JP2024003156A - gas barrier laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a gas barrier laminate having high gas barrier properties under high humidity.

SOLUTION: A gas barrier laminate includes a substrate, a barrier layer and a sealant layer in this order. The barrier layer includes a first barrier layer containing a resin and an inorganic laminar compound. The sealant layer includes a thermoplastic resin having a heat sealability.

SELECTED DRAWING: None

COPYRIGHT: (C)2024,JPO&INPIT

Description

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

Packaging materials for foods, cosmetics, etc. are required to have gas barrier properties, that is, properties that suppress the permeation of gases such as water vapor and oxygen, in order to prevent their deterioration. As a packaging material with high gas barrier properties, a laminate having a gas barrier layer formed on a base material using polyvinyl alcohol or a derivative thereof is known. Here, the term "gas barrier layer" refers to a layer used to suppress gas permeation.

Patent Document 1 discloses that an anchor layer is laminated on a layer made of a resin composition containing at least an inorganic layered compound and a resin, and a thermoplastic resin layer having heat sealability is laminated on the anchor layer by extrusion lamination. A film laminate is described which is characterized by comprising:

Japanese Patent Application Publication No. 2000-158602

The film laminate according to Patent Document 1 is said to have gas barrier properties and heat sealing properties, as well as excellent tearability. However, according to studies by the present inventors, it has been found that the film laminate described in Patent Document 1 has room for improvement in gas barrier properties under high humidity conditions, for example, relative humidity of 60% or more.

Therefore, an object of the present invention is to provide a gas barrier laminate having high gas barrier properties under high humidity.

The present inventors have made extensive studies to solve the above problems, and as a result, have arrived at the present invention. That is, the present invention provides the following preferred embodiments.

[1]
A gas barrier laminate comprising a base material, a barrier layer and a sealant layer in this order,
The barrier layer includes a first barrier layer containing a resin and an inorganic layered compound,
The sealant layer is a laminate including a thermoplastic resin having heat sealability.
[2]
The laminate according to [1], wherein the resin included in the first barrier layer includes a resin containing at least one functional group selected from the group consisting of a hydroxy group, a carboxy group, an amino group, and a sulfo group.
[3]
The laminate according to [1] or [2], wherein the resin contained in the first barrier layer includes a resin containing an amino group.
[4]
The laminate according to any one of [1] to [3], wherein the barrier layer and the sealant layer are in direct contact.
[5]
The laminate according to any one of [1] to [4], wherein the barrier layer includes a second barrier layer between the first barrier layer and the base material.
[6]
The laminate according to [5], wherein the second barrier layer contains an amino group-containing resin.
[7]
The laminate according to [5] or [6], wherein the amount of amino groups in the second barrier layer is 0.3 mmol/g or more.
[8]
The laminate according to [5] to [7], wherein the second barrier layer has a thickness of 0.001 to 10 μm.
[9]
The laminate according to any one of [1] to [3] and [5] to [8], which includes an anchor layer between the barrier layer and the sealant layer.
[10]
The laminate according to any one of [1] to [9], comprising an anchor layer between the base material and the barrier layer.
[11]
The thermoplastic resin having heat-sealing properties is at least one selected from the group consisting of polyolefin resins, polyacrylonitrile resins, polyester resins, ethylene-vinyl alcohol copolymers, metallocenes, and higher fatty acid polyolefins, [1] The laminate according to any one of to [10].
[12]
The base material is selected from the group consisting of polyolefin resin, polyester resin, amide resin, acrylic resin, polystyrene resin, hydrophobized cellulose resin, halogen-containing resin, hydrogen bonding resin, and engineering plastic resin. The laminate according to any one of [1] to [11], comprising a resin.
[13]
The laminate according to any one of [1] to [12], wherein the base material is a paper base material.
[14]
The laminate according to [13], which includes a sealing layer between the paper base material and the barrier layer.
[15]
The method for producing a gas barrier laminate according to any one of [1] to [14], which includes the step of laminating a sealant layer directly or indirectly on the barrier layer by extrusion lamination or hot roll lamination.

In each layer of the gas barrier laminate of the present invention, the chemical structure of each compound, especially the chemical structure of the functional group, changes due to the chemical reaction between the components, and the amount of the functional group also changes from the time of blending. There is. However, in this specification, for convenience, the compound names, functional group names, and amounts of components of each layer are expressed based on the chemical structure of each compound in an unreacted state before forming each layer.

According to the present invention, a gas barrier laminate having high gas barrier properties under high humidity can be provided.

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

[Gas barrier laminate]
The gas barrier laminate of the present invention includes a base material, a barrier layer, and a sealant layer in this order, the barrier layer includes a first barrier layer containing a resin and an inorganic layered compound, and the sealant layer has heat sealability. Contains a thermoplastic resin with

<Base material>
The gas barrier laminate of the present invention includes a base material. The base material is not particularly limited, and may be, for example, a base material containing resin or a paper base material.

In one embodiment of the present invention, the base material preferably contains a resin, and examples of the resin contained in the base material include polyethylene (low density, high density), ethylene-propylene copolymer, ethylene-butene copolymer. Polyolefin resins such as polymers, ethylene-hexene copolymers, ethylene-octene copolymers, polypropylene, ethylene-vinyl acetate copolymers, ethylene-methyl methacrylate copolymers, ionomer resins; polyethylene terephthalate, polybutylene terephthalate, polyethylene Polyester resins such as naphthalate; amide resins such as nylon-6, nylon-6,6, metaxylene diamine-adipic acid condensation polymer, polymethylmethacrylimide; acrylic resins such as polymethylmethacrylate; polystyrene, styrene - Polystyrene resins such as acrylonitrile copolymer, styrene-acrylonitrile-butadiene copolymer, polyacrylonitrile; Hydrophobized cellulose resins such as cellulose triacetate and cellulose diacetate; polyvinyl chloride, polyvinylidene chloride, polyvinylidene fluoride, Halogen-containing resins such as Teflon; hydrogen-bonding resins such as polyvinyl alcohol, ethylene-vinyl alcohol copolymers, cellulose derivatives; polycarbonate resins, polysulfone resins, polyethersulfone resins, polyetheretherketone resins, polyphenylene oxide resins, Examples include engineering plastic resins such as methylene oxide resin and liquid crystal resin. These resins can be used alone or in combination of two or more. Among these, polyolefin is preferred, and polyethylene and polypropylene are more preferred. These base materials may be subjected to surface treatment such as corona treatment or low-temperature plasma treatment in order to improve adhesion with the coating film.

In another embodiment of the invention, the substrate is preferably a paper substrate. The paper base material is not particularly limited, and includes, for example, kraft paper, high-quality paper, structured paper, glassine paper, parchment paper, synthetic paper, and various corrugated papers.
The basis weight of the paper base material is not particularly limited, but from the viewpoint of improving gas barrier properties, it is preferably 20 to 600 g/m ² , more preferably 30 to 300 g/m ² , and still more preferably 40 to 100 g/m ² . It's okay.

The thickness of the base material is 2 to 1000 μm, preferably 5 to 100 μm, more preferably 10 to 80 μm, and even more preferably 15 to 60 μm. Note that when the gas barrier laminate includes two or more base materials, the thickness of the base materials represents the thickness of one base material.

<Barrier layer>
The gas barrier laminate of the present invention includes a barrier layer.

(First barrier layer)
The barrier layer includes a first barrier layer containing a resin and an inorganic layered compound. The resin contained in the first barrier layer includes a resin containing at least one functional group selected from the group consisting of a hydroxy group, a carboxy group, an amino group, and a sulfo group (hereinafter also referred to as "resin A"). is preferred.

Resin A is not particularly limited as long as it contains at least one functional group selected from the group consisting of a hydroxy group, a carboxy group, an amino group, and a sulfo group. Resin A can be used alone or in combination of two or more. The amino group may be unsubstituted or substituted with an alkyl group or the like. Furthermore, the carboxy group, amino group, and sulfo group may all be in the form of a salt. Resin A may be a homopolymer or a copolymer, and the copolymer may be a block copolymer, an alternating copolymer, a random copolymer, or a combination thereof. The resin A contained in the first barrier layer has at least one functional group selected from the group consisting of a hydroxy group, a carboxy group, an amino group, and a sulfo group, thereby improving the gas barrier properties of the gas barrier laminate under high humidity. The peel strength of the gas barrier laminate can be improved.

Examples of the resin having at least one functional group selected from the group consisting of hydroxy group, carboxy group, and amino group include polyvinyl alcohol (PVA), vinylamine-vinyl alcohol copolymer, (meth)acrylic acid-vinyl alcohol Examples include copolymers, ethylene-vinyl alcohol copolymers (EVOH), polyacrylic acids, polymethacrylic acids, polysaccharides, and derivatives thereof. Examples of the resin having a sulfo group include derivatives obtained by substituting the hydroxy group with a sulfo group in a resin having a hydroxy group such as polyvinyl alcohol. These resins can be used alone or in combination of two or more.

In a preferred embodiment of the present invention, the resin A may have at least one functional group selected from the group consisting of a hydroxy group and an amino group, from the viewpoint of improving gas barrier properties and film durability under high humidity. Preferably, from the viewpoint of improving the peel strength of the gas barrier laminate, a resin containing an amino group (amino group-containing resin) is more preferable.

The amino group-containing resin is not particularly limited as long as it contains an amino group, such as vinylamine-vinyl alcohol copolymer; polyethyleneimine; ethylenically unsaturated resin such as vinylbenzene trimethylammonium chloride, aminoethyl acrylate hydrochloride, etc. Mono-, di-, or trialkylammonium salts, N-methylaminoethyl acrylate, N,N-dimethylaminoethyl methacrylate, N,N-dimethylaminomethyl-N-acrylamide, N,N-dimethylaminoethyl-N-acrylamide, etc. Examples include homopolymers of and copolymers thereof. The amino group-containing resin can be used alone or in combination of two or more. The amino group may be unsubstituted or substituted with an alkyl group or the like.

The amino group-containing resin preferably contains a resin containing a hydroxy group in addition to an amino group, more preferably a vinyl alcohol resin containing an amino group, from the viewpoint of improving gas barrier properties and peel strength under high humidity. more preferably contains a vinylamine-vinyl alcohol copolymer. The vinylamine-vinyl alcohol copolymer may be a random copolymer or a block copolymer, but from the viewpoint of manufacturability and cost, a random copolymer is preferable.

The amount of amino groups in the amino group-containing resin is preferably 0.3 mmol/g or more, for example 0.3 to 10 mmol/g, more preferably 0.5 to 10 mmol/g, even more preferably 0.8 ~8.0 mmol/g, even more preferably 1.0 to 8.0 mmol/g, particularly preferably 1.5 to 5.0 mmol/g, particularly more preferably 1.8 to 5.0 mmol/g, particularly preferably is 2.0 to 3.0 mmol/g. When the amount of amino groups is at least the above lower limit, gas barrier properties under high humidity can be easily improved. Moreover, the adhesiveness with the base material and/or the sealant layer is likely to be improved, and the peel strength of the gas barrier laminate is likely to be improved. The amount of amino groups in the amino group-containing resin can be measured by ¹ H NMR measurement, and can be calculated, for example, by the method described in Examples of International Publication No. 2023/042722.

