was fabricated in the same manner as in Example 2 except that NVF and PVA2 were mixed so that NVF/PVA2=80/20 (mass ratio).

<Example 11>

In preparation of the solution (A) in the first coating liquid, a gas barrier laminate was fabricated in the same manner as in Example 4, except that NVF and PVA2 were mixed so that NVF/PVA2=70/30 (mass ratio).

<Example 12>

In preparation of the solution (A) in the first coating liquid, a gas barrier laminate was produced in the same manner as in Example 4, except that NVF and PVA2 were mixed so that NVF/PVA2=50/50 (mass ratio).

<Example 13>

In preparation of the solution (A) in the first coating liquid, a gas barrier laminate was produced in the same manner as in Example 2 except that NVF and PVA2 were mixed so that NVF/PVA2=20/80 (mass ratio).

<Example 14>

In the first coating solution, a gas was produced in the same manner as in Example 2, except that a crosslinking agent (EX-920) was added to the solution (A) so that NVF/crosslinking agent = 90/10 (mass ratio). Barrier laminates.

<Example 15>

In the preparation of the dispersion liquid (C) in the second coating liquid, in addition to mixing the solution (A) and the dispersion liquid ( Except for B) and the crosslinking agent (EX-920), a gas barrier laminate was produced in the same manner as in Example 14.

<Comparative example 1>

A gas barrier laminate was produced in the same manner as in Example 2 except that the first layer was not formed between the substrate and the second layer.

<Comparative example 2>

In the preparation of the dispersion liquid (C) in the second coating liquid, in addition to mixing the solution (A) and the dispersion liquid (B) so that NVF/inorganic layered compound = 80/20 (mass ratio), and making the second A gas barrier laminate was produced in the same manner as in Comparative Example 1 except that the thickness of the two layers was 0.1 μm.

<Comparative example 3>

A gas barrier laminate was produced in the same manner as in Example 4 except that the first layer was not formed between the base material and the second layer.

<Comparative example 4>

A gas barrier laminate was produced in the same manner as in Example 1 except that the second layer was not formed on the first layer.

<Comparative example 5>

In preparation of the solution (A) in the first coating liquid, a gas barrier laminate was produced in the same manner as in Example 1 except that PVA2 was used instead of NVF and the second layer was not formed on the first layer.

<Comparative example 6>

In preparing the solution (A) in the first coating liquid, a gas barrier laminate was prepared in the same manner as in Comparative Example 4 except that NVF and PVA2 were mixed so that NVF/PVA2=10/90 (mass ratio).

<Comparative example 7>

In the preparation of the solution (A) in the first layer, in addition to using an urethane-based primer (manufactured by Toyo Morton Co., Ltd., main ingredient: EL-510-1-17K (polyester-based), 83% by mass; and a hardener : CAT-RT87 (polyisocyanate-based), 17% by mass) instead of NVF, and the second layer was not formed on the first layer, a gas barrier laminate was produced in the same manner as in Example 1.

<Comparative example 8>

In the preparation of the solution (A) in the first layer, in addition to using an urethane-based primer (manufactured by Toyo Morton Co., Ltd., main ingredient: EL-510-1-17K (polyester-based), 83% by mass; and a hardener : CAT-RT87 (polyisocyanate type), 17% by mass) instead of NVF, a gas barrier laminate was produced in the same manner as in Example 2.

Table 1 shows the measurement results and evaluation results of Examples and Comparative Examples. In addition, "cissing" in the table indicates that in the step of forming the first layer and/or the second layer, a phenomenon called "cissing" occurs. The coating liquid was pushed away to cause coating film defects (surface defects) such as dents, so that a gas barrier laminate could not be obtained or various evaluations could not be performed.

[Table 1]

As shown in Table 1, compared with Comparative Examples, it was confirmed that the gas barrier laminates obtained in Examples had lower oxygen permeability, higher gas barrier properties, and higher water-attached peel strength.

Claims (15)

A laminate, which is a gas barrier laminate sequentially comprising a substrate, a first layer, and a second layer, wherein, The first layer contains a resin containing amine groups, and the amount of amine groups in the first layer is 0.3 mmol/g or more, The second layer includes: a resin containing at least one functional group selected from the group consisting of hydroxyl group, carboxyl group, amino group and sulfonic acid group, and an inorganic layered compound. The laminate according to claim 1, wherein the content of the layered inorganic compound in the second layer is 1 to 50% by mass relative to the total mass of the second layer. The laminate according to Claim 1, wherein the resin contained in the second layer contains at least one functional group selected from the group consisting of hydroxyl groups and amine groups. The laminate according to claim 1, wherein the resin contained in the second layer includes a hydroxyl group-containing resin. The laminate according to claim 4, wherein the hydroxyl group-containing resin contained in the second layer is a vinyl alcohol-based resin. The laminate according to claim 4, wherein the hydroxyl group-containing resin contained in the second layer includes a resin containing amino groups in addition to hydroxyl groups. The laminate according to Claim 1, wherein the amount of amine groups (mmol/g) in the first layer is greater than the amount (mmol/g) of amine groups in the second layer. The laminate according to claim 1, wherein the first layer contains, in addition to the amino group-containing resin, a resin containing a hydroxyl group but not containing an amino group. The laminate according to Claim 8, wherein the resin containing hydroxyl groups but not containing amino groups contained in the first layer is a vinyl alcohol-based resin not containing amino groups. The laminate according to claim 1, wherein the amino group-containing resin contained in the first layer includes a resin containing hydroxyl groups in addition to amino groups. The laminate according to claim 1, wherein the amine group-containing resin contained in the first layer includes an ethyleneamine-vinyl alcohol copolymer. The laminate according to claim 1, wherein the content of the layered inorganic compound in the first layer is 50% by mass or less relative to the total mass of the first layer. The laminate according to any one of Claims 1 to 12, wherein the first layer and/or the second layer further comprise: selected from crosslinking agents, ultraviolet absorbers, antioxidants, surfactants and rust inhibitors At least one additive in the group formed. The laminate according to claim 13, wherein the crosslinking agent has an epoxy group. A method for manufacturing the laminate described in claim 1, comprising the following steps: The step of forming a first layer on the substrate, wherein the first layer comprises an amine group-containing resin; and A step of forming a second layer on the first layer, wherein the second layer includes: a resin having at least one functional group selected from the group consisting of hydroxyl, carboxyl, amino and sulfonic acid groups, and an inorganic layer compound.

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