WO2017104695A1

WO2017104695A1 - Gas barrier packaging material precursor, method for producing same, gas barrier packaging material, and method for producing package

Info

Publication number: WO2017104695A1
Application number: PCT/JP2016/087185
Authority: WO
Inventors: 晴香大森; 大森　望
Original assignee: 凸版印刷株式会社
Priority date: 2015-12-14
Filing date: 2016-12-14
Publication date: 2017-06-22
Also published as: JP6900906B2; JPWO2017104695A1

Abstract

This gas barrier packaging material precursor is provided with: a support; a gas barrier layer disposed directly on the support and containing a polycarboxylic acid polymer and at least one silicon compound selected from the group consisting of hydrolyzable silane compounds, hydrolyzates thereof, and their condensates; and a protective layer disposed directly on the gas barrier layer and containing a multivalent metal component, a polyester resin, and a dispersing agent. The water vapor transmission rate of the support at 40°C and a relative humidity of 90% is at least 100 g/m², the content of the multivalent metal component is 40 to 90 mass% with reference to the total mass of the protective layer, the content of the dispersing agent is 2 to 20 mass% with reference to the multivalent metal component, and the content of the silicon compound is 2 to 25 mass% with reference to the polycarboxylic acid polymer. In measurement of the infrared absorption spectrum of the gas barrier layer, the ratio (α／β) between the maximum peak height (α) for the absorbance in the wavenumber range of 1490 cm^–1 to 1659 cm^–1 and the maximum peak height (β) for the absorbance in the wavenumber range of 1660 cm^–1 to 1750 cm^–1 is at least 1 and less than 7.

Description

Precursor for gas barrier packaging material, method for producing the same, gas barrier packaging material, and method for producing the package

The present invention relates to a precursor for a gas barrier packaging material, a method for producing the same, a gas barrier packaging material, and a method for producing a package.
This application claims priority based on Japanese Patent Application Nos. 2015-243267 and 2015-243335 filed in Japan on December 14, 2015, the contents of which are incorporated herein by reference.

For packaging materials used for packaging foods, pharmaceuticals, etc., gas barrier properties are used to suppress the permeation of oxygen, water vapor, or other gases that react with the contents and prevent the contents from being altered. Desired.
Conventionally, as a packaging material having gas barrier properties, a film formed from a polymer containing a highly hydrophilic high-bonding group in the molecule, such as poly (meth) acrylic acid or polyvinyl alcohol, Multi-layer films having layers formed from coalescence are used. These films exhibit very good oxygen gas barrier properties under dry conditions. However, due to the hydrophilicity, there is a possibility that the oxygen gas barrier property is greatly lowered under high humidity conditions, and the resistance to humidity and hot water may be inferior.

In order to solve such a problem, a laminate in which a layer containing a polycarboxylic acid polymer and a layer containing a polyvalent metal compound are laminated on a support has been proposed. When such a laminate is subjected to a hydrothermal treatment such as a retort treatment, the ionic cross-linking of the polycarboxylic acid polymer by polyvalent metal ions proceeds by the reaction between layers, and has a high oxygen gas barrier property even under high humidity conditions. It is known to express. Various studies have been made on such a laminate and its manufacturing method (see, for example, Patent Documents 1 to 3).
Examination of the laminate as described above is usually carried out using a polyethylene terephthalate (PET) film as a support from the viewpoint of thermal (dimensional) stability, water absorption, price, etc. Often considered to be reproducible even on a support.

International Publication No. 2010/061705 Japanese Patent No. 4684891 International Publication No. 2010/001836

PET is very rigid. When a PET film is used as the support for the laminate, it is necessary to reduce the thickness of the PET film to some extent from the viewpoint of the flexibility of the packaging material. Such a PET film has low strength. Therefore, from the viewpoint of practical strength as a packaging material, it is necessary to laminate a polyamide-based resin film, and it takes time and cost to manufacture the packaging material.

In order to reduce the number of layers of the packaging material, the present inventors examined using a polyamide-based resin film as a support instead of a PET film. As a result, when the techniques disclosed in Patent Documents 1 to 3 and the like are applied to such a film, the oxygen gas barrier property is very often inferior to the case of using a PET film.
As a result of further studies, it has been found that the above problem is caused by the fact that the water vapor permeability of the film used for the support is higher than that of the PET film.

The present invention relates to a precursor for a gas barrier packaging material having a layer exhibiting an excellent oxygen barrier property by hot water treatment on a support having a high water vapor permeability, a method for producing the same, and the precursor for the gas barrier packaging material It aims at providing the manufacturing method of the gas-barrier packaging material and packaging body using this.

The precursor for a gas barrier packaging material according to the first aspect of the present invention comprises a support; provided directly on the support, a polycarboxylic acid polymer, a hydrolyzable silane compound, a hydrolyzate thereof, And a gas barrier layer comprising at least one silicon compound selected from the group consisting of these condensates; and a protective layer provided directly on the gas barrier layer and comprising a polyvalent metal component, a polyester resin, and a dispersant The water vapor permeability at 40 ° C. and relative humidity of 90% of the support is 100 g / m ² or more, and the content of the polyvalent metal component is 40 with respect to the total mass of the protective layer. Is 90% by mass, the dispersant content is 2-20% by mass with respect to the polyvalent metal component, and the silicon compound content is 2% with respect to the polycarboxylic acid polymer. ~ 25% by mass, Wherein when measuring the infrared absorption spectrum of the gas barrier layer, the maximum peak height in absorbance in the range of wave number ^1490cm ^-1 ~ ^1659cm -1 and (alpha), the absorbance in the wave number range of ^{1660 cm} -1 ~ 1750 cm ^-1 The ratio (α / β) to the maximum peak height (β) is 1 or more and less than 7.
The gas barrier packaging material according to the second aspect of the present invention comprises a support; provided directly on the support, a polycarboxylic acid polymer, a hydrolyzable silane compound, a hydrolyzate thereof, and these A gas barrier layer containing at least one silicon compound selected from the group consisting of condensates; a protective layer provided directly on the gas barrier layer and containing a polyvalent metal component, a polyester resin, and a dispersant; And the support has a water vapor transmission rate of 100 g / m ² or more at 40 ° C. and a relative humidity of 90%, and the content of the polyvalent metal component is 40 to 90 mass with respect to the total mass of the protective layer. %, The dispersant content is 2-20 mass% with respect to the polyvalent metal component, and the silicon compound content is 2-25 mass with respect to the polycarboxylic acid polymer. % When measuring the infrared absorption spectrum of the barrier layer, the maximum peak height in absorbance in the range of wave number ^1490cm ^-1 ~ ^1659cm -1 and (alpha), the maximum absorbance in the wave number range of ^{1660 cm} -1 ~ 1750 cm ^-1 The ratio (α / β) to the peak height (β) is 7 or more.
In the method for producing a precursor for a gas barrier packaging material according to the third aspect of the present invention, a polycarboxylic acid polymer, a hydrolyzable silane compound, a hydrolyzate thereof, and a condensate thereof are formed on the surface of a support. A gas barrier layer coating solution containing at least one silicon compound selected from the group consisting of the above and a liquid medium is applied and dried to form a gas barrier layer. A polyvalent metal component and polyester are formed on the surface of the gas barrier layer. A protective layer is formed by applying a coating liquid for a protective layer containing a resin, a dispersant, and water and drying, and the support has a water vapor permeability of 100 g at 40 ° C. and a relative humidity of 90%. / M ² or more, the content of the polyvalent metal component is 40 to 90% by mass with respect to the total solid content of the protective layer coating liquid, and the content of the dispersant is the polyvalent metal. 2 to 20% by weight with respect to the ingredients, The content of the silicon compound is 2 to 25% by mass with respect to the polycarboxylic acid polymer, and the degree of neutralization of the carboxyl group of the polycarboxylic acid polymer by a polyvalent metal is 0 mol%. .
In the method for producing a package according to the fourth aspect of the present invention, a package is obtained by packaging an article to be packaged using the precursor for gas barrier packaging material according to the first aspect, and performing hot water treatment.
The precursor for a gas barrier packaging material according to the fifth aspect of the present invention comprises: a support; an intermediate layer provided directly on the support and including a polyvalent metal component, a polyester resin, and a dispersant; A gas barrier layer provided directly on the layer and comprising a polycarboxylic acid polymer and at least one silicon compound selected from the group consisting of hydrolyzable silane compounds, hydrolysates thereof, and condensates thereof The water vapor permeability at 40 ° C. and 90% relative humidity of the support is 100 g / m ² or more, and the content of the polyvalent metal component is 40 with respect to the total mass of the intermediate layer. Is 90 mass%, the dispersant content is 2-20 mass% with respect to the polyvalent metal component, and the silicon compound content is 2 with respect to the polycarboxylic acid polymer. Up to 25% by mass, When measuring the infrared absorption spectrum of the gas barrier layer, the maximum absorbance of the maximum peak height in absorbance in the range of wave number ^1490cm ^-1 ~ ^1659cm -1 and (alpha), within the range of wave number ^{1660 cm} -1 ~ 1750 cm ^-1 The ratio (α / β) to the peak height (β) is 1 or more and less than 7.
The gas barrier packaging material according to the sixth aspect of the present invention comprises: a support; an intermediate layer provided directly on the support and including a polyvalent metal component, a polyester resin, and a dispersant; And a gas barrier layer comprising a polycarboxylic acid polymer and at least one silicon compound selected from the group consisting of a hydrolyzable silane compound, a hydrolyzate thereof, and a condensate thereof. And the support has a water vapor permeability of 100 g / m ² or more at 40 ° C. and a relative humidity of 90%, and the content of the polyvalent metal component is 40 to 90 mass with respect to the total mass of the intermediate layer. %, The dispersant content is 2-20% by mass with respect to the polyvalent metal component, and the silicon compound content is 2-25% by mass with respect to the polycarboxylic acid polymer. %, And the gas burr When measuring the infrared absorption spectrum of the ^layer, the maximum peak height absorbance in the range of 1490cm ^-1 ~ 1659cm -1 and ^(alpha), the maximum peak height in absorbance in the range of 1660 cm -1 ~ 1750 cm ^-1 The ratio (α / β) to (β) is 7 or more.
In the method for producing a precursor for a gas barrier packaging material according to the seventh aspect of the present invention, an intermediate layer coating solution containing a polyvalent metal component, a polyester resin, a dispersant, and a liquid medium is applied to the surface of a support. An intermediate layer is formed by drying, and at least one selected from the group consisting of a polycarboxylic acid polymer, a hydrolyzable silane compound, a hydrolyzate thereof, and a condensate thereof is formed on the surface of the intermediate layer. A gas barrier layer coating solution comprising a silicon compound and water is applied and dried to form a gas barrier layer, and the water vapor permeability of the support at 40 ° C. and 90% relative humidity is 100 g / m ^2. The content of the polyvalent metal component is 40 to 90% by mass with respect to the total solid content of the intermediate layer coating solution, and the content of the dispersant is based on the polyvalent metal component. 2 to 20% by mass, The content of the compound is 2 to 25% by mass with respect to the polycarboxylic acid polymer, and the degree of neutralization of the carboxyl group of the polycarboxylic acid polymer by a polyvalent metal is 20 to 50 mol%. .
The method for manufacturing a package according to the eighth aspect of the present invention uses the precursor for a gas barrier packaging material according to the fifth aspect to package an article to be packaged, and performs hot water treatment to obtain a package.

According to the above aspect of the present invention, it is possible to provide a precursor for a gas barrier packaging material having a layer exhibiting an excellent oxygen barrier property by hot water treatment on a support having a high water vapor permeability and a method for producing the same. Furthermore, according to the said aspect of this invention, the manufacturing method of the gas barrier packaging material and packaging body using the said precursor for gas barrier packaging materials can be provided.