When the amino group-containing resin contains a hydroxy group, the amount of hydroxy groups in the amino group-containing resin is preferably 1 to 50 mmol/g, more preferably 5 to 40 mmol/g, even more preferably 10 to 30 mmol/g, Even more preferably it is 15 to 25 mmol/g. When the amount of hydroxyl groups is at least the above lower limit, a crystal structure is easily formed in the first barrier layer by hydrogen bonding, and gas barrier properties under high humidity are easily improved. When the amount of hydroxyl groups is below the above upper limit, it is easy to suppress a decrease in surface activity of the resin containing hydroxyl groups in addition to amino groups, and it is easy to improve compatibility with hydrophobic materials. Note that the amount of hydroxyl groups in the resin can be measured by ¹ H NMR measurement.

When the amino group-containing resin contains a hydroxy group, the degree of saponification is 80% or more, more preferably 90%, from the viewpoint of easily increasing the crystallinity of the amino group-containing resin and easily improving gas barrier properties under high humidity. % or more, more preferably 95% or more, particularly preferably 98% or more, and may be 100% or less.

The number average molecular weight of the amino group-containing resin is preferably 5,000 or more and 100,000 or less, more preferably 10,000 or more and 50,000 or less, even more preferably 12,000 or more and 40,000 or less, and even more preferably It is 15,000 or more and 30,000 or less. The number average molecular weight can be measured by gel permeation chromatography (GPC).

Moreover, the amino group-containing resin can also be used in combination with an amino group-free resin that does not contain an amino group, as long as the effects of the present invention are not impaired. In this case, examples of the amino group-free resin include vinyl alcohol resins that do not contain amino groups, such as polyvinyl alcohol, (meth)acrylic acid-vinyl alcohol copolymer, and ethylene-vinyl alcohol copolymer. These can be used alone or in combination of two or more. Among these, the amino group-free resin is preferably a resin containing a hydroxyl group, more preferably a vinyl alcohol resin, and even more preferably vinyl alcohol.

In another preferred embodiment of the present invention, the resin A is a resin containing two or more functional groups selected from the group consisting of a hydroxy group, a carboxy group, an amino group, and a sulfo group from the viewpoint of gas barrier properties. component, and preferably a resin component containing a hydroxy group and a carboxy group. The resin component containing two or more functional groups may be a resin containing two or more functional groups in one molecule, or a resin containing a first functional group and a resin containing a second functional group. It may be a combination with. In the resin component containing two or more functional groups, it is preferable that the functional groups form a covalent bond or an ionic bond with each other.

When the resin component is a resin containing two or more of the functional groups in one molecule, examples of the resin include vinyl alcohol-acrylic acid copolymer, vinyl alcohol-methacrylic acid copolymer, vinyl alcohol-vinyl amine. Examples include copolymers, acrylic acid-vinylamine copolymers, and methacrylic acid-vinylamine copolymers.
When the resin component is a combination of a resin containing a first functional group and a resin containing a second functional group, the resin component may be selected from, for example, polyvinyl alcohol, polyacrylic acid, polymethacrylic acid, and polyvinylamine. It may be a combination of two or more resins selected from the group consisting of: Here, the resin containing the first functional group and the resin containing the second functional group may be oligomers.

The resin component is preferably a resin component containing a hydroxyl group and a carboxy group from the viewpoints of ease of solubility in an aqueous medium, ease of handling, water resistance, gas barrier property, and scratch resistance of the coating film. However, the "hydroxy group" does not include "-OH" in the carboxy group.

The resin component containing a hydroxy group and a carboxyl group may be a resin containing a hydroxy group and a carboxyl group in one molecule. Further, the resin component containing a hydroxy group and a carboxyl group may be a combination of a resin containing a hydroxy group and a resin containing a carboxyl group.

Examples of resins containing a hydroxy group and a carboxy group in one molecule include vinyl alcohol-acrylic acid copolymers and vinyl alcohol-methacrylic acid copolymers.

Examples of resins containing hydroxy groups include polyvinyl alcohol, ethylene-vinyl alcohol copolymers, and polysaccharides.

Polyvinyl alcohol is a polymer having monomer units derived from vinyl alcohol as a main component. Polyvinyl alcohol can be produced by hydrolyzing polyvinyl carboxylates such as polyvinyl acetate, polyvinyl trifluoroacetate, polyvinyl formate, and polyvinyl pivalate, or by hydrolyzing polyvinyl ethers such as polytert-butyl vinyl ether and polytrimethylsilyl vinyl ether. (For details on polyvinyl alcohol, see, for example, "The World of PVA" edited by Poval Kai, 1992, Kobunshi Publishing Co., Ltd.; Nagano et al., "Poval", 1981, Co., Ltd.) (You can refer to the Polymer Publishing Association).

From the viewpoint of gas barrier properties, the degree of saponification of polyvinyl alcohol is preferably 70 mol% or more, more preferably 85 mol% or more, and even more preferably 98 mol% or more.
The degree of saponification can be determined by the following formula.
Saponification degree (mol%) = {(number of hydroxyl groups in polyvinyl alcohol)/(total number of sites having ester bonds or sites having ether bonds remaining in polyvinyl alcohol and hydroxyl groups)} ×100...(formula)

The degree of polymerization of polyvinyl alcohol is preferably 100 or more and 5000 or less, and 200 or more and 3000 or less, from the viewpoint of film formability.

The ethylene-vinyl alcohol copolymer is a polymer having monomer units derived from ethylene and monomer units derived from vinyl alcohol.

Further, a polyvinyl alcohol derivative having a functional group other than a hydroxy group or a carboxy group may also be used. Examples of functional groups other than hydroxy or carboxy groups include amino groups, thiol groups, sulfonic acid groups, phosphoric acid groups, carboxylate groups, sulfonate ion groups, phosphate ion groups, ammonium groups, phosphonium groups, silyl groups, Examples include a siloxy group, an allyl group, a fluoroalkyl group, an alkoxy group, a carbonyl group, and a halogen group. A portion of the hydroxyl groups in polyvinyl alcohol may be replaced with one or more of the above functional groups.

Polysaccharides are biopolymers that are synthesized in biological systems by condensation polymerization of various monosaccharides, and also include those that are chemically modified based on them. Examples include cellulose and cellulose derivatives such as hydroxymethylcellulose, hydroxyethylcellulose, and carboxymethylcellulose, amylose, amylopectin, pullulan, curdlan, xanthan, chitin, and chitosan.

Examples of the resin containing a carboxyl group include polyacrylic acid, polymethacrylic acid, partially neutralized polyacrylic acid, partially neutralized polymethacrylic acid, and acrylic acid-methacrylic acid copolymer. These may be used alone or in combination of two or more types. The weight average molecular weight of the resin containing a carboxyl group is preferably 2,000 or more and 1,000,000 or less, more preferably 5,000 or more and 1,000,000 or less, from the viewpoint of film-forming properties and coating film scratch resistance.

Partially neutralized polyacrylic acid or partially neutralized polymethacrylic acid is produced by adding an alkali metal ion donating compound described below to an aqueous solution of polyacrylic acid or polymethacrylic acid to neutralize some of the carboxy groups. It can be obtained by converting it into an alkali metal salt. These can be made to have a desired degree of neutralization by adjusting the ratio of the amounts of polyacrylic acid or polymethacrylic acid and the alkali metal ion donating compound. The degree of neutralization is calculated by the following formula.
Neutralization degree = (A/B) x 100
A: Number of moles of carboxy groups that have been neutralized to become metal salts in 1 g of partially neutralized polyacrylic acid or partially neutralized polymethacrylic acid B: Partially neutralized polyacrylic acid or polymethacrylic acid Total number of moles of carboxy groups and carboxy groups that have been neutralized to become metal salts in 1 g of partially neutralized product

In addition, partially neutralized polyacrylic acid or partially neutralized polymethacrylic acid is produced by contacting an aqueous solution of completely neutralized polyacrylic acid or completely neutralized polymethacrylic acid with a hydrogen ion type ion exchange resin. It can also be obtained by The contacting method includes mixing an aqueous solution of completely neutralized polyacrylic acid or completely neutralized polymethacrylic acid with a hydrogen ion type ion exchange resin, stirring, and then removing the residue of the hydrogen ion type ion exchange resin. In this method, the desired amount can be obtained by adjusting the ratio of the completely neutralized polyacrylic acid or completely neutralized polymethacrylic acid to the hydrogen ion type ion exchange resin, the temperature of the aqueous solution, and the stirring time. The degree of neutralization can be made as follows. There is also a method in which an aqueous solution of completely neutralized polyacrylic acid or completely neutralized polymethacrylic acid is passed through a column packed with a hydrogen ion type ion exchange resin. A desired degree of neutralization can be achieved by adjusting the speed and temperature of the aqueous solution. Further, the degree of neutralization is calculated by the following formula.
Neutralization degree = (C/D) x 100
C: Number of moles of carboxy groups present as a metal salt in 1 g of partially neutralized polyacrylic acid or partially neutralized polymethacrylic acid D: Partially neutralized polyacrylic acid or partially neutralized polymethacrylic acid Total number of moles of carboxy groups generated by ion exchange and carboxy groups existing as metal salts in 1 g

The degree of neutralization of the partially neutralized polyacrylic acid and partially neutralized polymethacrylic acid is preferably 0.1% or more and 20% or less from the viewpoint of water resistance and transparency of the coating film.

The amount of hydroxy groups in the resin component containing hydroxy groups and carboxy groups is 30 mol% or more and 95 mol% or less, preferably 70 mol% or more and 95 mol% or less. The amount of carboxy groups in the resin component containing hydroxy groups and carboxy groups is 5 mol% or more and 70 mol% or less, preferably 5 mol% or more and 30 mol% or less. However, the total amount of hydroxy groups and carboxy groups contained in the resin component containing hydroxy groups and carboxy groups is 100 mol%.

The amount of hydroxy groups and the amount of carboxy groups in the resin component containing hydroxy groups and carboxy groups can be determined by known NMR methods, IR methods, and the like. For example, in the case of the IR method, a calibration curve can be obtained and calculated using a sample with a known molar ratio of hydroxy groups to carboxy groups. If the resin component containing hydroxy groups and carboxyl groups is a vinyl alcohol homopolymer with a degree of saponification of 98 mol% or more, and an acrylic acid homopolymer and/or a methacrylic acid homopolymer, the weight of each , the amount of hydroxy groups and the amount of carboxy groups can be calculated.

The total mass of hydroxy groups and carboxy groups in the resin component containing hydroxy groups and carboxy groups should be 30% by mass or more and 60% by mass or less from the viewpoint of water resistance, gas barrier properties, and scratch resistance of the coating film. is preferable, and more preferably 35% by mass or more and 55% by mass or less. However, the mass of the resin component containing the hydroxyl group and the carboxy group is 100% by mass. The carboxy group includes the above-mentioned carboxy group that has been neutralized to become a metal salt.

The total mass of hydroxy groups and carboxy groups contained in the resin component containing hydroxy groups and carboxy groups can be determined by a known NMR method, IR method, or the like. For example, in the case of the IR method, a calibration curve can be obtained and calculated using a polyol polymer with a known number of polyol units and a polycarboxylic acid polymer with a known number of polycarboxylic acid units. When using a vinyl alcohol homopolymer with a degree of saponification of 98 mol% or more and an acrylic acid homopolymer and/or a methacrylic acid homopolymer, calculate the mass of the hydroxy group and the mass of the carboxy group from the mass of each. The total amount can be used.

When resin A is a resin component containing a hydroxyl group and a carboxyl group, the first barrier layer may contain ammonium ions, alkali metal ions, or alkali It is preferable that earth metal ions are included. Examples of alkali metal ions include sodium ions, lithium ions, and potassium ions. Alkaline earth metal ions include calcium ions and magnesium ions.