It is a schematic cross section of the precursor for gas barrier packaging materials according to the first embodiment of the present invention. It is a schematic cross section of the gas barrier packaging material obtained from the precursor for gas barrier packaging material according to the first embodiment. It is a schematic cross section of the precursor for gas barrier packaging materials according to the second embodiment of the present invention. It is a schematic cross section of the gas barrier packaging material obtained from the precursor for gas barrier packaging material according to the second embodiment. It is a schematic cross section of the precursor for gas barrier packaging materials according to the third embodiment of the present invention. It is a schematic cross section of the gas barrier packaging material obtained from the precursor for gas barrier packaging material according to the third embodiment. It is a schematic cross section of the precursor for gas barrier packaging materials according to the fourth embodiment of the present invention. It is a schematic cross section of the gas barrier packaging material obtained from the precursor for gas barrier packaging material according to the fourth embodiment. It is a schematic cross section of the precursor for gas barrier packaging materials according to the fifth embodiment of the present invention. It is a schematic cross section of the gas barrier packaging material obtained from the precursor for gas barrier packaging material according to the fifth embodiment. It is a schematic cross section of the precursor for gas barrier packaging materials according to the sixth embodiment of the present invention. It is a schematic cross section of the gas barrier packaging material obtained from the precursor for gas barrier packaging material according to the sixth embodiment.

Hereinafter, a precursor for a gas barrier packaging material according to the first to sixth embodiments of the present invention (hereinafter also referred to as “precursor for packaging material”), a manufacturing method thereof, a gas barrier packaging material (hereinafter referred to as “packaging material”). And the manufacturing method of the package will be described with reference to the accompanying drawings.

<< First Embodiment >>
FIG. 1 is a schematic cross-sectional view of a packaging material precursor 10 according to a first embodiment of the present invention. FIG. 2 is a schematic cross-sectional view of the packaging material 11 obtained from the packaging material precursor 10.
The packaging material precursor 10 of the present embodiment has a laminated structure in which a support 1, a gas barrier layer 2, and a protective layer 3 are laminated adjacently in this order. That is, in the packaging material precursor 10 of the present embodiment, the gas barrier layer 2 is directly provided on the support 1, and the protective layer 3 is directly provided on the gas barrier layer 2.
The packaging material 11 is the same as the packaging material precursor 10 except that the packaging material 11 has the gas barrier layer 4 instead of the gas barrier layer 2.

<Precursor for packaging materials>
[Support]
Water vapor permeability of the support 1 is 100 g / ^{m 2} or more, 120 g / ^{m 2} or more. If the water vapor permeability of the support 1 is equal to or higher than the lower limit (100 g / m ² ), when the packaging material precursor 10 is subjected to hydrothermal treatment, the gas barrier layer 2 and the protective layer 3 are formed via the support 1. Sufficient moisture is supplied. Therefore, the ratio (α / β) described later of the gas barrier layer 2 can be set to 7 or more from the range of 1 or more and less than 7.
If the water vapor permeability of the support 1 is not less than the above lower limit (100 g / m ² ), the oxygen barrier property after the hot water treatment is good.
The water vapor permeability of the support 1 is a value measured under conditions of 40 ° C. and a relative humidity of 90%.

The material of the support 1 is not particularly limited as long as the water vapor permeability of the support 1 is 100 g / m ² or more, and examples thereof include plastics, papers, and rubbers. Among these materials, plastics are preferable from the viewpoint of adhesion between the support 1 and the gas barrier layer 2.

Examples of the plastics include polyamide polymers.
Examples of the polyamide polymer include nylon 6, nylon 66, nylon 12, nylon 6,66 copolymer, nylon 6,12 copolymer, metaxylene adipamide / nylon 6 copolymer, and the like.

The support 1 may be formed from a single layer or may be formed from a plurality of layers. When formed with a plurality of layers, the material forming each layer may be the same or different.
The form of the support 1 is not limited to a sheet (film, plate) as illustrated, and may be a bottle, a cup, a tray, a tank, a tube, or the like. The form of the support 1 is preferably a sheet.
As the support 1, for example, the plastics film can be used. This film may be stretched or unstretched.
From the viewpoint of adhesion to the gas barrier layer 2, the surface of the support 1 may be subjected to surface activation treatment such as corona treatment, flame treatment, and plasma treatment.

The thickness of the support 1 is usually 5 μm to 2 cm, although it varies depending on the application. When the form of the support 1 is a sheet, it is preferably 5 to 800 μm, more preferably 10 to 500 μm. In the case of a bottle, cup, tray or tank, 100 μm to 1 cm is preferable, and 150 μm to 8 mm is more preferable. In the case of a tube form, 20 μm to 2 cm is preferable. When the thickness of the support 1 is within the above range, workability and productivity are excellent.

[Gas barrier layer]
The gas barrier layer 2 includes at least one silicon compound selected from the group consisting of a polycarboxylic acid polymer, a hydrolyzable silane compound, a hydrolyzate thereof, and a condensate thereof (hereinafter referred to as “silicon compound (i ) ”))).
The gas barrier layer 2 may further contain other components than the polycarboxylic acid polymer and the silicon compound (i) as necessary.

(Polycarboxylic acid polymer)
The polycarboxylic acid polymer is a polymer having two or more carboxyl groups in the molecule. Examples of the polycarboxylic acid-based polymer include (co) polymers of ethylenically unsaturated carboxylic acids; copolymers of ethylenically unsaturated carboxylic acids and other ethylenically unsaturated monomers; alginic acid, carboxymethyl cellulose, Examples include acidic polysaccharides having a carboxyl group in the molecule such as pectin. As a polycarboxylic acid type polymer, you may use individually by 1 type, and may mix and use 2 or more types.

Examples of the ethylenically unsaturated carboxylic acid include acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, and crotonic acid.
Examples of other ethylenically unsaturated monomers copolymerizable with the ethylenically unsaturated carboxylic acid include ethylene, saturated carboxylic acid vinyl esters such as propylene and vinyl acetate, alkyl acrylates, alkyl methacrylates, and alkyls. Examples include itaconates, vinyl chloride, vinylidene chloride, styrene, acrylamide, acrylonitrile and the like.

The polycarboxylic acid polymer is derived from at least one polymerizable monomer selected from the group consisting of acrylic acid, maleic acid, methacrylic acid, itaconic acid, fumaric acid and crotonic acid from the viewpoint of gas barrier properties. A polymer (hereinafter also referred to as “polymer (X)”), or a mixture of two or more of the polymers (X). Preferably there is. The polymer (X) may be a homopolymer or a copolymer. The structural unit (x) is preferably a structural unit derived from at least one polymerizable monomer selected from the group consisting of acrylic acid, maleic acid, methacrylic acid and itaconic acid.
The polymer (X) may further contain other structural units other than the structural unit (x). Examples of the other structural unit include a structural unit derived from an ethylenically unsaturated monomer copolymerizable with the aforementioned ethylenically unsaturated carboxylic acid.
In the polymer (X), the content of the structural unit (x) is preferably 80 mol% or more, and 90 mol% or more with respect to the total of all the structural units constituting the polymer (X). Is more preferable, and may be 100 mol%.

The number average molecular weight of the polycarboxylic acid polymer is preferably 2,000 to 10,000,000, more preferably 5,000 to 1,000,000. When the number average molecular weight is 2,000 or more, the packaging material obtained from the packaging material precursor 10 is excellent in water resistance, and the gas barrier property and transparency due to moisture are less likely to be whitened. On the other hand, if the number average molecular weight is 10,000,000 or less, the viscosity of the coating solution can be sufficiently lowered when the gas barrier layer 2 is formed by coating a coating solution containing a polycarboxylic acid polymer or the like. Good properties.
The number average molecular weight is a polystyrene-reduced number average molecular weight determined by gel permeation chromatography (GPC).

A part of the carboxyl group of the polycarboxylic acid polymer in the gas barrier layer 2 is neutralized with a polyvalent metal ion to form a polyvalent metal salt. That is, a part of the carboxy group is ion-crosslinked with a polyvalent metal ion. The polyvalent metal is a metal having a valence of 2 or more, such as beryllium, alkaline earth metals such as magnesium and calcium, titanium, zirconium, chromium, manganese, iron, cobalt, nickel, copper, zinc, etc. Transition metals, aluminum and the like. From the viewpoints of gas barrier properties, resistance to high-temperature steam and hot water, and productivity, the polyvalent metal is preferably a divalent metal having a metal ion valence of 2. In terms of oxygen barrier properties, zinc and copper are preferable, and zinc is particularly preferable.
As long as the gas barrier property is not impaired, a part of the carboxyl group of the polycarboxylic acid polymer in the gas barrier layer 2 may be neutralized with at least one selected from the group consisting of monovalent metal ions and ammonium ions. Good. Examples of monovalent metal ions include alkali metals such as sodium and potassium.
The neutralization degree of the carboxyl group in the gas barrier layer 2 is about 50 mol% because the ratio (α / β) described later is 1 or more and less than 7.

(Silicon compound (i))
The silicon compound (i) is at least one selected from the group consisting of a hydrolyzable silane compound, a hydrolyzate thereof, and a condensate thereof. That is, the silicon compound (i) is at least one selected from the group consisting of a hydrolyzable silane compound, a hydrolyzate of the hydrolyzable silane compound, and a hydrolyzable silane compound and a condensate of the hydrolyzate. is there.
The silicon compound (i) contributes to improvement of water resistance and gas barrier properties of the packaging material obtained from the packaging material precursor 10.

The hydrolyzable silane compound is a compound that generates a silanol group (SiOH) by hydrolysis. The hydrolyzable silane compound is not particularly limited, and examples thereof include compounds represented by the following formula (i-1).
Si (OR ¹ ) _n (R ² ) _4-n (i-1)
(Wherein R ¹ is an alkyl group having 1 to 4 carbon atoms or an alkoxyalkyl group having 1 to 4 carbon atoms, R ² is an organic reactive group, and n is an integer of 1 to 4)

In formula (i-1), R ¹ is preferably a methyl group, an ethyl group, or a methoxyethyl group.
Examples of R ² include organic groups having reactive functional groups such as amino groups, (meth) acryl groups, epoxy groups, vinyl groups, mercapto groups, isocyanate groups, and isocyanurate groups. The (meth) acryl group indicates both an acrylic group and a methacryl group.
R ² is preferably an organic group having an epoxy group in terms of reactivity with the polyacrylic acid polymer. Examples of the organic group having an epoxy group include a 3-glycidoxypropyl group.
n is preferably 3.

Specific examples of the hydrolyzable silane compound include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3 -Glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylethyldiethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2- (Aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-acryloxyp Pills trimethoxysilane, 3-isocyanate propyl triethoxysilane, tris - (trimethoxysilylpropyl) isocyanurate. Any one of these hydrolyzable silane compounds may be used alone, or two or more thereof may be used in combination.

The silicon compound (i) may be a hydrolyzable silane compound itself, a hydrolyzate obtained by hydrolyzing the hydrolyzable silane compound, or a condensate thereof.
As the silicon compound (i), for example, a hydrolyzable silane compound subjected to hydrolysis and condensation reaction using a sol-gel method can be used.

In general, a hydrolyzable silane compound is easily hydrolyzed, and easily undergoes a condensation reaction in the presence of an acid or an alkali. For example, in the hydrolyzable silane compound represented by the formula (i-1), at least a part of the alkoxy group (OR ¹ ) is easily substituted with a hydroxyl group to become a hydrolyzate. Further, the hydrolyzate condenses to form a compound in which silicon atoms (Si) are bonded through oxygen. By repeating this condensation, a condensate is obtained. Hereinafter, a configuration in which a hydrolyzate of a hydrolyzable silane compound is condensed is also referred to as a hydrolysis condensate.
Therefore, the silicon compound (i) rarely exists only in the hydrolyzable silane compound, only the hydrolyzate thereof, or only the condensate thereof. That is, the silicon compound (i) often contains a hydrolyzable silane compound, a hydrolyzate thereof, and a hydrolysis condensate. In addition, the hydrolyzate often includes a partial hydrolyzate and a complete hydrolyzate.
The silicon compound (i) preferably contains at least a hydrolysis condensate.

(Other ingredients)
The other components other than the polycarboxylic acid polymer and the silicon compound (i) are not particularly limited, and various additives may be included.
Examples of the additive include a plasticizer, a resin, a dispersant, a surfactant, a softener, a stabilizer, an antiblocking agent, a film forming agent, an adhesive, and an oxygen absorber.