When the first barrier layer contains ammonium ions, alkali metal ions, or alkaline earth metal ions, the content thereof is preferably 0.2 parts by mass or more and 5 parts by mass or less, and 0.2 parts by mass or more. More preferably, it is 2 parts by mass or less. However, the mass of the resin in the first barrier layer is 100 parts by mass.

The alkali metal ions are derived from an alkali metal ion donating compound, the ammonium ions are derived from an ammonium ion donating compound, and the alkaline earth metal ions are derived from an alkaline earth metal ion donating compound. When resin A is a resin component containing a hydroxyl group and a carboxy group, the first barrier layer preferably contains an ammonium ion donating compound, an alkali metal ion donating compound, or an alkaline earth metal ion donating compound.

Examples of ammonium ion donating compounds include ammonium hydroxide and ammonium chloride. Examples of the alkali metal ion donating compound include sodium hydroxide, sodium hypophosphite, lithium hydroxide, potassium hydroxide, and the like. Examples of alkaline earth metal ion donating compounds include calcium hydroxide, calcium chloride, magnesium hydroxide, magnesium chloride, and the like. These may be used alone or in combination of two or more types.

Montmorillonite, which is a type of inorganic layered compound, contains sodium ions between its layers, so it also acts as an alkali metal ion donating compound. Therefore, when resin A is a resin component containing a hydroxy group and a carboxy group, the below-mentioned inorganic layered compound contained in the first barrier layer is preferably montmorillonite.

In one embodiment of the present invention, the content of resin A is preferably 40 to 90% by mass, more preferably 45 to 85% by mass, even more preferably 50 to 80% by mass, based on the total mass of the first barrier layer. Mass%. When the content of resin A is within the above range, the adhesion to the base material increases and the gas barrier properties of the gas barrier laminate tend to improve.

In addition to resin A, the first barrier layer contains an inorganic layered compound. Therefore, the gas barrier laminate of the present invention can maintain high gas barrier properties under high humidity. Inorganic layered compounds can be used alone or in combination of two or more. In the present invention, an inorganic layered compound refers to an inorganic compound in which unit crystal layers are stacked on top of each other to form a layered structure. A layered structure is a structure in which atoms are strongly bonded by covalent bonds and arranged densely, and are stacked almost parallel to each other by weak bonding forces such as van der Waals.

Examples of the inorganic layered compound include clay minerals, and clay minerals can be used alone or in combination of two or more. Examples of clay minerals include kaolinite, dickite, nacrite, halloysite, antigorite, chrysotile, pyrophyllite, montmorillonite, beidellite, nontronite, saponite, sauconite, stevensite, hectorite, tetrasilylic mica, and sodium. Examples include taeniolite, muscovite, margarite, talc, vermiculite, phlogopite, xanthophyllite, chlorite, and hydrotalcite. The clay mineral may be one whose dispersibility has been improved by treatment with an organic substance (for example, ion exchange, etc.).

In one embodiment of the present invention, the inorganic layered compound is preferably a smectite group clay mineral from the viewpoint of having a high aspect ratio, easily improving gas barrier properties, and from the viewpoint of availability. Examples of the smectite clay mineral include montmorillonite, beidellite, nontronite, saponite, sauconite, stevensite, and hectorite, and among these, montmorillonite is more preferred.

In one embodiment of the present invention, the thickness of the unit crystal layer of the inorganic layered compound is preferably 0.5 to 3.0 nm, more preferably 0.8 to 2.0 nm, even more preferably 1.0 to 1.0 nm. It is 5 nm. The thickness of the unit crystal layer can be measured by powder X-ray diffraction method or the like.

In one 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 even 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 laminate with good gas barrier properties and transparency. The average particle diameter of the inorganic layered compound is a volume-based median diameter (D ₅₀ ), and can be measured using a laser diffraction scattering particle size distribution analyzer.

In one embodiment of the present invention, the aspect ratio of the inorganic layered compound (average particle size of the inorganic layered compound/thickness of the unit crystal layer of the inorganic layered compound) is preferably 50 to 5000, more preferably 100 to 4000, and further Preferably it is 200 to 3000. When the aspect ratio is equal to or higher than the above lower limit, gas barrier properties are easily improved. Moreover, when the aspect ratio is below the above upper limit, it is easy to improve manufacturability and economical efficiency.

In one embodiment of the present invention, the content of the inorganic layered compound in the first barrier layer is preferably 1 to 50% by mass, more preferably 5 to 50% by mass, based on the total mass of the first barrier layer. %, more preferably 10 to 45% by weight, even more preferably 15 to 40% by weight, particularly preferably 20 to 35% by weight. When the content of the inorganic layered compound in the first barrier layer is at least the above lower limit, gas barrier properties under high humidity can be easily improved, and when it is below the above upper limit, the peel strength of the gas barrier laminate can be improved. Cheap.

In one embodiment of the present invention, from the viewpoint of improving gas barrier properties under high humidity, when resin A is an amino group-containing resin, the first barrier layer contains amino groups in addition to resin A and the inorganic layered compound. It is preferable to further include a compound (hereinafter also referred to as "compound C") containing a reactive functional group and a silanol group. By including such a compound, the amino group-containing resin and the inorganic layered compound combine to reduce the swelling of the gas barrier layer under high humidity, which worsens the labyrinth effect of the first barrier layer even under high humidity. is less likely to occur, and gas barrier properties are easily maintained.

In one embodiment of the present invention, the functional group that reacts with the amino group contained in compound C is at least one selected from an epoxy group, an isocyanate group, a carboxylic acid anhydride group, a halogenated alkyl group, and a halogenated acyl group. It is preferable that there be.

Examples of compound C include 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, and 8-glycidoxypropylmethyldimethoxysilane. Epoxysilane coupling agents such as glycidoxyoctyltrimethoxysilane and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane; (3-isocyanatopropyl)triethoxysilane, (3-isocyanatopropyl)trimethoxysilane; Isocyanate silane coupling agents such as methoxysilane; [(3-trimethoxysilyl)propyl]succinic anhydride, [(3-triethoxysilyl)propyl]succinic anhydride, [(3-dimethylmethoxysilyl)propyl ] Silane coupling agents containing carboxylic anhydride groups such as succinic anhydride; (chloromethyl)trimethoxysilane, (chloromethyl)triethoxysilane, (3-chloropropyl)triethoxysilane, (3-bromopropyl) Examples include halogenated alkyl group-containing silane coupling agents such as trimethoxysilane and (3-iodopropyl)trimethoxysilane; and hydrolysates of other halogenated acyl group-containing silane coupling agents. These coupling agents can be used alone or in combination of two or more. Among these, it is preferable to use an epoxysilane coupling agent because of its high reactivity with amino groups.

In one embodiment of the present invention, the ratio of the functional group that reacts with the amino group contained in compound C to the amino group contained in the amino group-containing resin is from 0.2 to 1.2, more preferably from 0.2 to 1.2 in terms of molar equivalent. It is 0.2 to 1.0, more preferably 0.3 to 0.8. When the ratio is not less than the above lower limit and not more than the upper limit, the functional group that reacts with the amino group contained in the compound C and the amino group contained in the amino group-containing resin are bonded, and the effect of reducing swelling of the gas barrier layer is obtained. Easily improves gas barrier properties under high humidity conditions.

In one embodiment of the present invention, the ratio of silanol groups contained in compound C to hydroxy groups contained in the inorganic layered compound is from 0.5 to 2.9, more preferably from 0.5 to 2.9, in terms of molar equivalents. 5, more preferably 0.8 to 2.1. When the ratio is greater than or equal to the lower limit and less than or equal to the upper limit, the silanol group contained in compound C and the hydroxyl group contained in the inorganic layered compound combine to reduce the swelling of the gas barrier layer, thereby improving gas barrier properties under high humidity. Easy to improve.

Compound C may react with and bond to an amino group-containing resin, compound C may react with and bond to an inorganic layered compound, and compound C may react with and bond to an amino group-containing resin and an inorganic layered compound, respectively. You can. Therefore, in one embodiment of the present invention, the first barrier layer is a reaction product of compound C and an amino group-containing resin; a reaction product of compound C and an inorganic layered compound; a reaction product of compound C, an amino group-containing resin, and an inorganic layered compound; It may contain at least one member selected from the group consisting of reactants of compounds. In addition, when compound C reacts and bonds with the amino group-containing resin and the inorganic layered compound, the amino group-containing resin and the inorganic layered compound are bonded together via compound C, so the interlayer metal of the inorganic layered compound Swelling of the resin film due to coordination of water molecules to ions is structurally suppressed, and gas barrier properties under high humidity can be further improved.

The first barrier layer may further contain at least one additive selected from the group consisting of ultraviolet absorbers, antioxidants, surfactants, and rust preventives, within a range that does not impair the effects of the present invention. The additive is preferably a surfactant and/or a rust preventive from the viewpoint of easily improving gas barrier properties under high humidity.

Examples of the ultraviolet absorber include at least one compound selected from the group consisting of benzophenone compounds, salicylate compounds, benzotriazole compounds, and triazine compounds. The ultraviolet absorbers can be used alone or in combination of two or more. As used herein, the term "based compound" refers to a derivative of a compound to which the "based compound" is attached. For example, a "benzophenone compound" refers to a compound having benzophenone as a parent skeleton and a substituent bonded to benzophenone.

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

Examples of the surfactant include anionic surfactants, cationic surfactants, zwitterionic surfactants, and nonionic surfactants.

Examples of the rust preventive include azoles, inorganic acids, organic acids, and the like. The inorganic acid and the organic acid may each be a salt. Azoles include imidazole, benzimidazole, 2-mercaptobenzimidazole, benzotriazole and the like. Examples of inorganic acids include boric acid, nitrous acid, and phosphonic acid.

The total content of additives contained in the first barrier layer is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and further Preferably it is 0.1 to 15% by mass.

In one embodiment of the invention, the thickness of the first barrier layer is preferably from 0.001 to 10 μm, more preferably from 0.01 to 5 μm, even more preferably from 0.05 to 1 μm.

(Second barrier layer)
In one embodiment of the invention, the barrier layer preferably includes a second barrier layer between the first barrier layer and the substrate, ie on the substrate side of the barrier layer. By including the second barrier layer between the first barrier layer and the base material, gas barrier properties under high humidity can be easily improved.

The second barrier layer includes resin. The resin contained in the second barrier layer is not particularly limited, and may be the same as the resin contained in the first barrier layer, for example. The resin contained in the second barrier layer preferably contains the resin A described above from the viewpoint of gas barrier properties of the gas barrier laminate under high humidity and peel strength of the gas barrier laminate. Furthermore, the resin A contained in the second barrier layer should have at least one functional group selected from the group consisting of a hydroxy group and an amino group, from the viewpoint of improving gas barrier properties and film durability under high humidity. is preferable, and from the viewpoint of improving the peel strength of the gas barrier laminate, a resin containing an amino group (amino group-containing resin) is more preferable.

In one embodiment of the present invention, the amount of amino groups in the second barrier layer is preferably 0.3 mmol/g or more. By forming a second barrier layer with a high concentration of amino groups between the first barrier layer and the base material, the barrier layer and the base material can be bonded together while maintaining the gas barrier properties of the resulting gas barrier laminate under high humidity. It is possible to improve the adhesion (peel strength) between the barrier layer and the substrate, especially the adhesion between the barrier layer and the base material in the presence of water (water peel strength). This is considered to be because when the amino group concentration of the second barrier layer is high, the second barrier layer acts not only as a gas barrier layer but also as a primer layer.