When the gas barrier layer 2 contains a plasticizer, the stretchability of the gas barrier layer 2 is improved, and the abuse resistance of the packaging material precursor 10 is improved.
As a plasticizer, it can be used by appropriately selecting from known plasticizers. Specific examples of the plasticizer include ethylene glycol, trimethylene glycol, propylene glycol, tetramethylene glycol, 1,3-butanediol, 2,3-butanediol, pentamethylene glycol, hexamethylene glycol, diethylene glycol, triethylene glycol, and the like. Examples include ethylene glycol, polyethylene glycol, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyethylene oxide, sorbitol, mannitol, dulcitol, erythritol, glycerin, lactic acid, fatty acid, starch, and phthalate ester. These may be used in a mixture as required.
Among these, polyethylene glycol, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, glycerin, and starch are preferable from the viewpoints of stretchability and gas barrier properties.

In addition, when the gas barrier layer 2 includes a compound having two or more hydroxyl groups such as polyvinyl alcohol as an additive, the hydroxyl group and a part of the carboxyl groups of the polycarboxylic acid polymer form an ester bond. It may be.

(Content of each component)
The content of the silicon compound (i) in the gas barrier layer 2 is 2 to 25% by mass, preferably 2 to 20% by mass, based on the polycarboxylic acid polymer (100% by mass). If content of silicon compound (i) is in the said range, it will be excellent in adhesiveness with the support body 1. FIG. Moreover, the water resistance of the packaging material obtained from the precursor 10 for packaging materials is more excellent, and it is hard to whiten when exposed to cold water.
Here, the mass of the silicon compound (i) other than the hydrolyzable silane compound is a mass in terms of the hydrolyzable silane compound. That is, the silicon compound (i) usually contains a hydrolyzable silane compound, a hydrolyzate thereof, and a condensate thereof, but the mass of the silicon compound (i) is converted to a hydrolyzable silane compound. This is the amount of the hydrolyzable silane compound charged.

The total content of the polycarboxylic acid polymer and the silicon compound (i) in the gas barrier layer 2 is preferably 70% by mass or more, more preferably 80% by mass or more, and 100% by mass with respect to the total mass of the gas barrier layer 2. %.
The mass of the silicon compound (i) other than the hydrolyzable silane compound is the mass in terms of the hydrolyzable silane compound as described above.

The content of other components in the gas barrier layer 2 is preferably 30% by mass or less and more preferably 20% by mass or less with respect to the polycarboxylic acid polymer (100% by mass).

(Maximum peak height ratio (α / β))
When measuring the infrared absorption spectrum of the gas barrier layer 2, the maximum peak height in absorbance in the range of wave number ^1490cm ^-1 ~ ^1659cm -1 and (alpha), the absorbance in the wave number range of ^{1660 cm} -1 ~ 1750 cm ^-1 The ratio (α / β) to the maximum peak height (β) is 1 or more and less than 7.

The maximum peak height (α) is a C═O stretching vibration having a wave number of 1560 cm ⁻¹ , which belongs to a carboxyl group (—COO ⁻ ) forming a salt (hereinafter also referred to as “carboxyl group salt”). In the infrared absorption spectrum, it is the maximum peak height of absorbance. That is, usually, salts of carboxyl groups (-COO ^-) C = O stretching vibration attributable to, in the infrared wave number range of wavenumber ^1490cm ^-1 ~ ^1659cm -1, absorption peaks with absorption maximum around 1560 cm ^-1 give.

The maximum peak height (β) is the maximum peak height of the absorbance of the infrared absorption spectrum that is separated from the maximum peak height (α). That is, the maximum peak height (β) is the maximum peak height of absorbance in the infrared absorption spectrum of C═O stretching vibration having a wave number of 1700 cm ⁻¹ , which belongs to a free carboxyl group (—COOH). That is, normally, C = O stretching vibration attributable to the free carboxyl group (-COOH) is an infrared wave number range of wave number ^{1660 cm} -1 ~ 1750 cm ^-1, giving an absorption peak having an absorption maximum in the vicinity of 1700 cm ^-1 .

The absorbance when the infrared absorption spectrum of the gas barrier layer 2 is measured is proportional to the amount of chemical species having infrared activity present in the gas barrier layer 2.
Therefore, the ratio (α / β) can be used as a measure representing the ratio of the carboxyl group polyvalent metal salt (—COO ⁻ ) to the free carboxyl group (—COOH) in the gas barrier layer 2. The larger the ratio (α / β), the higher the ratio of the carboxyl group polyvalent metal salt to the free carboxyl group.
When the ratio (α / β) is 1 or more and less than 7, the polyvalent metal salt of the carboxyl group with respect to all the carboxyl groups (carboxyl groups forming the salt and free carboxyl groups) of the polycarboxylic acid polymer It can be determined that the ratio, that is, the ratio of carboxy groups ion-crosslinked by polyvalent metal ions (the degree of ion crosslinking) is about 50 mol%.

When hot water treatment such as retort treatment and boil treatment is performed on the packaging material precursor 10, moisture is supplied to the gas barrier layer 2 and the protective layer 3. At this time, in the gas barrier layer 2, the expansion of the gas barrier layer 2 due to the supplied water and the ionic crosslinking of the carboxyl group of the polycarboxylic acid polymer by the polyvalent metal ions from the protective layer 3 proceed. Production of polyvalent metal ions in the protective layer 3 is related to H ⁺ produced by ionization of carboxyl groups of the polycarboxylic acid polymer of the gas barrier layer 2. Further, moisture and heat supplied to the gas barrier layer 2 are used for the ionization of the carboxyl group.
When the ratio (α / β) of the maximum peak height of absorbance of the gas barrier layer 2 before the hot water treatment is less than 1, the gas barrier layer 2 tends to expand during the hot water treatment because the degree of ionic crosslinking is low.
When the water vapor permeability of the support 1 is low, the amount of water supply is small, so even if the ratio (α / β) is less than 1, the ratio (α / β) becomes 7 or more before the gas barrier layer 2 expands much. The degree of ionic crosslinking increases. Therefore, a gas barrier layer having a high crosslink density and a high gas barrier property is obtained.
However, when the water vapor permeability of the support 1 is as high as 100 g / m ² or more, if the ratio (α / β) is less than 1, the amount of moisture supplied during the hot water treatment is large, so the ratio (α / β ) Expands before the gas barrier layer 2 becomes 7 or more. For this reason, the crosslink density of the gas barrier layer is lowered, resulting in insufficient gas barrier properties.
When the ratio (α / β) is 1 or more, excellent gas barrier properties are exhibited by the hot water treatment. This is because the carboxy group of the polycarboxylic acid polymer is ionically crosslinked by about 50 mol% before the hot water treatment, so that the expansion of the gas barrier layer 2 during the hot water treatment is suppressed and the crosslinking density is increased. it is conceivable that.
If the ratio (α / β) is less than 7, the flexibility of the gas barrier layer 2 is good, and the packaging material precursor 10 is easily processed into a bag or the like.

The ratio (α / β) is an infrared absorption spectrum of the gas barrier layer 2 is measured, the maximum peak absorbance in the wave number range of ^1490cm ^-1 ~ ^1659cm -1 height (alpha) and the wavenumber ^1660cm ^-1 ~ ^1750cm -1 The maximum peak height (β) of absorbance within the range can be measured and determined.
The infrared absorption spectrum can be measured by using a known method such as a transmission method, an ATR method (attenuated total reflection method), a KBr pellet method, a diffuse reflection method, or a photoacoustic method (PAS method). For example, an infrared absorption spectrum can be measured by the ATR method using an Auto Image manufactured by Perkin Elmer as a Fourier transform infrared spectroscopy (FT-IT) analyzer. For the infrared absorption spectrum measurement method using FT-IR, reference can be made to, for example, “Fundamentals and Practices of FT-IR” by Mitsuo Tasumi.

As a method for measuring an infrared absorption spectrum, a transmission method or an ATR method is preferable from the viewpoint of simplicity.
A typical method for measuring the infrared absorption spectrum includes a method of measuring the surface of the gas barrier layer 2 by the ATR method. The measurement conditions of the infrared absorption spectrum at this time include measurement conditions using Ge (germanium), an incident angle of 45 degrees, a resolution of 4 cm ⁻¹ , and an integration count of 10 from the viewpoint of penetration depth.
When the infrared absorption spectrum is measured by the transmission method, the infrared absorption spectrum in a state where the gas barrier layer 2 and the protective layer 3 are removed from the packaging material precursor 10 is compared with the infrared absorption spectrum of the packaging material precursor 10. . In this case, it is preferable to use the infrared absorption spectrum in a state where the gas barrier layer 2 and the protective layer 3 are removed from the packaging material precursor 10 as the background. The gas barrier layer 2 and the protective layer 3 can be removed from the packaging material precursor 10 with a strong acid or a strong base, such as hydrochloric acid or a sodium hydroxide aqueous solution.
In the infrared absorption spectrum, the maximum peak height of absorbance, a value obtained by measuring the line connecting the absorbance of the absorbance and the wave number 1900 cm ^-1 in wave number 900 cm ^-1 in a straight line as a baseline.

The infrared absorption spectrum is mainly derived from the chemical structure of the carboxyl group, and is less affected by the metal species of the salt. Therefore, when a part of the carboxy group of the polycarboxylic acid polymer in the gas barrier layer 2 is a monovalent metal salt such as a sodium salt within a range not impairing the gas barrier property, the monovalent carboxyl group metal salt (-COO ^-) C = O stretching vibration attributable to, in the infrared wave number range of wavenumber ^1490cm ^-1 ~ ^1659cm -1, giving an absorption peak having an absorption maximum in the vicinity of 1560 cm ^-1.
The metal species present in the gas barrier layer 2 can be confirmed by ICP (high frequency inductively coupled plasma) emission spectroscopic analysis, EDX (energy dispersive X-ray) spectroscopy, or the like.

Mass per unit area of the gas barrier layer 2 is preferably 0.1 ~ 10 g / ^{m 2,} more preferably 0.1 ~ 6 g / ^{m 2,} more preferably 0.1 ~ 2g / ^{m 2.} When the mass per unit area of the gas barrier layer 2 is within the above range, the gas barrier property is more excellent.

The thickness of the gas barrier layer 2 is preferably 0.05 to 5 μm, more preferably 0.1 to 3 μm, and further preferably 0.1 to 1 μm. When the thickness of the gas barrier layer 2 is within the above range, the gas barrier property is more excellent.

[Protective layer]
The protective layer 3 includes a polyvalent metal component, a polyester resin, and a dispersant.
It is preferable that the protective layer 3 further contains an isocyanate compound.
The protective layer 3 may further include a component other than the polyvalent metal component, the polyester resin, the dispersant, and the isocyanate compound.

(Polyvalent metal component)
The polyvalent metal component functions as a supply source of polyvalent metal ions. The polyvalent metal ions ion-crosslink carboxyl groups of the polycarboxylic acid polymer contained in the gas barrier layer 2 to improve gas barrier properties.
Examples of the polyvalent metal component include a single polyvalent metal atom and a polyvalent metal compound.
The polyvalent metal is a metal having a valence of 2 or more, such as beryllium, alkaline earth metals such as magnesium and calcium, titanium, zirconium, chromium, manganese, iron, cobalt, nickel, copper, zinc, etc. Transition metals, aluminum and the like. From the viewpoints of gas barrier properties, resistance to high-temperature steam and hot water, and productivity, the polyvalent metal is preferably a divalent metal having a metal ion valence of 2. In terms of oxygen barrier properties, zinc and copper are preferable, and zinc is particularly preferable.

Specific examples of the polyvalent metal compound include oxides, hydroxides, carbonates, organic acid salts and inorganic acid salts of the polyvalent metals, ammonium complexes and secondary to quaternary amine complexes of the polyvalent metals, Complex carbonates and organic acid salts, polyvalent metal alkyl alkoxides, and the like. Organic acid salts include acetate, oxalate, citrate, lactate, phosphate, phosphite, hypophosphite, stearate, monoethylenically unsaturated carboxylate, etc. Can be mentioned. Examples of inorganic acid salts include chlorides, sulfates and nitrates.
As the polyvalent metal compound, zinc oxide, copper oxide, and calcium carbonate are preferable in terms of oxygen barrier properties.