The amount of amino groups in the second barrier layer is, for example, 0.3 to 10 mmol/g, preferably 0.5 to 10 mmol/g, more preferably 0.8 to 8.0 mmol/g, and even more preferably 1.0 -8.0 mmol/g, even more preferably 1.5-5.0 mmol/g, particularly preferably 1.8-5.0 mmol/g, particularly more preferably 2.0-3.0 mmol/g. When the amount of amino groups is within the above range, particularly above the lower limit, the amino groups in the second barrier layer and the functional groups such as carbonyl groups, aldehyde groups, carboxy groups, and ester groups that may exist on the surface of the substrate Since the reaction with the second barrier layer easily progresses and the adhesion or adhesion between the second barrier layer and the base material increases, it is easy to improve the gas barrier properties and water peel strength of the gas barrier laminate under high humidity.
The amount of amino groups in the second barrier layer is determined by the amount of amino groups (mmol/g) in the resin containing amino groups contained in the second barrier layer, the proportion of resin containing amino groups contained in the second barrier layer, etc. It can be adjusted by
The amount of amino groups (mmol/g) in the second barrier layer can be calculated by performing ¹ H NMR measurement of the amount (mmol/g) of amino groups in the amino group-containing resin contained in the second barrier layer. , for example, by the method described in Examples of International Publication No. 2023/042722.

In one embodiment of the present invention, the amount of amino groups (mmol/g) in the second barrier layer is preferably higher than the amount (mmol/g) of amino groups in the first barrier layer. When the amount of amino groups per gram of the second barrier layer is higher than the amount of amino groups per gram of the first barrier layer, gas barrier properties and water peel strength under high humidity are likely to be improved.

In one embodiment of the present invention, the second barrier layer preferably contains an amino group-containing resin. The amino group-containing resin is not particularly limited as long as it contains an amino group, and includes, for example, vinylamine-vinyl alcohol copolymer; polyethyleneimine; ethylenically unsaturated monomers such as vinylbenzene trimethylammonium chloride and aminoethyl acrylate hydrochloride. , di- or trialkylammonium salts, N-methylaminoethyl acrylate, N,N-dimethylaminoethyl methacrylate, N,N-dimethylaminomethyl-N-acrylamide, N,N-dimethylaminoethyl-N-acrylamide, etc. Examples include homopolymers and copolymers thereof. These amino group-containing resins can be used alone or in combination of two or more. Note that the amino group may be unsubstituted or substituted with an alkyl group or the like.

In one embodiment of the present invention, the amino group-containing resin preferably contains a resin containing a hydroxy group in addition to an amino group, and more preferably, from the viewpoint of easily improving gas barrier properties and water peel strength under high humidity. contains a vinyl alcohol resin containing an amino group, more preferably a vinylamine-vinyl alcohol copolymer. The vinylamine-vinyl alcohol copolymer may be a random copolymer or a block copolymer, but from the viewpoint of manufacturability and cost, a random copolymer is preferable.

In one embodiment of the present invention, the amount of amino groups in the resin containing hydroxy groups in addition to amino groups is preferably 0.3 to 10 mmol/g, more preferably 0.5 to 10 mmol/g, even more preferably 0.8 to 8.0 mmol/g, even more preferably 1.0 to 8.0 mmol/g, particularly preferably 1.5 to 5.0 mmol/g, particularly more preferably 1.8 to 5.0 mmol/g , particularly preferably 2.0 to 3.0 mmol/g. When the amount of amino groups is within the above range, particularly above the lower limit, it is easy to increase the amount of amino groups in the second barrier layer, and it is easy to improve the gas barrier properties and water peel strength of the gas barrier laminate under high humidity. . Note that the amount of amino groups in the resin can be measured by 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 1 to 50 mmol/g, more preferably 5 to 40 mmol/g, even more preferably 10 to 30 mmol/g. g, even more preferably 15 to 25 mmol/g. When the amount of hydroxyl groups is at least the above lower limit, a crystal structure is easily formed in the second barrier layer by hydrogen bonding, and gas barrier properties under high humidity are easily improved. When the amount of hydroxyl groups is below the above upper limit, it is easy to suppress a decrease in surface activity of the resin containing hydroxyl groups in addition to amino groups, and it is easy to improve compatibility with hydrophobic materials. Note that the amount of hydroxyl groups in the resin can be measured by ¹ H NMR measurement.

In one embodiment of the present invention, the degree of saponification of the vinyl alcohol resin containing amino groups is preferably from the viewpoint of easily increasing the crystallinity of the vinyl alcohol resin containing amino groups and improving gas barrier properties. It may be 80 to 100%, more preferably 90 to 100%, even more preferably 95 to 100%, particularly preferably 98 to 100%.

In one embodiment of the present invention, when the amino group-containing resin includes a resin containing hydroxy groups in addition to amino groups, the amount of hydroxy groups in addition to amino groups based on the total mass of the amino group-containing resin contained in the second barrier layer is The content of the group-containing resin is preferably 60 to 100% by mass, more preferably 80 to 100% by mass, and still more preferably 90 to 100% by mass, from the viewpoint of easily improving gas barrier properties and water peel strength under high humidity. 100% by weight, even more preferably 95-100% by weight, particularly preferably 99-100% by weight.

In one embodiment of the present invention, the amino group-containing resin may include a resin that contains an amino group and does not contain a hydroxy group, from the viewpoint of easily improving the peel strength, particularly the water-wet peel strength. A resin containing an amino group but not containing a hydroxyl group is a resin that has at least one of a primary amine, a secondary amine, or a tertiary amine in the main chain, side chain, or terminal, and has a hydroxyl group. Examples of such resins include polyethyleneimine, polyvinylamine, polyallylamine, polydiallylamine, polyvinylamidine, and polylysine. Among these resins, polyethyleneimine and polydiallylamine, which are classified as main chain amines, and polyvinylamine and polyallylamine, which are classified as side chain amines, are preferred. Among these resins, polyethyleneimine, polyvinylamine, and polyallylamine are preferred from the viewpoint of availability.

In one embodiment of the present invention, the amount of amino groups in the resin containing amino groups but not containing hydroxy groups is preferably 0.3 to 10 mmol/g, more preferably 0.5 to 10 mmol/g, and even more preferably is 0.8 to 8.0 mmol/g, even more preferably 1.0 to 8.0 mmol/g, particularly preferably 1.5 to 5.0 mmol/g, particularly more preferably 1.8 to 5.0 mmol/g. g, particularly preferably 2.0 to 3.0 mmol/g. When the amount of amino groups is within the above range, particularly above the lower limit, it is easy to increase the amount of amino groups in the second barrier layer, and it is easy to improve the gas barrier properties and water peel strength of the gas barrier laminate under high humidity. .

In one embodiment of the present invention, when the amino group-containing resin contains an amino group-free resin, the amino group-containing resin contains an amino group-containing resin with respect to the total mass of the amino group-containing resin contained in the second barrier layer. The content of the resin that does not contain groups is preferably 5 to 99% by mass, more preferably 10 to 99% by mass, and even more preferably 20 to 80% by mass, from the viewpoint of easily improving peel strength, especially water-wet peel strength. , particularly preferably 50 to 60% by mass.

In one embodiment of the present invention, the amino group-containing resin contained in the second barrier layer includes both a resin containing a hydroxy group in addition to an amino group and a resin containing an amino group but not containing a hydroxy group. may also include only one of them. When the amino group-containing resin contains both a resin containing a hydroxy group in addition to an amino group and a resin containing an amino group but not a hydroxy group, the content ratio [resin containing a hydroxy group in addition to an amino group] : [Resin containing an amino group and not containing a hydroxyl group] (mass ratio) is preferably 99:1 to 1:99, more preferably 80:20 to 20:80, even more preferably 70:30 to 30: It may be 70.

In one embodiment of the present invention, the number average molecular weight of the amino group-containing resin is preferably 5,000 or more and 100,000 or less, more preferably 10,000 or more and 50,000 or less, even more preferably 12,000 or more and 40,000 or more, 000 or less, and even more preferably 15,000 or more and 30,000 or less. The number average molecular weight of the amino group-containing resin can be measured by gel permeation chromatography (GPC).

In one embodiment of the present invention, the amount of amino groups in the entire amino group-containing resin contained in the second barrier layer is preferably 0.3 to 10 mmol/g, more preferably 0.5 to 10 mmol/g, and even more preferably is 0.8 to 8.0 mmol/g, even more preferably 1.0 to 8.0 mmol/g, particularly preferably 1.5 to 5.0 mmol/g, particularly more preferably 1.8 to 5.0 mmol/g. g, particularly preferably 2.0 to 3.0 mmol/g. When the amount of amino groups is within the above range, particularly above the lower limit, it is easy to increase the amount of amino groups in the second barrier layer, and it is easy to improve the gas barrier properties and water peel strength of the gas barrier laminate under high humidity. .

In one embodiment of the present invention, the content of the amino group-containing resin in the second barrier layer is preferably 20 to 100% by mass, more preferably 50 to 100% by mass, based on the total mass of the second barrier layer. % by weight, more preferably 65-100% by weight, even more preferably 80-100% by weight, particularly preferably 90-100% by weight.

In one embodiment of the present invention, the resin A contained in the first barrier 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 second barrier layer. It is preferable to include. For example, when the amino group-containing resin contained in the second barrier layer is a vinylamine-vinyl alcohol copolymer and the resin A contained in the first barrier layer is polyvinyl alcohol, the polyvinyl alcohol is a vinylamine-vinyl alcohol copolymer. Since it contains a vinyl alcohol unit that is one of the vinyl amine units and vinyl alcohol units that constitute the copolymer, the polyvinyl alcohol contained in the first barrier layer is different from the vinyl amine-vinyl alcohol contained in the second barrier layer. It can be said that it contains a structural unit having the same structure as at least one of the structural units constituting the copolymer. When resin A contained in the first barrier layer contains a constitutional unit having the same structure as at least one of the constitutional units constituting the amino group-containing resin contained in the second barrier layer, the resin A constitutes the second barrier layer. The compatibility between the amino group-containing resin and the resin A constituting the first barrier layer increases, making it difficult to form an interface between the first barrier layer and the second barrier layer, resulting in high humidity in the gas barrier laminate. It is easy to improve the gas barrier properties and water peel strength underneath.
In one embodiment of the present invention, from the viewpoint of easily improving gas barrier properties and water peel strength under high humidity, the amino group-containing resin contained in the second barrier layer and the resin A contained in the first barrier layer are It is preferable that the amino group-containing resin contained in the second barrier layer and the resin A contained in the first barrier layer both contain a vinyl alcohol resin containing at least a vinyl alcohol unit as a constituent unit. It is more preferable that

In one embodiment of the present invention, the second barrier layer may contain a resin that does not contain an amino group (an amino group-free resin) in addition to the amino group-containing resin. Examples of the amino group-free resin that can be included in the second barrier layer include vinyl alcohol-based resins that do not contain amino groups, such as polyvinyl alcohol, (meth)acrylic acid-vinyl alcohol copolymer, and ethylene-vinyl alcohol copolymer. Examples include resin. These resins may be used alone or in combination of two or more. Among these resins, the amino group-free resin is preferably a resin containing a hydroxy group but not an amino group, more preferably a vinyl alcohol resin that does not contain an amino group, and even 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 1 to 50 mmol/g, more preferably 5 to 40 mmol/g, even more preferably 10 to 30 mmol/g. g, even more preferably 15 to 25 mmol/g. When the amount of hydroxyl groups is at least the above lower limit, a crystal structure is easily formed in the second barrier layer by hydrogen bonding, and gas barrier properties under high humidity are easily improved.
Moreover, when the amount of hydroxyl groups is below the above upper limit, it is easy to suppress a decrease in surface activity, and it is easy to increase compatibility with a hydrophobic material.

In one embodiment of the present invention, the degree of saponification of the vinyl alcohol resin that does not contain amino groups is preferably 80% or more, more preferably 90 to 100%, even more preferably 95 to 100%, particularly preferably 98 to 100%. It may be %.

In one embodiment of the present invention, the number average molecular weight of the amino group-free resin is preferably 10,000 or more and 150,000 or less, more preferably 30,000 or more and 100,000 or less, and still more preferably 50,000 or more and 70,000 or more. ,000 or less. The number average molecular weight of the amino group-free resin can be measured by gel permeation chromatography (GPC).

In one embodiment of the present invention, the total amount of resin (amino group-containing resin and optional amino group-free resin) contained in the second barrier layer is preferably based on the total mass of the second barrier layer. is 50 to 100% by weight, more preferably 60 to 100% by weight, even more preferably 70 to 100% by weight, even more preferably 80 to 100% by weight, particularly preferably 90 to 100% by weight.

In one embodiment of the present invention, the content of the amino group-containing resin in the resin included in the second barrier layer is preferably 20 to 100 mass based on the total mass of the resin included in the second barrier layer. %, more preferably 50 to 100% by weight, still more preferably 70 to 100% by weight, even more preferably 80 to 100% by weight, particularly preferably 90 to 100% by weight.

In one embodiment of the present invention, the amount of amino groups in the resin contained in the second barrier layer is preferably 0.5 to 10 mmol/g, more preferably 0.8 to 10 mmol/g, even more preferably 1. 0 to 8.0 mmol/g, even more preferably 1.5 to 8.0 mmol/g, particularly preferably 1.8 to 5.0 mmol/g, particularly more preferably 2.0 to 3.0 mmol/g . When the amount of amino groups is within the above range, particularly above the lower limit, it is easy to increase the amount of amino groups in the second barrier layer, and it is easy to improve the gas barrier properties and water peel strength of the gas barrier laminate under high humidity. .

In one embodiment of the present invention, the second barrier layer may further contain an inorganic layered compound from the viewpoint of easily improving gas barrier properties under high humidity. The inorganic layered compound that may be included in the second barrier layer is not particularly limited, and may be the same as the inorganic layered compound included in the first barrier layer, including preferred embodiments.

In one embodiment of the present invention, the content of the inorganic layered compound in the second barrier layer is preferably set relative to the total mass of the second barrier layer from the viewpoint of easily improving gas barrier properties under high humidity. is 0.1 to 50% by weight, more preferably 1 to 50% by weight, even more preferably 5 to 35% by weight, even more preferably 10 to 35% by weight, particularly preferably 15% to 20% by weight. good.
In one embodiment of the present invention, the content of the inorganic layered compound in the second barrier layer is preferably set relative to the total mass of the second barrier layer from the viewpoint of easily improving the water peel strength. is 0 to 50% by mass, more preferably 0 to 35% by mass, even more preferably 0 to 20% by mass, even more preferably 0 to 10% by mass, particularly preferably 0 to 5% by mass, particularly more preferably 0 to 35% by mass. 1% by weight, and the second barrier layer may be substantially free of inorganic layered compounds.

In one embodiment of the present invention, the second barrier layer may further include at least one additive selected from the group consisting of a crosslinker, a UV absorber, an antioxidant, a surfactant, and a rust inhibitor. . The additive is preferably a crosslinking agent, a surfactant, and/or a rust inhibitor, and more preferably contains at least a crosslinking agent, from the viewpoint of easily improving gas barrier properties and water peel strength.

The crosslinking agent may be an organic crosslinking agent or an inorganic crosslinking agent, but is preferably an organic crosslinking agent. As the organic crosslinking agent, a polyfunctional monomer having a functional group that can react with the amino group of the amino group-containing resin and/or the hydroxy group optionally contained in the amino group-containing resin, such as an epoxy group, a vinyl group, (meth) Examples include polyfunctional monomers having at least two functional groups selected from the group consisting of an acrylic group, an aldehyde group, an isocyanate group, and/or an allyl group. Examples of the polyfunctional monomer include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, resorcinol diglycidyl ether, 1,6-hexanediol diglycidyl ether, sorbitol polyglycidyl ether, and glycerol polyglycidyl ether. Compounds with epoxy groups such as ether, diglycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, and pentaerythritol 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-decane Compounds with (meth)acrylic groups such as diol dimethacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, and cyanoethyl acrylate; compounds with allyl groups such as 1,2,4-trialyl trimellitate and triallyl isocyanurate. Examples include compounds that have These crosslinking agents may be used alone or in combination of two or more. Among these crosslinking agents, the crosslinking agent is preferably a compound having an epoxy group, more preferably a bifunctional epoxy compound, a polyfunctional (trifunctional or more) epoxy compound, and even more preferably a bifunctional epoxy compound.

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

The content of the crosslinking agent in the second barrier layer is preferably 0.5 to 30% by mass, more preferably 0.5 to 30% by mass, based on the total mass of the second barrier layer, from the viewpoint of easily improving the water peel strength. The amount is 1 to 30% by weight, more preferably 3 to 20% by weight, even more preferably 5 to 20% by weight, particularly preferably 8 to 15% by weight.

Examples of the ultraviolet absorber, antioxidant, rust preventive, and surfactant include those that can be included in the first barrier layer, and preferred embodiments include those that can be included in the first barrier layer. The same is true.

In one embodiment of the present invention, the total amount of additives contained in the second barrier layer is preferably 0.1 to 30% by mass, more preferably 1 to 20% by mass, based on the total mass of the second barrier layer. % by weight, more preferably from 5 to 15% by weight.

In one embodiment of the present invention, the amount of sodium (Na) in the second barrier layer is preferably 0 to 2500 ppm, more preferably 0 to 1500 ppm, even more preferably It may be 0 to 1000 ppm. When the amount of Na in the second barrier layer is below the above upper limit, it is easy to obtain a gas barrier laminate having excellent gas barrier properties. The amount of Na in the second barrier layer can be adjusted by adjusting the amount of Na in the coating solution forming the second barrier layer. For example, the amount of Na in the coating solution can be reduced by cation exchange treatment or the like. Further, the amount of Na in the second barrier layer can be measured by inductively coupled plasma emission spectrometry using an ICP emission spectrometer.

In one embodiment of the invention, the thickness of the second barrier layer is preferably 0.001 to 20 μm, more preferably 0.01 to 10 μm, even more preferably 0.05 to 5 μm, even more preferably 0.01 to 20 μm. 08 to 3 μm.

In one embodiment of the invention, the thickness of the second barrier layer is preferably greater than the thickness of the first barrier layer.

In one embodiment of the invention, the thickness of the barrier layer (total thickness of the first barrier layer and optionally included second barrier layer) is preferably 0.001 to 20 μm, more preferably 0.001 to 20 μm. 01 to 10 μm, more preferably 0.05 to 5 μm, even more preferably 0.08 to 3 μm.

<Sealant layer>
The gas barrier laminate of the present invention includes a sealant layer containing a thermoplastic resin having heat sealability. Thermoplastic resins with heat sealing properties include polyethylene (low density, high density), ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-hexene copolymer, ethylene-4-methyl-1-pentene. Copolymers, ethylene-octene copolymers, polypropylene, ethylene-vinyl acetate copolymers, ethylene-methyl methacrylate copolymers, ethylene-methyl acrylate copolymers, ethylene-acrylic acid copolymers, ionomer resins, etc. polyolefin resins; polyacrylonitrile resins (PAN); polyester resins; ethylene-vinyl alcohol copolymers; metallocenes; and higher fatty acid polyolefins (HAO). These resins can be used alone or in combination of two or more. Among these, polyolefin is preferred, and polyethylene and polypropylene are more preferred.

In one embodiment of the invention, the thickness of the sealant layer is preferably between 5 and 100 μm, more preferably between 10 and 80 μm, even more preferably between 15 and 70 μm.

<Gas barrier laminate>
The gas barrier laminate of the present invention includes a base material, a barrier layer, and a sealant layer in this order, and the barrier layer includes a first barrier layer and optionally a second barrier layer.

In one embodiment of the present invention, other layers such as an anchor layer and a sealing layer may be present between the base material, barrier layer, and sealant layer. For example, an anchor layer may be included between the base material and the barrier layer and/or between the barrier layer and the sealant layer, and a sealant may be included between the base material (particularly the paper base material) and the barrier layer. layers may be included.

The anchor layer is not particularly limited as long as it can improve the adhesiveness between the base material and the barrier layer and/or the adhesiveness between the barrier layer and the sealant layer. For example, the anchor layer can be formed using various compounds (anchor coating agents) such as polyethyleneimine compounds, polyolefin compounds, alkyl titanate compounds, polybutadiene compounds, and urethane compounds. From this point of view, those obtained by reacting an isocyanate compound with an active hydrogen compound are preferred.

Examples of the isocyanate compound include tolylene diisocyanate (TDI), 4,4'-diphenylmethane diisocyanate (MDI), xylylene diisocyanate (XDI), hexamethylene diisocyanate (HDI), and 4,4'-methylenebiscyclohexyl isocyanate (H12MDI). ), isophorone diisocyanate (IPDI), and the like.

Examples of active hydrogen compounds include low molecular weight polyols such as ethylene glycol, diethylene glycol, dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, and trimethylolpropane; polyethylene glycol, polyoxypropylene Polyether polyols such as glycol, ethylene oxide/propylene oxide copolymers, polytetramethylene ether glycol; polyester polyols such as poly-β-methyl-δ-valerolactone, polycaprolactone, polyesters from diols/diacids; etc. Can be mentioned.

As the active hydrogen compound, low molecular weight polyols are particularly preferred, and among them, diols are more preferred. Here, diols include ethylene glycol, diethylene glycol, dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, etc., and dibasic acids include adipic acid, azelaic acid, and sebacic acid. , isophthalic acid, terephthalic acid and the like. Other polyols include active hydrogen compounds such as castor oil, liquid polybutadiene, epoxy resin, polycarbonate diol, acrylic polyol, and neoprene.

The mixing ratio of the isocyanate compound and the active hydrogen compound is not particularly limited, but is preferably determined in consideration of the equivalence relationship between the isocyanate group and the active hydrogen group, such as -OH group, -NH group, -COOH group. . For example, if the number of moles of the isocyanate group is AN and the number of moles of the active hydrogen group of the active hydrogen compound is BN, then the ratio R of the number of moles of the isocyanate group to the number of moles of the active hydrogen group (R=AN/BN) is: It is preferably 0.001 or more from the viewpoint of adhesive strength, and preferably 10 or less from the viewpoint of adhesiveness and blocking. It is more preferable that the ratio R of the number of moles is within the range of 0.01 or more and 1 or less. The number of moles of isocyanate groups and active hydrogen groups can be determined by ¹ H-NMR and ¹³ C-NMR.

The thickness of the anchor layer is not particularly limited, and may be preferably 0.01 to 5 μm, more preferably 0.03 to 2.0 μm, and still more preferably 0.05 to 1.0 μm.

The sealing layer is not particularly limited as long as it can improve the adhesion between the base material, especially the paper base material, and the barrier layer. Examples of binder resins included in the sealing layer include various copolymers such as styrene/butadiene, styrene/acrylic, ethylene/vinyl acetate, polyvinyl alcohol resin, cellulose resin, and paraffin (WAX). Can be mentioned. Among these, hydroxyl group-containing resins such as polyvinyl alcohol resins are preferred.