In view of transparency, oxygen barrier property, etc. of the precursor 10 for packaging material, it is preferable to use an ultrafine polyvalent metal component.
“Ultrafine particles” mean particles having an average primary particle diameter of 1 nm to 1000 nm as measured by a laser diffraction scattering method.
The average primary particle size of the ultrafine particles is preferably 200 nm or less, more preferably 150 nm or less, and particularly preferably 100 nm or less. The average primary particle diameter of the ultrafine particles is preferably 5 nm or more. If the average primary particle size of the ultrafine particles is not more than the above upper limit (200 nm), the transparency of the protective layer 3 is more excellent. Moreover, the dispersibility of the ultrafine particles in the coating liquid for the protective layer is excellent, and the liquid stability is good.
Commercially available products may be used as the ultrafine particles of the polyvalent metal component. For example, as a commercial product of zinc oxide ultrafine particles, FINEX (registered trademark) 50 (manufactured by Sakai Chemical Industry Co., Ltd., average primary particle diameter 20 nm) and ZINCOX SUPER F-2 (manufactured by Hakusui Tech Co., Ltd., average primary particle diameter 65 nm) Etc.

(Polyester resin)
The polyester resin functions as a binder for the polyvalent metal component. When the binder is a polyester resin, the transparency of the precursor 10 for packaging material is excellent as compared with the case where another binder is used.
Examples of the polyester resin include a copolymer (polycondensate) of one or both of a polybasic acid and a polybasic acid anhydride and a polyhydric alcohol. The polybasic acid, polybasic acid anhydride, and polyhydric alcohol that form the polyester resin may each be one kind or two or more kinds.

There is no limitation in particular as a polybasic acid, For example, an aromatic polybasic acid, an aliphatic polybasic acid, an alicyclic polybasic acid etc. are mentioned. Moreover, as a polybasic acid, a bifunctional polybasic acid may be used, or a trifunctional or more polybasic acid may be used.
Examples of the bifunctional aromatic polybasic acid, that is, aromatic dicarboxylic acid, include terephthalic acid, isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, biphenyldicarboxylic acid, and the like. Examples of the bifunctional aliphatic polybasic acid, that is, the aliphatic dicarboxylic acid, include saturated oxalic acid, saturated aliphatic dicarboxylic acid such as succinic acid, adipic acid, sebacic acid, dodecanedioic acid, eicosane diacid, and hydrogenated dimer acid. And fumaric acid, and unsaturated aliphatic dicarboxylic acids such as maleic acid, itaconic acid, citraconic acid, and dimer acid. Examples of the bifunctional alicyclic polybasic acid, ie, alicyclic dicarboxylic acid, include 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, and 2,5-norbornene. Examples thereof include dicarboxylic acid and tetrahydrophthalic acid.
Examples of the tribasic or higher polybasic acid include trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid, trimesic acid, ethylene glycol bis (anhydrotrimellitate), glycerol tris (anhydrotrimellitate), 1 2,3,4-butanetetracarboxylic acid and the like.

There is no limitation in particular as a polybasic acid anhydride, For example, the acid anhydride of the above-mentioned polybasic acid is mentioned. As the polybasic acid anhydride, a bifunctional polybasic acid anhydride or a trifunctional or higher polybasic acid anhydride may be used.
Examples of acid anhydrides of bifunctional polybasic acids include phthalic anhydride, succinic anhydride, maleic anhydride, itaconic anhydride, citraconic anhydride, 2,5-norbornene dicarboxylic acid anhydride, tetrahydrophthalic anhydride Etc. Examples of the acid anhydride of a tribasic or more polybasic acid include trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, and the like.

From the viewpoint of suppressing gelation during the production of the polyester resin, the acid anhydride of the tribasic acid or polybasic acid and the tribasic acid tribasic acid or more is added to 100 mol% of the polybasic acid and polybasic acid anhydride. The total amount is preferably 5 mol% or less. That is, the total amount of the bifunctional polybasic acid and the acid anhydride of the bifunctional polybasic acid is preferably 95 mol% or more.

Of the polybasic acids and polybasic acid anhydrides, aromatic dicarboxylic acids and acid anhydrides of aromatic dicarboxylic acids such as phthalic anhydride are preferred.

The polyhydric alcohol is not particularly limited, and a bifunctional polyhydric alcohol or a trifunctional or higher polyhydric alcohol may be used.
Examples of the bifunctional polyhydric alcohol include aliphatic glycols having 2 to 10 carbon atoms, alicyclic glycols having 6 to 12 carbon atoms, ether bond-containing glycols, ethylene oxide or propylene oxide adducts of bisphenols, and the like. It is done.
Examples of the aliphatic glycol having 2 to 10 carbon atoms include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 2-methyl-1,3-propanediol, 1, Examples include 5-heptanediol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,9-nonanediol, 2-ethyl-2-butylpropanediol, and the like. Examples of the alicyclic glycol having 6 to 12 carbon atoms include 1,4-cyclohexanedimethanol. Examples of the ether bond-containing glycol include diethylene glycol, triethylene glycol, dipropylene glycol, polytetramethylene glycol, polyethylene glycol, and polypropylene glycol. Examples of the bisphenols in the ethylene oxide or propylene oxide adduct of bisphenols include 2,2-bis (4- (2-hydroxyethoxy) phenyl) propane, bisphenol A, bisphenol S, and the like.
Examples of the trifunctional or higher polyhydric alcohol include glycerin, trimethylolethane, trimethylolpropane, and pentaerythritol.

From the viewpoint of suppressing gelation during the production of the polyester resin, the amount of the trifunctional or higher polyhydric alcohol is preferably 5 mol% or less with respect to 100 mol% of the polyhydric alcohol. That is, the amount of the bifunctional polyhydric alcohol is preferably 95 mol% or more.

As the polyhydric alcohol, ethylene glycol and neopentyl glycol are preferable because of their low cost.
The total amount of ethylene glycol and neopentyl glycol in 100 mol% of the polyhydric alcohol is preferably 50 mol% or more, more preferably 70 mol% or more, and may be 100 mol%.

In the polyester resin, at least one selected from the group consisting of a monocarboxylic acid, a monoalcohol, a lactone, and a hydroxycarboxylic acid together with one or both of the aforementioned polybasic acid and polybasic acid anhydride and a polyhydric alcohol. May be copolymerized. Specific examples of monocarboxylic acids, monoalcohols, lactones or hydroxycarboxylic acids include lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, benzoic acid, p-tert-butylbenzoic acid Examples include acid, cyclohexane acid, 4-hydroxyphenyl stearic acid, stearyl alcohol, 2-phenoxyethanol, ε-caprolactone, lactic acid, β-hydroxybutyric acid, p-hydroxybenzoic acid and the like.

The copolymerization (polycondensation) of either one or both of a polybasic acid and a polybasic acid anhydride and a polyhydric alcohol can be performed by a known method. For example, the esterification reaction is carried out by reacting all the monomers and at least one of their low polymers in an inert atmosphere at 180 to 260 ° C. for about 2.5 to 10 hours. Examples thereof include a method in which a polycondensation reaction proceeds in the presence of a transesterification reaction catalyst at a temperature of 220 to 280 ° C. under a reduced pressure of 130 Pa or less until a desired molecular weight is reached to obtain a polyester resin.

Examples of a method for imparting a desired acid value or hydroxyl value to a polyester resin include a method in which a polybasic acid or a polyhydric alcohol is further added to the polycondensation reaction and depolymerization is performed in an inert atmosphere. It is done. When a polybasic acid is added, the acid value increases, and when a polyhydric alcohol is added, the hydroxyl value increases.
When depolymerized, bubbles are generated in the resin, and at the time of dispensing, there are cases where pelletization cannot be performed due to the bubbles. In such a case, after depolymerization, the system may be depressurized and defoamed again. The degree of decompression at the time of re-depressurization is preferably 67,000 Pa or less, and more preferably 10,000 Pa or less. If the degree of vacuum is higher than 67,000 Pa, it takes a long time to degas even if the pressure is reduced again.
Further, as a method for imparting an acid value to the polyester resin, there may be mentioned a method in which a polybasic acid anhydride is further added following the above polycondensation reaction, and an addition reaction is performed with a hydroxyl group of the polyester resin in an inert atmosphere.

As the polyester resin, a polyester resin having a carboxyl group introduced by at least one of depolymerization using a polybasic acid and addition reaction using a polybasic acid anhydride is preferable. By introducing a carboxyl group by at least one of depolymerization and addition reaction, the molecular weight and acid value of the polyester resin can be easily controlled.
It is preferable that the polybasic acid used in the depolymerization includes a tribasic or higher polybasic acid.
By using a tribasic or higher polybasic acid, a desired acid value can be imparted while suppressing a decrease in the molecular weight of the polyester resin due to depolymerization. Further, by using a tribasic acid or polybasic acid or an acid anhydride of a trifunctional or more polybasic acid for depolymerization or addition reaction, details are unknown, but an aqueous dispersion having more excellent storage stability. Can be obtained.

Examples of the polybasic acid or acid anhydride of the polybasic acid used in at least one of the depolymerization and the addition reaction include the same as those mentioned above. Among them, aromatic polybasic acids and acid anhydrides of aromatic polybasic acids are preferable, terephthalic acid that is an aromatic dicarboxylic acid, isophthalic acid, phthalic anhydride that is an acid anhydride of an aromatic dicarboxylic acid, trifunctional Trimellitic acid which is a polybasic acid and trimellitic anhydride which is an acid anhydride of a trifunctional polybasic acid are preferable. In particular, when trimellitic anhydride is used, depolymerization and addition reaction are considered to occur in parallel. Therefore, it is particularly preferable to use trimellitic anhydride because a desired acid value can be imparted while minimizing the decrease in molecular weight of the polyester resin due to depolymerization.

The acid value of the polyester resin is preferably 15 mgKOH / g or less, more preferably 10 mgKOH / g or less, and particularly preferably 8 mgKOH / g or less. If an acid value is below the said upper limit (15 mgKOH / g), the water resistance of the precursor 10 for packaging materials which has the protective layer 3 will be excellent.
Although there is no particular limitation on the lower limit of the acid value of the polyester resin, it is usually 0.05 mgKOH / g or more on the limit of measurement accuracy.
The acid value of the polyester resin is measured according to JIS K0070: 1992.

The polyester resin may contain a hydroxyl group as long as the water resistance of the protective layer 3 is not impaired.
The hydroxyl value of the polyester resin is preferably 30 mgKOH / g or less, and more preferably 20 mgKOH / g or less. The lower limit of the hydroxyl value of the polyester resin is not particularly limited, but is usually 0.05 mgKOH / g or more due to the limit of measurement accuracy.

The glass transition temperature (Tg) of the polyester resin is preferably −30 ° C. or higher, more preferably 20 ° C. or higher, and particularly preferably 50 ° C. or higher. When Tg is equal to or higher than the lower limit (−30 ° C.), the packaging material precursor 10 having the protective layer 3 has excellent water resistance and heat resistance.
The upper limit of the glass transition temperature (Tg) of the polyester resin is not particularly limited, but is typically 80 ° C. or lower.

The number average molecular weight of the polyester resin is preferably 5,000 to 50,000, more preferably 9,000 to 40,000, and particularly preferably 10,000 to 30,000. When the number average molecular weight is within the above range, the water resistance and heat resistance of the packaging material precursor 10 having the protective layer 3 are more excellent.
The polyester resin contained in the protective layer 3 may be one type or two or more types.

The polyester resin contained in the protective layer 3 is preferably derived from an aqueous polyester resin dispersion. When the polyester resin derived from the aqueous polyester resin dispersion is contained, the hot water resistance of the protective layer 3 is more excellent.
The aqueous polyester resin dispersion contains a polyester resin and water as a dispersion medium.
The aqueous polyester resin dispersion preferably further contains a basic compound in order to satisfactorily disperse the polyester resin in water.
The aqueous polyester resin dispersion may further contain other components. Other components are not particularly limited. For example, surfactants, organic solvents, curing agents, compounds having a protective colloid effect, pigments such as titanium oxide, zinc white, and carbon black, dyes, aqueous urethane resins, aqueous Examples thereof include aqueous resins such as olefin resins and aqueous acrylic resins.
As the polyester resin aqueous dispersion, commercially available products may be used. For example, Elitel (registered trademark) KT-8803, Elitel KT-0507, Elitel KT-9204 (above, manufactured by Unitika Ltd.), Bironal (registered trademark) ) MD-1200, Vylonal MD-1480 (above, manufactured by Toyobo Co., Ltd.), Pesresin A124GP (manufactured by Takamatsu Yushi Co., Ltd.), and the like.

(Dispersant)
The dispersant contributes to the improvement of the dispersibility of the polyvalent metal component in the protective layer coating liquid containing the above-described polyvalent metal component and the polyester resin, and consequently the dispersibility of the polyvalent metal component in the protective layer 3. By uniformly dispersing the polyvalent metal component in the protective layer 3, the transparency of the protective layer 3 and the gas barrier property of the packaging material precursor 10 after the hot water treatment are enhanced.
The dispersant is preferably at least one selected from the group consisting of polycarboxylic acid sodium salt and polycarboxylic acid ammonium salt. Polycarboxylic acid sodium salt and polycarboxylic acid ammonium salt have high adsorbability on the polyvalent metal component surface. In addition, since an electric repulsion due to ionization after adsorbing on the surface of the polyvalent metal component is likely to occur, it contributes to suitable dispersion of the polyvalent metal component. The polycarboxylic acid sodium salt and the polycarboxylic acid ammonium salt have properties that are physically and chemically similar to the polycarboxylic acid polymer contained in the gas barrier layer 2. Therefore, when the protective layer 3 is formed adjacent to the gas barrier layer 2, it is possible to obtain a packaging material precursor 10 that is less susceptible to poor transparency due to the reaction between the layers and that is excellent in transparency.

As polycarboxylic acid in polycarboxylic acid sodium salt or polycarboxylic acid ammonium salt, the homopolymer or copolymer of unsaturated carboxylic acid is mentioned, for example.
Examples of the unsaturated carboxylic acid include acrylic acid, maleic acid, methacrylic acid, itaconic acid, fumaric acid, crotonic acid and the like.
The copolymer of unsaturated carboxylic acid includes a copolymer of two or more unsaturated carboxylic acids, a copolymer of one or more unsaturated carboxylic acids and one or more other monomers, and the like. Can be mentioned. The copolymer of two or more unsaturated carboxylic acids may be a copolymer of two or more unsaturated carboxylic acids and another monomer.

The polycarboxylic acid sodium salt may be a polycarboxylic acid sodium salt obtained by neutralizing a carboxyl group of a polycarboxylic acid obtained by (co) polymerizing an unsaturated carboxylic acid with sodium. Polycarboxylic acid sodium salt obtained by (co) polymerizing the sodium salt of an acid may also be used.
The polycarboxylic acid ammonium salt may be a polycarboxylic acid ammonium salt obtained by neutralizing a carboxyl group of a polycarboxylic acid obtained by (co) polymerizing an unsaturated carboxylic acid with ammonia. It may be a polycarboxylic acid ammonium salt obtained by (co) polymerizing an ammonium salt of an acid.
A dispersing agent may be used individually by 1 type, and 2 or more types may be mixed and used for it.

(Isocyanate compound)
The isocyanate compound means a compound having at least one isocyanate group in the molecule. When the protective layer 3 contains an isocyanate compound, the film forming property of the protective layer 3, the hot water resistance, and the adhesion with the gas barrier layer 2 are more excellent.
The isocyanate compound is preferably a polyisocyanate compound having at least two isocyanate groups in the molecule, such as phenylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, naphthylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, hydrogen. Examples thereof include organic diisocyanate compounds such as added diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate, hydrogenated toluene diisocyanate or tetramethylene xylylene diisocyanate, and derivatives of the organic polyisocyanate compound.

When the protective layer 3 is formed using a protective layer coating solution containing water, it is preferable to use an isocyanate compound (water-dispersible isocyanate compound) having dispersibility in water. As the water-dispersible isocyanate compound, for example, (1) a part of the isocyanate group of the organic polyisocyanate compound is modified with a hydrophilic group such as polyethylene oxide, carboxy group, or sulfonic acid group to be a self-emulsifying type. An isocyanate compound, (2) an isocyanate compound in which the organic polyisocyanate compound is forcibly emulsified with a surfactant or the like so that it can be dispersed in water, (3) various prepolymers derived from the organic polyisocyanate compound, (4 ) A compound in which a part of the isocyanate group in the organic polyisocyanate is blocked with a blocking agent such as alcohols, phenols, oximes, mercaptans, amides, imides or lactams, so-called blocked polyisocyanate compounds Etc.
An isocyanate compound may be used individually by 1 type, and may be used in combination of 2 or more type.

(Other ingredients)
Examples of other components include softeners, stabilizers, film forming agents, thickeners, and the like.

(Content of each component)
The content of the polyvalent metal component in the protective layer 3 is 40 to 90% by mass, preferably 50 to 85% by mass, and more preferably 60 to 80% by mass with respect to the total mass of the protective layer 3. If content of a polyvalent metal component is in the said range, the gas barrier property of the packaging material obtained by carrying out the hot water process of the precursor 10 for packaging materials will be more excellent.

The content of the polyester resin in the protective layer 3 is preferably 10 to 60% by mass and more preferably 20 to 40% by mass with respect to the total mass of the protective layer 3. If content of a polyester resin is in the said range, the water resistance of the precursor 10 for packaging materials, heat resistance, and transparency will be more excellent.

The content of the dispersant in the protective layer 3 is 2 to 20% by mass, preferably 2 to 15% by mass, and more preferably 2 to 10% by mass with respect to the polyvalent metal component. When the content of the dispersant is within the above range, the dispersibility of the polyvalent metal component in the protective layer coating liquid, and thus the uniformity of the dispersion of the polyvalent metal component in the protective layer 3 is further improved. Therefore, the transparency of the protective layer 3 and the gas barrier property of the packaging material obtained by hydrothermal treatment of the packaging material precursor 10 are more excellent.

When the protective layer 3 contains an isocyanate compound, the content of the isocyanate compound in the protective layer 3 is preferably 1 to 20% by mass and more preferably 2 to 15% by mass with respect to the total mass of the protective layer 3. If content of an isocyanate compound is in the said range, the film-forming property of the protective layer 3, hot water resistance, and adhesiveness with the gas barrier layer 2 will be more excellent. Moreover, the gas barrier property of the packaging material obtained by carrying out the hot water process of the packaging material precursor 10 is more excellent. In addition, when another substrate is laminated on the protective layer 3 via an adhesive layer as shown in a third embodiment to be described later, the adhesion to other substrates is also excellent.

The total content of the polyvalent metal component, the polyester resin, the dispersant, and the isocyanate compound in the protective layer 3 is preferably larger than 95% by mass and larger than 97% by mass with respect to the total mass of the protective layer 3. More preferably, it may be 100% by mass.
The content of other components in the protective layer 3 is preferably less than 5% by mass and more preferably less than 3% by mass with respect to the total mass of the protective layer 3.

Mass per unit area of the protective layer 3 is preferably 0.1 ~ 10g / ^{m 2,} more preferably 0.1 ~ 6g / ^{m 2,} more preferably 0.1 ~ 2g / ^{m 2.} If the mass per unit area of the protective layer 3 is not less than the above lower limit (0.1 g / m ² ), the gas barrier property is more excellent, and if it is not more than the above upper limit (10 g / m ² ), the appearance is good. is there.

The thickness of the protective layer 3 is preferably 0.05 to 5 μm, more preferably 0.1 to 3 μm, and further preferably 0.1 to 1 μm. If the thickness of the protective layer 3 is not less than the above lower limit (0.05 μm), the gas barrier property is more excellent, and if it is not more than the above upper limit (5 μm), the appearance is good.

[Method for producing precursor for packaging material]
The packaging material precursor 10 can be manufactured, for example, by a manufacturing method including the following steps (α1) and (α2).
(Α1): A step of forming the gas barrier layer 2 by applying the following coating liquid for gas barrier layer on one surface of the support 1 and drying it.
(Α2): A step of forming the protective layer 3 by applying the following protective layer coating liquid on the surface of the gas barrier layer 2 and drying it.

(Gas barrier layer coating solution)
The gas barrier layer coating liquid contains a polycarboxylic acid polymer, a silicon compound (i), and a liquid medium. The gas barrier layer coating solution may further contain other components than the polycarboxylic acid polymer and the silicon compound (i) as necessary.

The polycarboxylic acid polymer in the gas barrier layer coating solution is the same as the polycarboxylic acid polymer in the gas barrier layer 2 except that the neutralization degree of the carboxyl group with the polyvalent metal is 0 mol%. There are also preferred embodiments.
When the coating liquid for the protective layer is applied to the surface of the gas barrier layer 2, polyvalent metal ions and moisture are supplied, and an ionic crosslinking reaction with the polyvalent metal ions of the carboxyl group of the polycarboxylic acid polymer proceeds. At this time, the lower the degree of neutralization of the carboxyl group, the easier the ion crosslinking reaction proceeds.
When the degree of neutralization is greater than 0 mol% and less than or equal to 40 mol%, the ionic cross-linking reaction is difficult to proceed when the protective layer coating liquid is applied onto the gas barrier layer 2, and the ratio (α / β) is 1 or more. Difficult to do.
If the degree of neutralization is greater than 40 mol%, the gas barrier layer coating solution gels, making application difficult.

In addition, it is considered that the carboxyl group of the polycarboxylic acid polymer is more easily ion-crosslinked as it is closer to the coating surface of the protective layer coating solution. Therefore, it is considered that the degree of ionic crosslinking by the polyvalent metal in the gas barrier layer 2 increases as the protective layer 3 is closer. For example, when the neutralization degree is 0 mol%, in the gas barrier layer 2, the ionic crosslinking degree changes from 0 mol% to 100 mol% from the vicinity of the interface with the support 1 to the vicinity of the interface with the protective layer 3, It is conceivable that the ionic crosslinking degree as a whole is about 50 mol%. On the other hand, when the neutralization degree is about 20 mol%, in the gas barrier layer 2, the ionic crosslinking degree is about 20 mol% to about 25 mol% from the vicinity of the interface with the support 1 to the vicinity of the interface with the protective layer 3. It can be considered that only changes.

The silicon compound (i) and other components in the gas barrier layer coating liquid are the same as the silicon compound (i) and other components in the gas barrier layer 2, respectively, and the preferred embodiments are also the same.

The liquid medium is not particularly limited, and water, an organic solvent, a mixed solvent of water and an organic solvent, or the like can be used. When the silicon compound (i) contains a hydrolyzable silane compound, the liquid medium preferably contains water in order to perform a hydrolysis reaction of the hydrolyzable silane compound.

The organic solvent is preferably at least one selected from the group consisting of lower alcohols having 1 to 5 carbon atoms and lower ketones having 3 to 5 carbon atoms. Specific examples include methanol, ethanol, propanol, 2-propanol, n-butanol, isobutanol, sec-butanol, tert-butanol, acetone, and methyl ethyl ketone.

As a mixed solvent of water and an organic solvent, a mixed solvent using the above-described organic solvent is preferable, and a mixed solvent of water and a lower alcohol having 1 to 5 carbon atoms is more preferable.
As a mixed solvent, water is present in an amount of 20 to 95% by mass, and the organic solvent is present in an amount of 80 to 5% by mass (provided that the total of water and the organic solvent is 100% by mass). Is preferred.

As the liquid medium, water is preferable in terms of solubility and cost of the polycarboxylic acid polymer. From the viewpoint of the solubility of the hydrolyzable silane compound and the coating properties of the gas barrier layer coating solution, it is preferable to contain a lower alcohol having 1 to 5 carbon atoms. Accordingly, water or a mixed solvent of water and a lower alcohol having 1 to 5 carbon atoms is preferable.

The content of the silicon compound (i) in the gas barrier layer coating solution is 2 to 25% by mass, preferably 2 to 20% by mass, based on the polycarboxylic acid polymer (100% by mass). When the content of the silicon compound (i) is within the above range, the adhesion between the gas barrier layer 2 and the support 1 is excellent. Moreover, the water resistance of the packaging material obtained from the precursor 10 for packaging materials is more excellent, and it is hard to whiten when exposed to cold water.
Here, the mass of the silicon compound (i) other than the hydrolyzable silane compound is the mass in terms of the hydrolyzable silane compound as described above.

The content of other components in the gas barrier layer coating solution is preferably 30% by mass or less, more preferably 20% by mass or less, relative to the polycarboxylic acid polymer (100% by mass).