The hydroxyl group-containing resin such as polyvinyl alcohol resin may be completely saponified polyvinyl alcohol, partially saponified polyvinyl alcohol, ethylene copolymerized polyvinyl alcohol, etc., and has a functional group other than hydroxy group in addition to a hydroxy group. It may also be a polyvinyl alcohol derivative. Examples of functional groups other than hydroxy groups include carboxy groups, amino groups, thiol groups, sulfonic acid groups, phosphoric acid groups, carboxylate groups, sulfonate ion groups, phosphate ion groups, ammonium groups, phosphonium groups, silyl groups, Examples include a siloxy group, an allyl group, a fluoroalkyl group, an alkoxy group, a carbonyl group, and a halogen group. A portion of the hydroxyl groups in polyvinyl alcohol may be replaced with one or more of the above functional groups.

The thickness of the sealing layer is not particularly limited, and may be preferably 1 to 20 μm, more preferably 2 to 15 μm, and still more preferably 3 to 10 μm.

In one preferred embodiment of the invention, the barrier layer and the sealant layer are preferably in direct contact. Direct contact between the barrier layer and the sealant layer eliminates the need for an anchor layer or sealing layer. In a more preferred embodiment of the present invention, when the barrier layer and the sealant layer are in direct contact with each other, the barrier layer In particular, the resin contained in the first barrier layer that is in direct contact with the sealant layer is preferably an amino group-containing resin. The sealant layer is hydrophobic, such as polyolefin, as described above. However, when a gas barrier laminate is manufactured by a method that includes a step of directly laminating a sealant layer on a barrier layer by extrusion lamination or hot roll lamination as described below, the surface of the sealant layer is damaged due to the high temperature in extrusion lamination or hot roll lamination. It is oxidized and imparts hydrophilic functional groups to the surface of the sealant layer. In this case, it is considered that the adhesive strength between the barrier layer and the sealant layer can be increased due to the interaction between the hydrophilic functional groups on the surface of the sealant layer and the amino groups of the barrier layer.

In a preferred embodiment of the present invention in which the barrier layer and the sealant layer are in direct contact, the laminated structure of the gas barrier laminate of the present invention includes, for example, "base material/first barrier layer/sealant layer", "base material /second barrier layer/first barrier layer/sealant layer", "base material/anchor layer or sealing layer/first barrier layer/sealant layer", "base material/anchor layer or sealing layer/first 2 barrier layer/first barrier layer/sealant layer" and the like. Each layer and base material may each be a single layer or two or more layers, but a single layer is preferable. In this specification, "substrate/first barrier layer" refers to an embodiment in which the substrate and the first barrier layer are in direct contact. The same applies to other expressions. In addition, in this specification, "anchor layer or sealing layer" is preferably a sealing layer when the base material is a paper base material, and an anchor layer when the base material is other than a paper base material. .

In another preferred embodiment of the present invention, it is preferable to include a second barrier layer between the first barrier layer and the base material. /second barrier layer/first barrier layer/sealant layer", "base material/anchor layer or sealing layer/second barrier layer/first barrier layer/sealant layer", "base material/second barrier layer/first barrier layer/anchor layer/sealant layer", "base material/anchor layer or filler layer/second barrier layer/first barrier layer/anchor layer/sealant layer", etc. . Each layer and base material may each be a single layer or two or more layers, but a single layer is preferable.

Further, in an embodiment of the present invention, the gas barrier laminate of the present invention includes, for example, "base material/first barrier layer/anchor layer/sealant layer", "base material/anchor layer or sealing layer/first It may have a laminated structure such as "barrier layer/anchor layer/sealant layer". Each layer and base material may each be a single layer or two or more layers, but a single layer is preferable.

In one embodiment of the present invention, the thickness of the gas barrier laminate of the present invention is preferably 30 to 1200 μm, more preferably 40 to 500 μm, even more preferably 50 to 120 μm.

The gas barrier laminate of the present invention has good gas barrier properties under high humidity. In one embodiment of the present invention, the oxygen permeability of the gas barrier laminate of the present invention, measured based on JIS K7126-2-2006 at a temperature of 23°C and a relative humidity of 65% RH, is preferably 0 to 50 cc/ (m ² ·day · atm), more preferably 0 to 20 cc/(m ² ·day · atm), even more preferably 0 to 10 cc/(m ² ·day · atm), even more preferably 0 to 6 cc/(m 2 ·day · atm) ²・day・atm), more preferably 0 to 4cc/(m ²・day・atm), even more preferably 0 to 2cc/(m ²・day・atm), particularly preferably 0 to 1cc/(m ²・day・atm). The lower the oxygen permeability, the better the gas barrier properties of the gas barrier laminate.

The peel strength (laminate strength) of the gas barrier laminate of the present invention is preferably 0.1 to 10 N/15 mm, more preferably 0.5 to 10 N/15 mm, still more preferably 1 to 10 N/15 mm, even more preferably 2 ~10N/15mm, particularly preferably 3~10N/15mm, particularly more preferably 4~10N/15mm. The peel strength can be measured according to the test method specified in JIS-K6854-3:1999 "Adhesives - Peel adhesive strength test method - Part 3: T-type peel", for example, measured by the method described in Examples can.

[Method for manufacturing gas barrier laminate]
The gas barrier laminate of the present invention is not particularly limited and can be manufactured by a known method, but in a preferred embodiment of the present invention, the gas barrier laminate of the present invention is formed on a barrier layer by extrusion lamination or hot roll lamination. It can be manufactured by a method including a step of directly or indirectly laminating a sealant layer.

The method for producing a gas barrier laminate of the present invention includes, before the step of directly or indirectly laminating a sealant layer on the barrier layer, laminating a barrier layer on the base material and optionally an anchor layer or a sealing layer, The method may include a step of obtaining a gas barrier laminate precursor including a base material, a barrier layer, and optionally an anchor layer and a sealing layer. Examples of the laminate structure of the gas barrier laminate precursor include "base material/barrier layer", "base material/anchor layer or sealing layer/barrier layer", and "base material/anchor layer or sealing layer/barrier layer/anchor". "layer" and "substrate/barrier layer/anchor layer", etc., and even if the barrier layer contains only the first barrier layer, it may contain both the first barrier layer and the second barrier layer. You can stay there.

The method of laminating the barrier layer, anchor layer, and/or filler layer on the base material is not particularly limited, and for example, a coating liquid that can form a barrier layer, anchor layer, and/or filler layer on the base material may be used. By applying and drying the applied layer, a coating film of a barrier layer, an anchor layer, and/or a sealing layer can be formed and laminated. In addition, when the barrier layer includes a second barrier layer, a coating solution capable of forming the first barrier layer is applied onto the second barrier layer formed on the base material, and the coating layer is dried. By this, the first barrier layer can be formed on the second barrier layer. Similarly, when a barrier layer is laminated on an anchor layer or a sealing layer, a coating liquid capable of forming a barrier layer is applied to the anchor layer or a sealing layer, and when an anchor layer is laminated on a barrier layer, Each layer can be formed by applying a coating liquid capable of forming an anchor layer to the barrier layer and drying it.

Each coating liquid contains a liquid medium in addition to the components contained in each of the barrier layer, anchor layer, and sealing layer. Regarding components other than the liquid medium contained in each coating liquid, the description regarding each component contained in each layer similarly applies. For example, the coating liquid that can form the first barrier layer includes a resin, an inorganic layered compound, a liquid medium, and optionally a compound containing a functional group that reacts with an amino group and a silanol group and an additive. Regarding the resin, the inorganic layered compound, the compound containing a functional group that reacts with an amino group and a silanol group, and the additive, the description regarding each component in the section (first barrier layer) is the same. This applies to

The liquid medium preferably includes water and a liquid organic medium. As used herein, the term "liquid medium" refers to a medium that is liquid at 25°C and 1 atm, and the term "liquid organic medium" refers to an organic compound that is liquid at 25°C and 1 atm.

Examples of the liquid organic medium include monohydric alcohol, glycol, dimethylformamide, dimethyl sulfoxide, and acetone. The liquid organic medium can be used alone or in combination of two or more. Examples of the monohydric alcohol include methanol, ethanol, 1-propanol, 2-propanol, and 1-butanol.

When the liquid medium contains a liquid organic medium, the content of the liquid organic medium is preferably 1 to 70 parts by weight, more preferably 5 to 60 parts by weight, and even more preferably 10 parts by weight, based on 100 parts by weight of the liquid medium. ~50 parts by mass.

The liquid medium preferably contains water and at least one monohydric alcohol selected from the group consisting of methanol, ethanol, 1-propanol, 2-propanol and 1-butanol, and preferably contains water and ethanol. More preferred. When the liquid medium contains water and a monohydric alcohol, the total amount of the monohydric alcohol contained in the liquid medium is preferably per 100 parts by mass of the liquid medium from the viewpoint of stability of the coating liquid and drying time of the coating film. The amount is 1 to 70 parts by weight, more preferably 5 to 60 parts by weight, and even more preferably 10 to 50 parts by weight.

The content of the liquid medium is preferably 90 to 99.5% by weight, more preferably 91 to 99% by weight, even more preferably 92 to 98% by weight, based on the total weight of the coating liquid. Therefore, the solid content of the coating liquid is preferably 0.5 to 10% by weight, more preferably 1 to 9% by weight, and even more preferably 2 to 8% by weight, based on the total weight of the coating liquid. When the content of the liquid medium and the solid content of the coating liquid are within the above ranges, gas barrier properties and film forming properties under high humidity can be easily improved.

Each coating solution contains components such as a resin, an inorganic layered compound, and a liquid medium in the case of the coating solution for the first barrier layer, and optionally a functional group that reacts with an amino group and a silanol. It can be prepared by mixing and stirring a compound containing a group and an additive. The mixing order and mixing method of each component are not particularly limited, and can be prepared, for example, by the following methods (1) to (3).
(1) A method in which a resin solution is produced by mixing a resin and a liquid medium, stirring while heating, adding an inorganic layered compound or additive to the obtained resin solution, and stirring the obtained dispersion. (2) When containing an inorganic layered compound and/or additive, prepare a dispersion containing the inorganic layered compound and/or additive by mixing the inorganic layered compound and/or additive with a liquid medium and stirring. A method of mixing and stirring the obtained dispersion and a resin solution separately prepared in the same manner as the above method (1).
(3) When containing an inorganic layered compound and/or an additive, prepare a dispersion containing the inorganic layered compound and/or additive in the same manner as in method (2) above, and add a resin to the resulting dispersion. , a method in which the resin is dissolved in the liquid medium in the dispersion by stirring while heating.

The temperature when dissolving the resin in the liquid medium or the liquid medium in the dispersion containing the inorganic layered compound and/or additives is preferably 50 to 100°C, more preferably 60 to 100°C, and the stirring speed is preferably 300 to 5,000 rpm, 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 is 10 to 120 minutes, more preferably 20 to 110 minutes.

The temperature when dispersing the inorganic layered compound and/or additive in the liquid medium or resin solution is preferably 20 to 100°C, more preferably 30 to 80°C, and the stirring speed is preferably 500 to 50°C. ,000 rpm, more preferably 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.

When the 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 containing the inorganic layered compound using a high-pressure dispersion device. Examples of the high-pressure dispersion treatment include an ultra-high-pressure homogenizer manufactured by Microfluidics Corporation, a Nanomizer manufactured by Nanomizer, a Manton-Gorlin type high-pressure dispersion device, and a homogenizer manufactured by Izumi Food Machinery. Here, the high-pressure dispersion treatment is a treatment in which high shear and/or high pressure is applied to the dispersion liquid by passing the dispersion liquid through a plurality of thin tubes at high speed.

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

In preparing the coating liquid, it is preferable to perform a cation exchange treatment to reduce the amount of Na in the coating liquid. Cation exchange treatment can be performed using a cation exchange resin.

Examples of the cation exchange resin include resins into which a functional group having cation exchange ability is introduced. Cation exchange resins can be classified according to the acidity of their functional groups. Specifically, cation exchange resins can be classified into strongly acidic cation exchange resins having a sulfo 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 into which a functional group having cation exchange ability is introduced include styrene resins, acrylic resins, methacrylic resins, and the like. Furthermore, cation exchange resins are classified into gel type and macroporous type depending on the resin structure such as degree of crosslinking and porosity. The cation exchange resin that can be used in preparing the coating solution is not particularly limited, and commercially available products may be used. Commercially available products include, for example, "Duolite C255LFH" manufactured by Rohm and Haas, "Diaion SK1B" manufactured by Mitsubishi Chemical, and "Amberlite IR120B" manufactured by Dow Chemical. The amount of cation exchange resin used and the time of cation exchange treatment can be adjusted as appropriate depending on the target amount of Na.

The method of applying the coating liquid is not particularly limited, and may be a batch method or a continuous method, such as gravure methods such as direct gravure method and reverse gravure method, and two-roll beat coating. method, roll coating method such as bottom feed 3-line reverse coating method, doctor knife method, die coating method, bar coating method, dipping method, spray coating method, curtain coating method, spin coating method, flexo coating method, screen coating method, brush coating method Alternatively, a method using a brush may be mentioned.

The method of drying the coating film formed by applying the coating liquid is not particularly limited, but it is preferably carried out by heating using a drying oven or heater. The drying temperature is preferably 50 to 150°C, more preferably 60 to 150°C, and even 70 to 140°C, and the drying time is preferably 0.1 to 120 seconds, more preferably 0.2 to 100 seconds. More preferably, the time is 0.5 to 70 seconds. The drying is preferably carried out in an atmospheric atmosphere at normal pressure.

The method for manufacturing a gas barrier laminate of the present invention includes the step of laminating a sealant layer directly or indirectly on a barrier layer by extrusion lamination or hot roll lamination. More specifically, the method for producing a gas barrier laminate of the present invention includes a gas barrier laminate precursor in which a barrier layer and optionally an anchor layer or a filler layer are laminated on a base material by extrusion lamination or hot roll lamination. It is preferable to include a step of laminating a sealant layer directly or indirectly on the first barrier layer on the barrier layer side (that is, the surface opposite to the base material) via an anchor layer or the like.

In one embodiment of the present invention, the method for producing a gas barrier laminate of the present invention preferably includes the step of laminating a sealant layer directly on the barrier layer by extrusion lamination or hot roll lamination. Moreover, it is preferable that the resin contained in the barrier layer with which the sealant layer is in direct contact, that is, the first barrier layer, contains an amino group-containing resin. In the manufacturing method of the present invention, the surface of the sealant layer is oxidized by heating during extrusion lamination or thermal lamination, and hydrophilic functional groups are generated on the surface of the sealant layer. Therefore, when the first barrier layer contains an amino group-containing resin according to the manufacturing method of the present invention, the barrier The adhesive strength between the sealant layer and the sealant layer can be increased, and a gas barrier laminate having high peel strength can be obtained without including an anchor layer or the like.

The extrusion device for extrusion laminate used in extrusion laminate is not particularly limited, and for example, a conventionally known extrusion device equipped with an extrusion die and/or a die such as a T-die can be used.

The extrusion resin temperature in extrusion lamination is not particularly limited and may be set as appropriate, for example, from 200 to 400°C, preferably from 230 to 370°C, more preferably from 250 to 350°C.

The roll temperature of the hot roll laminate is not particularly limited and may be set as appropriate, for example, from 100 to 450°C, preferably from 120 to 300°C, more preferably from 140 to 220°C.

EXAMPLES Hereinafter, the present invention will be described in more detail based on Examples and Comparative Examples, but the present invention is not limited to the following Examples.

[Preparation of coating liquid]
(1) Coating liquid (1)
NVF (vinylamine-vinyl alcohol copolymer, "Selvol Ultiloc 5003" (trade name) manufactured by Sekisui Specialty Chemicals America, LLC) was prepared by a method according to paragraphs [0092] to [0096] of JP-A-2023-101229. , random copolymer, amount of amino groups in NVF: 2.3 mmol/g, amount of hydroxyl groups in NVF: 20 mmol/g, number average molecular weight: 20,000, degree of saponification: 99.0%), high purity Montmorillonite (Kunipia G (trade name) manufactured by Kunimine Industries, unit crystal layer thickness a: 1.2156 nm, average particle size: 560 nm, aspect ratio: 460), ion exchange water (specific electrical conductivity: 0. 7 μs/cm or less) and ethanol was prepared.

(2) Coating liquid (2)
A coating liquid (2) containing NVF, high-purity montmorillonite, ion-exchanged water, ethanol, and 3-glycidoxypropyltrimethoxysilane was prepared by a method according to paragraph [0098] of JP-A-2023-101229.

(3) Coating liquid (3)
Coating liquid (3) containing polyvinyl alcohol, polyacrylic acid, high purity montmorillonite, nonionic surfactant, ion exchange water and isopropanol was prepared by a method according to paragraph [0150] of International Publication No. 2017/038456. did.

(4) Coating liquid (4)
A coating liquid (4) containing NVF, ion-exchanged water, and ethanol was prepared by a method according to paragraph [0118] of International Publication No. 2023/042722.

(5) Coating liquid (5)
Coating solution (4) was prepared in the same manner as coating solution (4), except that fully saponified polyvinyl alcohol (PVA117, manufactured by Kuraray Co., Ltd.) was used instead of NVF. ) was prepared.

(6) Preparation of coating liquid (6) Coating liquid (4) was prepared with the exception that partially saponified polyvinyl alcohol (“PVA217” manufactured by Kuraray Co., Ltd.) was used instead of NVF in the preparation of coating liquid (4). Coating liquid (6) was prepared in the same manner as above.

(7) Preparation of coating liquid (7) Coating liquid (4) was prepared except that hydrophobic group-containing polyvinyl alcohol (“RS2117” manufactured by Kuraray Co., Ltd.) was used instead of NVF. Coating liquid (7) was prepared in the same manner as in ).

〔Evaluation methods〕
The characteristics of the gas barrier laminates obtained in Examples, Comparative Examples, and Reference Examples were measured and evaluated as follows.

<Gas barrier properties of gas barrier laminate>
The gas barrier properties of the gas barrier laminates obtained in Examples, Comparative Examples, and Reference Examples were evaluated by oxygen permeability. The oxygen permeability was measured based on JIS K7126-2-2006 under the conditions of 23° C. and 65% RH using an oxygen permeability measuring device ("OX-TRANML" manufactured by MOCON). The results are shown in Tables 1 to 3.

<Measurement of peel strength of gas barrier laminate>
The gas barrier laminates obtained in Examples and Comparative Examples were cut into strips with a width of 15 mm, and a part of the obtained strip-shaped laminate for peel strength evaluation was cut by hand, taking care not to break the base material or sealant. A distance of 5 mm or more was peeled off. Thereafter, the sealant and the base material of the laminate for peel strength evaluation were respectively sandwiched between chucks of a testing machine, with the base material side facing down and the sealant side facing up. The peel strength between the base material and the sealant was measured at 23°C according to the test method specified in Japanese Industrial Standard JIS-K6854-3:1999 "Adhesives - Peel adhesion strength test method - Part 3: T-peel". , 50% RH, and tensile speed were measured using a small tabletop testing machine ("EX-LX" manufactured by Shimadzu Corporation) under the conditions of 300 mm/min. The results are shown in Tables 1 and 2. Note that cases in which the base material or sealant was broken and the peel strength could not be measured are described as "broken."

<Example 1>
Coating liquid (2) was applied with a bar coater to the corona-treated surface of a 40 μm thick unstretched polyethylene film (hereinafter referred to as “LLDPE”) (“FCD” manufactured by Mitsui Chemicals Tocello Co., Ltd.), and the coated layer was heated with hot air. A gas barrier layer was formed by heat treatment and drying in an oven, and a gas barrier laminate precursor 1 of base material/coating film (coating film thickness: 0.4 μm) was obtained. Drying was performed at 80° C. for 5 minutes under normal pressure.
Thereafter, the corona-treated surface of a 70 μm thick unstretched polypropylene film (hereinafter referred to as "CPP-1") ("ZK207" manufactured by Toray Film Kako Co., Ltd.) was directed toward the coating film side of the gas barrier laminate precursor 1. The base material/coating film (first barrier A gas barrier laminate having a coating thickness of 0.4 μm)/CPP-1 (sealant layer) was obtained.

<Example 2>
A gas barrier laminate was produced in the same manner as in Example 1, except that the number of passes through the hot roll laminator was changed to four.

<Example 3>
A gas barrier laminate was produced in the same manner as in Example 1, except that the roll temperature of the hot roll laminator was changed to 150°C.

<Example 4>
A gas barrier laminate was produced in the same manner as in Example 3, except that the number of passes through the hot roll laminator was changed to four.

<Example 5>
Coating liquid (2) was applied with a bar coater to the corona-treated surface of a 20 μm thick biaxially oriented polypropylene film (hereinafter referred to as “OPP”) (“P2102” manufactured by Toyobo Co., Ltd.), and the coated layer was heated in a hot air oven. A gas barrier layer was formed by heat treatment and drying in a vacuum chamber, and a gas barrier laminate precursor of a base material/coating film (coating film thickness: 0.4 μm) was obtained. Drying was performed at 80° C. for 5 minutes under normal pressure.
Then, overlap the CPP-1 with the corona-treated side facing the coating side of the gas barrier laminate precursor and pass it through twice using a hot roll laminator at a roll temperature of 180°C and a roll speed of 0.5 m/min. Thus, a gas barrier laminate of base material/coating film (first barrier layer, coating film thickness: 0.4 μm)/CPP (sealant layer) was obtained.

<Example 6>
A gas barrier laminate was produced in the same manner as in Example 5, except that the number of passes through the hot roll laminator was changed to four.

<Example 7>
A gas barrier laminate was produced in the same manner as in Example 5, except that LLDPE was used instead of CPP-1 and the roll temperature of the hot roll laminator was changed to 160°C.

<Example 8>
Coating liquid (2) was applied to the corona-treated surface of a 25 μm thick special polyethylene film (produced by a method according to paragraph [0136] of International Publication No. 2022/209424, hereinafter referred to as "PE-1"). It was coated with a bar coater, and the coated layer was heat-treated and dried in a hot air oven to form a gas barrier layer, thereby obtaining a gas barrier laminate precursor of the base material/coating film (coating film thickness: 0.4 μm). . Drying was performed at 80° C. for 5 minutes under normal pressure. Thereafter, the corona-treated side of the LLDPE with a thickness of 40 μm was stacked with the gas barrier laminate precursor facing the coating side, and using a hot roll laminator, the roll temperature was 160°C and the roll speed was 0.5 m/min twice. By passing it through, a gas barrier laminate of PE-1 (base material)/paint film (first barrier layer, paint film thickness: 0.4 μm)/LLDPE (sealant layer) was obtained.

<Example 9>
Using coating liquid (3) instead of coating liquid (2), changing the coating film thickness to 0.5 μm, using CPP-1 instead of LLDPE, and the roll temperature of the hot roll laminator. A gas barrier laminate was produced in the same manner as in Example 8, except that the temperature was changed to 180° C. and the number of passes through the hot roll laminator was changed to three times.