In the gas barrier layer coating solution, from the viewpoint of gas barrier properties and coating properties, the polycarboxylic acid polymer in the gas barrier layer coating solution, the silicon compound (i), and other components included as necessary Is preferably 0.5 to 50% by mass, more preferably 0.8 to 30% by mass, based on the total mass of the gas barrier layer coating liquid. It is particularly preferably 1.0 to 20% by mass.

The total content of the polycarboxylic acid polymer and the silicon compound (i) in the gas barrier layer coating solution is preferably 70% by mass or more, more preferably 80% by mass or more, based on the solid content mass in the gas barrier layer coating solution. Is more preferable, and may be 100% by mass.
The mass of the silicon compound (i) other than the hydrolyzable silane compound is the mass in terms of the hydrolyzable silane compound as described above.

The coating liquid for gas barrier layer can be prepared by mixing each component.
When a polyvalent metal component is added during the preparation of the gas barrier layer coating solution, the carboxyl group is neutralized by the reaction of the polycarboxylic acid polymer and the polyvalent metal component in the gas barrier layer coating solution. Is not 0 mol%. Therefore, a polyvalent metal component is not blended in the gas barrier layer coating liquid.
When the gas barrier layer coating liquid contains a hydrolytic condensate as the silicon compound (i), the hydrolyzable silane compound is directly mixed with the liquid containing the polycarboxylic acid polymer and water to form a gas barrier layer coating liquid. May be prepared. Also, by adding water to the hydrolyzable silane compound, hydrolysis and subsequent condensation reaction are performed, and the resulting hydrolyzed condensate is mixed with a polycarboxylic acid polymer to prepare a gas barrier layer coating solution. May be.

(Protective layer coating solution)
The coating liquid for protective layers contains a polyvalent metal component, a polyester resin, a dispersant, and water. The protective layer coating liquid preferably further contains an isocyanate compound. The coating liquid for protective layer may further contain other components other than the polyvalent metal component, the polyester resin, the dispersant, and the isocyanate compound as necessary. The protective layer coating solution may further contain an organic solvent.

The polyvalent metal component, the polyester resin, the dispersant, the isocyanate compound, and other components are the same as the polyvalent metal component, the polyester resin, the dispersant, the isocyanate compound, and other components, respectively, in the protective layer 3 described above. The preferred embodiment is also the same.
Examples of the organic solvent include ethanol, 2-propanol, ethylene glycol monobutyl ether and the like from the viewpoint of improving coating properties and drying efficiency. When these organic solvents are contained in the coating liquid for the protective layer, they may be contained singly or in combination of two or more.
The content of the organic solvent is such that water is present in an amount of 20 to 95% by mass, and the organic solvent is present in an amount of 80 to 5% by mass when the total of water and the organic solvent is 100% by mass. An amount is preferred.

The solid concentration of the protective layer coating solution is preferably 3 to 30% by mass, more preferably 5 to 20% by mass.
Solid content concentration is the ratio of the total solid content with respect to the whole quantity (100 mass%) of the coating liquid for protective layers.
The total solid content of the protective layer coating liquid is the total amount of the polyvalent metal component in the protective layer coating liquid, the polyester resin, the dispersant, the isocyanate compound, and the other components that are solid ( Including the case of not containing an isocyanate compound and the case of not containing a solid component among other components).

The content of the polyvalent metal component in the protective layer coating solution is 40 to 90% by weight, preferably 50 to 85% by weight, preferably 60 to 85% by weight based on the total solid content (100% by weight) of the protective layer coating solution. 80 mass% is more preferable.

The content of the polyester resin in the protective layer coating solution is preferably 10 to 60% by mass, more preferably 20 to 40% by mass, based on the total solid content of the protective layer coating solution.

The content of the dispersant in the protective layer coating solution is 2 to 20% by mass, preferably 2 to 15% by mass, and more preferably 2 to 10% by mass with respect to the polyvalent metal component.

When the protective layer coating solution contains an isocyanate compound, the content of the isocyanate compound in the protective layer coating solution is preferably 1 to 20% by mass, preferably 2 to 15% by mass, based on the total solid content of the protective layer coating solution. Is more preferable.

Among the other components in the protective layer coating solution, the content of the solid component is preferably less than 5% by mass and more preferably less than 3% by mass with respect to the total solid content of the protective layer coating solution. That is, the total amount of the polyvalent metal component, the polyester resin, the dispersant, and the isocyanate compound in the protective layer coating liquid is preferably greater than 95% by mass and greater than 97% by mass with respect to the total solid content. More preferred.

The method for preparing the protective layer coating liquid is not particularly limited, and the protective layer coating liquid can be obtained by mixing the above-described components uniformly.

In this embodiment, the polyester resin is preferably derived from the aqueous polyester resin dispersion as described above. That is, the method for preparing the protective layer coating liquid is preferably a method of mixing a polyvalent metal component, an aqueous polyester resin dispersion, a dispersant, and, if necessary, water, an isocyanate compound, and other components.

The following method is mentioned as a preferable example of the preparation method of the coating liquid for protective layers. First, zinc oxide ultrafine particles and a dispersing agent are added to distilled water to break up and disperse the aggregation of primary particles of zinc oxide ultrafine particles. As a result, an aqueous dispersion of zinc oxide ultrafine particles is obtained, and distilled water, an aqueous polyester resin dispersion, and a water-dispersible isocyanate compound are added to the aqueous dispersion of zinc oxide ultrafine particles and stirred. If necessary, an organic solvent such as 2-propanol is added and stirred to obtain a protective layer coating solution.
A bead mill, a high-speed stirrer, or the like can be used for crushing the aggregates when obtaining the aqueous dispersion of zinc oxide ultrafine particles. In particular, when a bead mill is used, the haze of the resulting packaging material precursor tends to be small, which is preferable.

Other preferable examples of the method for preparing the protective layer coating liquid include the following methods. First, distilled water is added to a water-dispersible isocyanate compound in advance and stirred to obtain an aqueous dispersion of the water-dispersible isocyanate compound. Separately, an aqueous dispersion of zinc oxide ultrafine particles is obtained in the same manner as described above, and an aqueous polyester resin dispersion is added to the aqueous dispersion of zinc oxide ultrafine particles. The aqueous dispersion of the water-dispersible isocyanate compound is added to the obtained dispersion and stirred. If necessary, an organic solvent such as 2-propanol is added and stirred to obtain a protective layer coating solution.

(Process (α1))
The gas barrier layer 2 is formed by applying the gas barrier layer coating liquid on the support 1 and removing the liquid medium of the gas barrier layer coating liquid by drying.
The coating method of the gas barrier layer coating liquid is not particularly limited. For example, the casting method, dipping method, roll coating method, gravure coating method, screen printing method, reverse coating method, spray coating method, kit coating method, die coating method. Method, metering bar coating method, chamber doctor combined coating method, curtain coating method and the like.

The drying method is not particularly limited, and examples thereof include a hot air drying method, a hot roll contact method, an infrared heating method, and a microwave heating method. The methods may be performed alone or in combination. The drying temperature is not particularly limited, but when the above-mentioned water or a mixed solvent of water and an organic solvent is used as a solvent, it is usually preferably 50 to 160 ° C. The pressure during drying is usually preferably normal pressure or reduced pressure, and preferably normal pressure from the viewpoint of facility simplicity.

For the purpose of increasing the proportion of the condensate in the silicon compound (i) contained in the gas barrier layer 2, heat treatment may be performed when drying is completed (or almost completed). The heat treatment is usually carried out at a temperature of 120 to 240 ° C., preferably 150 to 230 ° C., usually 10 seconds to 30 minutes, preferably 20 seconds to 20 minutes.
The drying and heat treatment have portions where conditions such as temperature overlap, but these do not need to be clearly distinguished and may be performed continuously.

(Process (α2))
The protective layer is applied by applying the protective layer coating liquid to the surface of the gas barrier layer 2 formed in the step (α1) and removing the water (including the organic solvent in the case of including the organic solvent) by drying. 3 is formed.
The coating method for the protective layer coating liquid is not particularly limited. For example, a casting method, dipping method, roll coating method, gravure coating method, screen printing method, reverse coating method, spray coating method, kit coating method, die coating method. Method, metering bar coating method, chamber doctor combined coating method, curtain coating method and the like.

The drying method is not particularly limited, and examples thereof include a hot air drying method, a hot roll contact method, an infrared heating method, and a microwave heating method, and these methods may be performed alone or in combination. The drying temperature is not particularly limited, but is usually preferably 50 to 160 ° C. The pressure during drying is usually preferably normal pressure or reduced pressure, and preferably normal pressure from the viewpoint of facility simplicity.

[Use]
The packaging material precursor 10 is useful as a packaging material precursor as shown below, or for the production of a package in which an article to be packaged is packaged with a packaging material.

<Packaging materials>
The packaging material 11 is the same as the packaging material precursor 10 except that it has the gas barrier layer 4 instead of the gas barrier layer 2, and the support 1, the gas barrier layer 4, and the protective layer 3 are laminated adjacently in this order. A laminated structure is provided.

Gas barrier layer 4 of the packaging material 11, the maximum peak height in absorbance within the range of the wave number ^1490cm ^-1 ~ ^1659cm -1 and (alpha), the maximum peak absorbance in the range of the wave number ^{1660 cm} -1 ~ 1750 cm ^-1 It is the same as the gas barrier layer 2 of the precursor 10 for packaging material, except that the ratio (α / β) to the height (β) is 7 or more.

The packaging material 11 can be obtained by subjecting the packaging material precursor 10 to a hot water treatment.
Examples of the hot water treatment include retort treatment and boil treatment. The retort process and the boil process will be described in detail in the subsequent manufacturing method of the package.
When the packaging material precursor 10 is hydrothermally treated, moisture is supplied to the gas barrier layer 2 and the protective layer 3. Therefore, ionic crosslinking by polyvalent metal ions of the carboxyl group of the polycarboxylic acid polymer contained in the gas barrier layer 2 proceeds, and the ratio (α / β) increases from a range of 1 to less than 7 to 7 or more, and the gas barrier layer 2 becomes the gas barrier layer 4. Thereby, the packaging material 11 is obtained.

If the ratio (α / β) of the gas barrier layer 2 before the hot water treatment is 1 or more and less than 7, the gas barrier layer 2 is unlikely to expand due to moisture supplied via the support 1. If the ratio (α / β) after the hydrothermal treatment is 7 or more, the ionic crosslinking degree of the carboxyl group of the polycarboxylic acid polymer is sufficiently high. Therefore, the crosslink density of the gas barrier layer 4 after the hot water treatment is sufficiently high, and the gas barrier layer 4 exhibits excellent gas barrier properties even under high humidity conditions.

The oxygen permeability of the packaging material 11, that is, the packaging material precursor 10 after the hot water treatment is preferably 50 cm ³ (STP) / (m ² · day · MPa) or less, and 20 cm ³ (STP). ) / (M ² · day · MPa) or less, more preferably 10 cm ³ (STP) / (m ² · day · MPa) or less. The lower the oxygen permeability, the better. The lower limit is not particularly limited, but it is usually 0.1 cm ³ / (m ² · day · MPa) or more.
The oxygen permeability is a value measured under conditions of a temperature of 30 ° C. and a relative humidity (RH) of 70% in accordance with ASTM F1927-98 (2004). (STP) means standard conditions (0 ° C., 1 atm) for defining the volume of oxygen.

<Manufacturing method of package>
A package body in which the packaged material is packaged with the packaging material 11 can be obtained by packaging the packaged material using the packaging material precursor 10 and subjecting the packaged material to hot water treatment.
The package is not particularly limited, but is preferably an article that easily deteriorates due to the influence of oxygen, water vapor, or the like, for example, an article such as a food, a precision metal part such as a beverage, a medicine, or an electronic part, and a food is particularly preferred. Examples of food include miso, pickles, liquid soup, and processed meat.
It does not specifically limit as a method of packaging a to-be-packaged object. For example, the precursor 10 for packaging materials is processed into the bag shape which has opening, the to-be-packaged object is accommodated in this, and the method of sealing an opening is mentioned.

Examples of the hot water treatment include retort treatment and boil treatment.
Hereinafter, although the conditions of a retort process and a boil process are demonstrated, the said conditions can be suitably changed according to a to-be-packaged object.
Retort treatment is a method of sterilizing microorganisms such as molds, yeasts, and bacteria in order to preserve foods and the like in general. Usually, the packaging material precursor 10 in which an article to be packaged is packaged is sterilized under pressure at 105 to 140 ° C. and 0.15 to 0.3 MPa for 10 to 120 minutes. The retort apparatus includes a steam type using heated steam, a hot water type using pressurized superheated water, and the like, and can be appropriately used depending on the sterilization conditions of food to be packaged.
The boil treatment is a method of sterilizing with wet heat to preserve foods and the like. Usually, although depending on the package, the packaging material precursor 10 in which the package is packaged is sterilized at 60 to 100 ° C. under atmospheric pressure for 10 to 120 minutes. The boil treatment is usually performed using a hot water tank. There are a batch type which is immersed in a hot water tank at a constant temperature and taken out after a predetermined time, and a continuous type which is sterilized through a tunnel type through the hot water tank.

<< Second Embodiment >>
FIG. 3 is a schematic cross-sectional view of the packaging material precursor 20 according to the second embodiment of the present invention. FIG. 4 is a schematic cross-sectional view of the packaging material 21 obtained from the packaging material precursor 20. In the embodiment described below, the same reference numerals are given to the components corresponding to the previous embodiment, and the detailed description thereof is omitted.
The packaging material precursor 20 of the present embodiment has a laminated structure in which the support 7, the gas barrier layer 2, and the protective layer 3 are laminated adjacently in this order. That is, in the packaging material precursor 20 of the present embodiment, the gas barrier layer 2 is directly provided on the support 7, and the protective layer 3 is directly provided on the gas barrier layer 2.
The support 7 has a base material 5 and an anchor coat layer 6 provided adjacent to one side (gas barrier layer 2 side) of the base material 5.
The packaging material 21 is the same as the packaging material precursor 20 except that the gas barrier layer 2 is the gas barrier layer 4.

<Precursor for packaging materials>
(Support)
The water vapor permeability of the support 7 is 100 g / m ² or more, and more preferably 120 g / m ² or more, like the water vapor permeability of the support 1.

As the base material 5 which comprises the support body 7, the structure similar to the support body 1 of 1st Embodiment is mentioned. However, the water vapor transmission rate in the state where the anchor coat layer 6 is laminated needs to be 100 g / m ² or more.

The anchor coat layer 6 is provided in order to improve the adhesion between the substrate 5 and the gas barrier layer 2.
Examples of the material constituting the anchor coat layer 6 include alkyd resins, melamine resins, acrylic resins, nitrified cotton, polyurethane resins, polyester resins, phenol resins, amino resins, fluororesins, epoxy resins, and carbodiimide group-containing resins. Examples of the resin include polyurethane resins, polyester resins, acrylic resins, epoxy resins, and carbodiimide group-containing resins. These resins may be used alone or in combination of two or more.

As the resin, a polyurethane resin is particularly preferable. As the polyol constituting the polyurethane resin, a polyester-based polyol is preferable. Examples of the polyester polyol include a polyester polyol obtained by reacting a polyvalent carboxylic acid or the like with a glycol. Examples of the polyisocyanate constituting the polyurethane resin include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, hexamethylene diisocyanate, xylylene. Examples include range isocyanate and isophorone diisocyanate.
The anchor coat layer 6 may contain a carbodiimide group-containing resin from the viewpoint of adhesion with the gas barrier layer 2.
If necessary, additives such as a curing agent and a hydrolyzable silane compound may be added to the resin. Examples of the hydrolyzable silane compound include those described above.

The thickness of the anchor coat layer 6 is preferably 0.01 to 1 μm, more preferably 0.05 to 1 μm, from the viewpoint of adhesion and appearance.
The mass per unit area of the anchor coat layer 6 is preferably 0.01 to 1 g / m ² and more preferably 0.05 to 1 g / m ² from the viewpoint of adhesion and appearance.

[Method for producing precursor for packaging material]
The packaging material precursor 20 can be manufactured, for example, by a manufacturing method including the following steps (β1), (β2), and (β3).
(Β1): A step of obtaining the support 7 by forming the anchor coat layer 6 on one surface of the substrate 5.
(Β2): A step of forming the gas barrier layer 2 by applying a coating liquid for gas barrier layer on the surface of the support 7 on the anchor coat layer 6 side and drying.
(Β3): A step of forming the protective layer 3 by applying a coating liquid for the protective layer on the surface of the gas barrier layer 2 and drying it.
The gas barrier layer coating liquid and the protective layer coating liquid are the same as in the first embodiment.

(Process (β1))
The formation method of the anchor coat layer 6 is not particularly limited, and a known method can be appropriately selected. For example, the anchor coat layer 6 can be formed by applying and drying an anchor coat layer coating solution.
Examples of the coating solution for the anchor coat layer include a coating solution containing the above-described resin or its precursor, a solvent, and an additive as necessary. As the resin or its precursor, a polyurethane-based, polyester-based or acrylic-based polymer material is preferable. Among these, a two-component anchor coating agent containing a main component containing a polyester-based polyol and a curing agent containing an isocyanate, which is a polyurethane-based polymer material, is preferable.

(Process (β2))
The step (β2) can be performed in the same manner as the step (α1) in the first embodiment.

(Process (β3))
The step (β3) can be performed in the same manner as the step (α2) in the first embodiment.

After forming the anchor coat layer 6 on the substrate 5 in the step (β1), after forming the gas barrier layer 2 in the step (β2), or after forming the protective layer 3 in the step (β3), An aging treatment may be performed. Examples of the aging treatment include a treatment of holding at a temperature of usually 30 to 200 ° C., preferably 30 to 150 ° C. for 0.5 to 10 days, preferably 1 to 7 days.

For the purpose of increasing the proportion of the condensate in the silicon compound (i) contained in the gas barrier layer 2, when the drying in the step (β2) is completed (or almost completed), or the step (β2) or (β3) Thereafter, the aging treatment may be performed, and heat treatment may be performed when the aging treatment is completed. The heat treatment is usually carried out at a temperature of 120 to 240 ° C., preferably 150 to 230 ° C., usually 10 seconds to 30 minutes, preferably 20 seconds to 20 minutes.
The drying, heat treatment, and aging treatment have portions where conditions such as temperature overlap, but these do not need to be clearly distinguished and may be performed continuously.

[Use]
The packaging material precursor 20 is useful as a precursor for the packaging material 21 or for producing a package in which an article to be packaged is packaged with the packaging material 21.

<Packaging materials>
The packaging material 21 is the same as the packaging material precursor 20 except that the gas barrier layer 4 is provided instead of the gas barrier layer 2, and the support 7, the gas barrier layer 4, and the protective layer 3 are laminated adjacently in this order. A laminated structure is provided.

The packaging material 21 can be obtained by subjecting the packaging material precursor 20 to hot water treatment.
The hot water treatment is the same as described above.
The preferable oxygen permeability of the packaging material 21, that is, the packaging material precursor 20 after the hot water treatment is the same as that of the first embodiment.

<Manufacturing method of package>
A package body in which the package object is packaged with the packaging material 21 can be obtained by packaging the package object using the packaging material precursor 20 and subjecting the packaged material to hot water treatment.
Packaging and hot water treatment of an article to be packaged can be performed as in the first embodiment.

«Third embodiment»
FIG. 5 is a schematic cross-sectional view of the packaging material precursor 30 according to the third embodiment of the present invention. FIG. 6 is a schematic cross-sectional view of the packaging material 31 obtained from the packaging material precursor 30.
The packaging material precursor 30 of the present embodiment includes a laminated structure in which the support 1, the gas barrier layer 2, and the protective layer 3 are laminated adjacently in this order, and the adhesive layer 9 on the surface of the laminated structure on the protective layer 3 side. The other base material 8 laminated | stacked via is provided. That is, in the packaging material precursor 30 of the present embodiment, the gas barrier layer 2 is directly provided on the support 1, and the protective layer 3 is directly provided on the gas barrier layer 2.
The packaging material 31 is the same as the packaging material precursor 30 except that the gas barrier layer 2 is the gas barrier layer 4.

<Precursor for packaging materials>
(Other base materials)
The other base material 8 is used for imparting arbitrary physical properties to the packaging material precursor 30 and the packaging material 31. Specifically, the other base material 8 can provide strength, sealability, easy-opening property at the time of sealing, design property, light blocking property, moisture-proof property, and the like. Furthermore, when performing a retort process, a boil process, etc., the protective layer 3 is not directly exposed to a hot water or a vapor | steam, and an external appearance becomes favorable.

The other substrate 8 is appropriately selected depending on the purpose, but plastic films are preferable. The other substrate 8 may be a laminate having two or more layers.
Examples of the material of the other base material 8 include polyolefin, nylon, and inorganic vapor-deposited nylon.
The thickness of the other substrate 8 is preferably 1 to 1000 μm, and more preferably 5 to 500 μm.

(Adhesive layer)
The adhesive layer is a layer that adheres the protective layer 3 and the other substrate 8.
The material of the adhesive layer 9 is not particularly limited. For example, when another substrate 8 is laminated by a dry laminating method, the adhesive layer 9 can be formed using a one-pack type or two-pack type polyurethane adhesive or acrylic adhesive. In the case of laminating another substrate 8 by the extrusion laminating method, an adhesive resin such as an ethylene-vinyl acetate copolymer, an ethylene-acrylic acid copolymer, an ethylene-methacrylic acid copolymer, or an ionomer resin. Can be used to form the adhesive layer 9.

[Method for producing precursor for packaging material]
The packaging material precursor 30 can be manufactured, for example, by a manufacturing method including the following steps (γ1), (γ2), and (γ3).
(Γ1): A step of forming the gas barrier layer 2 by applying the following coating liquid for gas barrier layer on one surface of the support 1 and drying it.
(Γ2): A step of forming the protective layer 3 by applying the following protective layer coating liquid on the surface of the gas barrier layer 2 and drying it.
(Γ3): A step of laminating another substrate 8 on the protective layer 3 via the adhesive layer 9.

(Process (γ1))
The step (γ1) can be performed in the same manner as the step (α1) in the first embodiment.

(Process (γ2))
Step (γ2) can be performed in the same manner as step (α2) in the first embodiment.

(Process (γ3))
The method for laminating the other substrate 8 is not particularly limited, and examples thereof include a dry laminating method and an extrusion laminating method.
The method for applying the adhesive in the dry laminating method is not particularly limited, and examples thereof include a gravure coating method.

[Use]
The packaging material precursor 30 is useful as a precursor for the packaging material 31 or for producing a package in which an object to be packaged is packaged with the packaging material 31.

<Packaging materials>
The packaging material 31 is the same as the packaging material precursor 30 except that the packaging material 31 has the gas barrier layer 4 instead of the gas barrier layer 2. The packaging material 31 includes a laminated structure in which the support 1, the gas barrier layer 4, and the protective layer 3 are laminated adjacent to each other in this order, and other layers laminated on the surface of the laminated structure on the protective layer 3 side through an adhesive layer 9 A substrate 8.

The packaging material 31 can be obtained by subjecting the packaging material precursor 30 to hot water treatment.
The hot water treatment is the same as described above.
The preferable oxygen permeability of the packaging material 31, that is, the packaging material precursor 30 after the hot water treatment is the same as that of the first embodiment.

<Manufacturing method of package>
A package body in which the packaged material is packaged with the packaging material 31 can be obtained by packaging the packaged material using the packaging material precursor 30 and subjecting the packaged material to hot water treatment.
Packaging and hot water treatment of an article to be packaged can be performed as in the first embodiment.
When the other base material 8 functions as a sealant layer, it can be made into a bag shape by heat-sealing the outer edge with the other base material 8 side surfaces of the packaging material precursor 30 facing each other. Examples of the form of the bag include a three-side seal, a four-side seal, a standing pouch, and pillow packaging.

<< Fourth Embodiment >>
FIG. 7 is a schematic cross-sectional view of the packaging material precursor 110 according to the fourth embodiment of the present invention. FIG. 8 is a schematic cross-sectional view of the packaging material 111 obtained from the packaging material precursor 110.
The packaging material precursor 110 of the present embodiment has a laminated structure in which a support 101, an intermediate layer 103, and a gas barrier layer 102 are laminated adjacently in this order. That is, in the packaging material precursor 110 of this embodiment, the intermediate layer 103 is directly provided on the support 101 and the gas barrier layer 102 is directly provided on the intermediate layer 103.
The packaging material 111 is the same as the packaging material precursor 110 except that the gas barrier layer 102 is the gas barrier layer 104.