<Example 10>
Coating liquid (2) is applied to the corona-treated surface of CPP-1 using a bar coater, and the applied layer is heat-treated in a hot air oven and dried to form a gas barrier layer. A gas barrier laminate precursor having a thickness of 0.4 μm was obtained. Drying was performed at 80° C. for 5 minutes under normal pressure. Then, overlap the CPP-1 with the corona-treated side facing the coating side of the gas barrier laminate precursor and pass it through twice using a hot roll laminator at a roll temperature of 180°C and a roll speed of 0.5 m/min. Thus, a gas barrier laminate of CPP-1 (base material)/paint film (first barrier layer, paint film thickness: 0.4 μm)/CPP-1 (sealant layer) was obtained.

<Example 11>
A gas barrier laminate was produced in the same manner as in Example 10, except that the coating film thickness was changed to 0.2 μm.

<Example 12>
Coating liquid (4) is applied to the corona-treated surface of OPP using a bar coater, and the applied layer is heat-treated and dried in a hot air oven to form a first layer (second barrier layer). / A laminate of the first layer (second barrier layer, coating thickness: 1.0 μm) was obtained. Drying was performed at 80° C. for 5 minutes under normal pressure. After that, the coating liquid (2) was applied with a bar coater, and the applied layer was heat-treated and dried in a hot air oven to form a gas barrier layer. ) / coating film (coating film thickness: 0.4 μm) gas barrier laminate precursor was obtained. Drying was performed at 80° C. for 2 minutes under normal pressure. Thereafter, a 50 μm thick unstretched polypropylene film (hereinafter referred to as "CPP-2") ("P1111" manufactured by Toyobo Co., Ltd.) was stacked with the corona-treated side facing the coating side of the gas barrier laminate precursor. OPP (base material)/first layer (second barrier layer, coating film thickness: 1.0 μm) was obtained by passing it twice using a hot roll laminator at a roll temperature of 180°C and a roll speed of 0.5 m/min. ) / coating film (first barrier layer, coating thickness: 0.4 μm) / CPP-2 (sealant layer) gas barrier laminate was obtained.

<Example 13>
Coating liquid (5) was applied with a bar coater to a paper base material (hereinafter referred to as "paper") ("Tomoe River S" manufactured by Miyoshi Paper Co., Ltd.) with a weight of 52 g/ ^m2 , and the coated layer was placed in a hot air oven. The first layer was formed by heat treatment and drying to obtain a laminate of base material/first layer (coating film thickness: 5 μm). Drying was performed at 110° C. for 2 minutes under normal pressure. Thereafter, the coating liquid (1) was applied with a bar coater, and the coating layer was heat-treated and dried in a hot air oven to form a gas barrier layer. A gas barrier laminate precursor having a coating film (film thickness: 1.0 μm) was obtained. Drying was performed at 80° C. for 2 minutes under normal pressure. Then, overlap the CPP-2 with the corona-treated side facing the coating side of the gas barrier laminate precursor and pass it through twice using a hot roll laminator at a roll temperature of 180°C and a roll speed of 0.5 m/min. So, paper base material / first layer (filling layer, coating thickness: 5 μm) / coating film (first barrier layer, coating thickness: 1.0 μm) / CPP-2 (sealant layer) gas barrier. A laminate was obtained.

<Comparative example 1>
A gas barrier laminate was produced in the same manner as in Example 5, except that the coating liquid (2) was not applied with a bar coater.

<Comparative example 2>
A gas barrier laminate was produced in the same manner as in Example 1, except that the coating liquid (2) was not applied with a bar coater.

<Comparative example 3>
A gas barrier laminate was produced in the same manner as in Example 3, except that the coating liquid (2) was not applied with a bar coater.

<Comparative example 4>
A gas barrier laminate was produced in the same manner as in Example 7, except that the coating liquid (2) was not applied with a bar coater.

<Example 14>
Coating liquid (1) is applied to the corona-treated surface of OPP using a gravure coater, and the applied layer is dried in a hot air oven to form a gas barrier layer. A gas barrier laminate precursor having a thickness of 2 μm) was obtained. Drying was performed at 80° C. under normal pressure. Thereafter, a polyethylene layer (hereinafter referred to as "PE") with a film thickness of 20 μm is formed on the coating film side of the gas barrier laminate precursor by extrusion lamination, and the base material/coating film (first barrier layer, coating film thickness A gas barrier laminate having a thickness of 0.2 μm/polyethylene layer (sealant layer) was obtained. Extrusion lamination was performed at a line speed of 120 m/min and an extrusion resin temperature of 340°C.

<Example 15>
A gas barrier laminate was produced in the same manner as in Example 14, except that the coating film thickness was changed to 0.4 μm.

<Example 16>
Coating solution (1) was applied with a gravure coater to the corona-treated surface of a 12 μm thick biaxially oriented polyethylene terephthalate film (hereinafter referred to as “OPET”) (“E5102” manufactured by Toyobo Co., Ltd.), and the coated layer was coated with hot air. A gas barrier layer was formed by drying in an oven, and a gas barrier laminate precursor having a base material/coating film (coating film thickness: 0.2 μm) was obtained. Drying was performed at 80° C. under normal pressure. Thereafter, a PE layer with a thickness of 20 μm was formed on the coating side of the gas barrier laminate precursor by extrusion lamination, and the base material/coating film (first barrier layer, coating thickness: 0.2 μm)/PE layer (Sealant layer) gas barrier laminate was obtained. Extrusion lamination was performed at a line speed of 120 m/min and an extrusion resin temperature of 340°C.

<Example 17>
A gas barrier laminate was produced in the same manner as in Example 16, except that the coating thickness was changed to 0.4 μm.

<Example 18>
Coating liquid (1) was applied with a gravure coater to the corona-treated surface of a 15 μm thick biaxially stretched nylon film (hereinafter referred to as “ONY”) (“N1102” manufactured by Toyobo Co., Ltd.), and the coated layer was heated in a hot air oven. A gas barrier layer was formed by drying in a vacuum chamber, and a gas barrier laminate precursor having a base material/coating film (coating film thickness: 0.2 μm) was obtained. Drying was performed at 80° C. under normal pressure. Thereafter, a PE layer with a thickness of 20 μm was formed on the coating side of the gas barrier laminate precursor by extrusion lamination, and the base material/coating film (first barrier layer, coating thickness: 0.2 μm)/PE layer (Sealant layer) gas barrier laminate was obtained. Extrusion lamination was performed at a line speed of 120 m/min and an extrusion resin temperature of 340°C.

<Example 19>
A gas barrier laminate was produced in the same manner as in Example 18, except that the coating thickness was changed to 0.4 μm.

<Reference example 1>
Coating liquid (5) was applied with a bar coater to a paper base material (hereinafter referred to as "paper") ("Tomoe River S" manufactured by Miyoshi Paper Co., Ltd.) with a weight of 52 g/ ^m2 , and the coated layer was placed in a hot air oven. The first layer was formed by heat treatment and drying to obtain a laminate of base material/first layer (coating film thickness: 5 μm). Drying was performed at 110° C. for 2 minutes under normal pressure. After that, coating liquid (3) is applied with a bar coater, and the coating layer is heat-treated in a hot air oven and dried to form a gas barrier layer. A gas barrier laminate having a thickness of 0.5 μm)/coating film (coating thickness: 0.5 μm) was obtained. Drying was performed at 80° C. for 2 minutes under normal pressure.

<Reference example 2>
A gas barrier laminate was produced in the same manner as in Reference Example 1, except that coating liquid (1) was used instead of coating liquid (3).

<Reference example 3>
A gas barrier laminate was produced in the same manner as in Reference Example 1, except that coating liquid (6) was used instead of coating liquid (5).

<Reference example 4>
A gas barrier laminate was produced in the same manner as in Reference Example 3, except that coating liquid (1) was used instead of coating liquid (3).

<Reference example 5>
A gas barrier laminate was produced in the same manner as in Reference Example 1, except that coating liquid (7) was used instead of coating liquid (5).

<Reference example 6>
A gas barrier laminate was produced in the same manner as in Reference Example 5, except that coating liquid (1) was used instead of coating liquid (3).

<Reference example 7>
A gas barrier laminate was produced in the same manner as in Reference Example 1, except that coating liquid (4) was used instead of coating liquid (5).

<Reference example 8>
A gas barrier laminate was produced in the same manner as in Reference Example 7, except that coating liquid (1) was used instead of coating liquid (3).

<Reference example 9>
A gas barrier laminate was produced in the same manner as in Reference Example 1, except that the coating liquid (3) was not applied with a bar coater.

<Reference example 10>
A gas barrier laminate was produced in the same manner as in Reference Example 3, except that the coating liquid (3) was not applied with a bar coater.

<Reference example 11>
A gas barrier laminate was produced in the same manner as in Reference Example 5, except that the coating liquid (3) was not applied with a bar coater.

<Reference example 12>
A gas barrier laminate was produced in the same manner as in Reference Example 7, except that the coating liquid (3) was not applied with a bar coater.

As shown in Tables 1 to 3, the gas barrier laminates obtained in the examples had lower oxygen permeability at a relative humidity of 65% than the comparative examples, confirming that they had high gas barrier properties even under high humidity. Ta. Furthermore, the gas barrier laminate of the present invention has good peel strength even without an anchor layer, especially when the first barrier layer contains an amino group-containing resin, and has good peel strength between the base material and the sealant layer. It was confirmed that the adhesive property was high.

Claims (15)

A gas barrier laminate comprising a base material, a barrier layer and a sealant layer in this order,
The barrier layer includes a first barrier layer containing a resin and an inorganic layered compound,
The sealant layer is a laminate including a thermoplastic resin having heat sealability. The laminate according to claim 1, wherein the resin included in the first barrier layer includes a resin containing at least one functional group selected from the group consisting of a hydroxy group, a carboxy group, an amino group, and a sulfo group. The laminate according to claim 1, wherein the resin contained in the first barrier layer includes a resin containing an amino group. The laminate of claim 1, wherein the barrier layer and the sealant layer are in direct contact. The laminate according to claim 1, wherein the barrier layer includes a second barrier layer between the first barrier layer and the substrate. The laminate according to claim 5, wherein the second barrier layer contains an amino group-containing resin. The laminate according to claim 6, wherein the amount of amino groups in the second barrier layer is 0.3 mmol/g or more. The laminate according to claim 5, wherein the second barrier layer has a thickness of 0.001 to 10 μm. The laminate of claim 1, comprising an anchor layer between the barrier layer and the sealant layer. The laminate according to claim 1, comprising an anchor layer between the substrate and the barrier layer. Claim 1, wherein the thermoplastic resin having heat-sealing properties is at least one selected from the group consisting of polyolefin resins, polyacrylonitrile resins, polyester resins, ethylene-vinyl alcohol copolymers, metallocenes, and higher fatty acid polyolefins. The laminate described in . The base material is selected from the group consisting of polyolefin resin, polyester resin, amide resin, acrylic resin, polystyrene resin, hydrophobized cellulose resin, halogen-containing resin, hydrogen bonding resin, and engineering plastic resin. The laminate according to claim 1, comprising a resin. The laminate according to claim 1, wherein the base material is a paper base material. The laminate according to claim 13, comprising a sealing layer between the paper base material and the barrier layer. The method for producing a gas barrier laminate according to any one of claims 1 to 14, comprising the step of laminating a sealant layer directly or indirectly on the barrier layer by extrusion lamination or hot roll lamination.