<Precursor for packaging materials>
[Support]
The support body 101 of this embodiment has the same configuration as the support body 1 of the first embodiment.

[Middle layer]
The intermediate layer 103 of this embodiment is formed on one surface of the support 101. Other than that, it has the same configuration as the protective layer of the first embodiment. That is, the intermediate layer 103 includes the same polyvalent metal component as that of the protective layer of the first embodiment, a polyester resin, and a dispersant. The intermediate layer 103 preferably further contains the same isocyanate compound as that of the protective layer of the first embodiment.
The intermediate layer 103 may further include other components other than the polyvalent metal component, the polyester resin, the dispersant, and the isocyanate compound, similarly to the protective layer of the first embodiment. When the isocyanate compound is contained in the intermediate layer 103, the film formability of the intermediate layer 103, the hot water resistance, and the adhesion with the gas barrier layer 102 and the support 101 are further improved.

[Gas barrier layer]
The gas barrier layer 102 of this embodiment is formed on the intermediate layer 103 formed on one surface of the support 101. Other than that, it has the same configuration as the gas barrier layer 2 of the first embodiment. That is, the gas barrier layer 102 of the present embodiment is a group consisting of the same polycarboxylic acid polymer as the gas barrier layer 2 of the first embodiment, a hydrolyzable silane compound, a hydrolyzate thereof, and a condensate thereof. It is a layer containing at least one selected silicon compound (hereinafter also referred to as “silicon compound (i)”).
The gas barrier layer 102 may further contain other components other than the polycarboxylic acid-based polymer and the silicon compound (i) as necessary, like the gas barrier layer 2 of the first embodiment.

[Method for producing precursor for packaging material]
The packaging material precursor 110 can be manufactured, for example, by a manufacturing method including the following steps (α11) and (α12).
(Α11): A step of forming the intermediate layer 103 by applying the following intermediate layer coating solution on one surface of the support 101 and drying it.
(Α12): A step of forming the gas barrier layer 102 by applying the following gas barrier layer coating liquid onto the surface of the gas barrier layer 102 and drying it.

(Interlayer coating solution)
The intermediate layer coating solution contains a polyvalent metal component, a polyester resin, a dispersant, and a liquid medium. The intermediate layer coating solution preferably further contains an isocyanate compound. The intermediate layer coating solution may further contain other components other than the polyvalent metal component, the polyester resin, the dispersant, and the isocyanate compound, if necessary.

The polyvalent metal component, the polyester resin, the dispersant, the isocyanate compound, and other components are the same as the polyvalent metal component, the polyester resin, the dispersant, the isocyanate compound, and the other components in the intermediate layer 103, respectively. Is the same.

The liquid medium is not particularly limited, and water, an organic solvent, a mixed solvent of water and an organic solvent, or the like can be used.
Examples of the organic solvent include ethanol, 2-propanol, ethylene glycol monobutyl ether and the like from the viewpoint of improving coatability and drying efficiency. When these organic solvents are contained in the intermediate layer coating solution, they may be contained singly or in combination of two or more.
As the liquid medium, water or a mixed solvent of water and an organic solvent is preferable. The mixed solvent of water and organic solvent is preferably a mixed solvent using the organic solvent described above, wherein water is present in an amount of 20 to 95% by mass, and the organic solvent is present in an amount of 80 to 5% by mass. Those are particularly preferred.

The solid content concentration of the coating solution for the intermediate layer is preferably 3 to 30% by mass, and more preferably 5 to 20% by mass.
Solid content concentration is the ratio of the total solid content with respect to the whole quantity (100 mass%) of the coating liquid for intermediate | middle layers.
The total solid content of the intermediate layer coating liquid is the total amount of the polyvalent metal component in the intermediate layer coating liquid, the polyester resin, the dispersant, the isocyanate compound, and the other components that are solid ( Including the case of not containing an isocyanate compound and the case of not containing a solid component among other components).

The content of the polyvalent metal component in the intermediate layer coating solution is 40 to 90% by mass, preferably 50 to 85% by mass, preferably 60 to 85% by mass with respect to the total solid content (100% by mass) of the intermediate layer coating solution. 80 mass% is more preferable.

The content of the polyester resin in the intermediate layer coating solution is preferably 10 to 60% by mass, more preferably 20 to 40% by mass, based on the total solid content of the intermediate layer coating solution.

The content of the dispersant in the intermediate layer coating solution is 2 to 20% by mass, preferably 2 to 15% by mass, and more preferably 2 to 10% by mass with respect to the polyvalent metal component.

When the intermediate layer coating solution contains an isocyanate compound, the content of the isocyanate compound in the intermediate layer coating solution is preferably 1 to 20% by mass, preferably 2 to 15% by mass, based on the total solid content of the intermediate layer coating solution. Is more preferable.

In the intermediate layer coating liquid, the content of the other components that are solids is preferably less than 5% by mass and more preferably less than 3% by mass with respect to the total solid content of the intermediate layer coating liquid. That is, the total amount of the polyvalent metal component, the polyester resin, the dispersant, and the isocyanate compound in the intermediate layer coating liquid is preferably more than 95% by mass and more preferably more than 97% by mass with respect to the total solid content.

The method for preparing the intermediate layer coating liquid is not particularly limited, and the intermediate layer coating liquid can be obtained by mixing the above-described components uniformly.

In the present invention, the polyester resin is preferably derived from the aqueous polyester resin dispersion as described above, and the method for preparing the intermediate layer coating liquid includes a polyvalent metal component, an aqueous polyester resin dispersion, a dispersant, and A method in which water, an isocyanate compound, and other components are mixed as necessary is preferable.

As a preferable example of the method for preparing the coating liquid for the intermediate layer, zinc oxide ultrafine particles are obtained by adding zinc oxide ultrafine particles and a dispersant to distilled water, and crushing and dispersing the primary particles of zinc oxide ultrafine particles. A distilled dispersion, an aqueous polyester resin dispersion and a water-dispersible isocyanate compound are added to the aqueous dispersion of zinc oxide ultrafine particles and stirred. If necessary, an organic solvent such as isopropyl alcohol is added. In addition, a method of obtaining a coating solution for an intermediate layer by stirring is mentioned.
A bead mill, a high-speed stirrer, or the like can be used for crushing the aggregates when obtaining the aqueous dispersion of zinc oxide ultrafine particles. In particular, when a bead mill is used, the haze of the resulting packaging material precursor tends to be small, which is preferable.

As another preferable example of the method for preparing the intermediate layer coating solution, distilled water is added to the water-dispersible isocyanate compound in advance and stirred to obtain an aqueous dispersion of the water-dispersible isocyanate compound. An aqueous dispersion of zinc oxide ultrafine particles is obtained by the method, an aqueous polyester resin dispersion is added to the aqueous dispersion of ultrafine zinc oxide, and the aqueous dispersion of the water-dispersible isocyanate compound is added to the obtained dispersion. And a method of obtaining an intermediate layer coating liquid by adding an organic solvent such as isopropyl alcohol and stirring as necessary.

(Gas barrier layer coating solution)
The gas barrier layer coating liquid of the present embodiment contains a polycarboxylic acid polymer, a silicon compound (i), and water. The gas barrier layer coating solution may further contain other components than the polycarboxylic acid polymer and the silicon compound (i) as necessary. The gas barrier layer coating liquid may further contain an organic solvent.

The polycarboxylic acid polymer in the gas barrier layer coating liquid is the same as the polycarboxylic acid polymer in the gas barrier layer 102 except that the neutralization degree of the carboxyl group with the polyvalent metal is 20 to 50 mol%. There are also preferred embodiments.
When a gas barrier layer coating liquid containing a polycarboxylic acid polymer is applied to the surface of the intermediate layer 103, polyvalent metal ions are supplied from the intermediate layer 103 until the coating liquid dries, and the polycarboxylic acid polymer The ion cross-linking reaction by polyvalent metal ions of the carboxyl group proceeds. At this time, the lower the degree of neutralization of the carboxyl group, the easier the ion crosslinking reaction proceeds.
When the degree of neutralization is less than 20 mol%, the ionic crosslinking reaction proceeds rapidly, and the ratio (α / β) of the gas barrier layer 102 becomes 50 mol% or more.
If the neutralization degree is greater than 50 mol%, the gas barrier layer coating solution gels, making application difficult.

In addition, it is considered that the carboxyl group of the polycarboxylic acid polymer is more easily ionically cross-linked as the intermediate layer 103 is closer. Therefore, it is considered that the degree of ionic crosslinking by the polyvalent metal in the gas barrier layer 102 increases as the distance from the intermediate layer 103 increases. For example, when the degree of neutralization is 20 mol%, in the gas barrier layer 102, the degree of ionic crosslinking changes from 100 mol% to 20 mol% from the vicinity of the interface with the intermediate layer 103 to the surface on the opposite side. It is conceivable that the degree of ionic crosslinking is about 50 mol%.
On the other hand, when the neutralization degree is 0 mol%, the carboxyl group is completely ion-crosslinked before drying, and the degree of ionic cross-linking from the vicinity of the interface with the intermediate layer 103 to the vicinity of the surface on the opposite side. It is considered that the degree of ionic crosslinking is 100 mol%.

The silicon compound (i) and other components in the gas barrier layer coating solution are the same as the silicon compound (i) and other components in the gas barrier layer 102, respectively, and the preferred embodiments are also the same.

The organic solvent is preferably at least one selected from the group consisting of lower alcohols having 1 to 5 carbon atoms and lower ketones having 3 to 5 carbon atoms. Specific examples include methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, acetone, and methyl ethyl ketone.
From the viewpoint of applicability of the gas barrier layer coating solution, it is particularly preferable to contain a lower alcohol having 1 to 5 carbon atoms as the organic solvent.
The content of the organic solvent is such that water is present in an amount of 20 to 95% by mass, and the organic solvent is present in an amount of 80 to 5% by mass when the total of water and the organic solvent is 100% by mass. An amount is preferred.

The content of the silicon compound (i) in the gas barrier layer coating solution is 2 to 25% by mass, preferably 2 to 20% by mass, based on the polycarboxylic acid polymer (100% by mass). If the content of the silicon compound (i) is within the above range, the adhesion between the gas barrier layer 102 and the support 101 is excellent, and the water resistance of the packaging material obtained from the packaging material precursor 110 is more excellent, Difficult to whiten when exposed to cold water.
Here, the mass of the silicon compound (i) other than the hydrolyzable silane compound is the mass in terms of the hydrolyzable silane compound as described above.

The gas barrier layer coating liquid of this embodiment can be prepared by mixing each component.
A polycarboxylic acid polymer having a neutralization degree of 20 to 50 mol% may be used, or a gas barrier layer using a polycarboxylic acid polymer having a neutralization degree of 0 mol%. The neutralization degree may be 20 to 50 mol% when preparing the coating liquid. For example, when a polycarboxylic acid polymer having a neutralization degree of 0 mol%, a polyvalent metal component, and water are mixed, the polycarboxylic acid polymer reacts with the polyvalent metal component to neutralize the carboxyl group. The The degree of neutralization can be adjusted by the blending amount of the polyvalent metal component.
When the gas barrier layer coating liquid contains a hydrolytic condensate as the silicon compound (i), the hydrolyzable silane compound is directly mixed with the liquid containing the polycarboxylic acid polymer and water to form a gas barrier layer coating liquid. The water barrier is added to the hydrolyzable silane compound to perform hydrolysis and subsequent condensation reaction, and the resulting hydrolyzed condensate is mixed with a polycarboxylic acid polymer to form a gas barrier layer. A coating solution may be prepared.

(Process (α11))
The intermediate layer 103 is formed by applying the intermediate layer coating liquid on the support 101 and removing the liquid medium of the intermediate layer coating liquid by drying.
The coating method of the intermediate layer coating liquid is not particularly limited, and for example, a casting method, dipping method, roll coating method, gravure coating method, screen printing method, reverse coating method, spray coating method, kit coating method, die coating method. , Metal ring bar coating method, chamber doctor combined coating method, curtain coating method and the like.

(Process (α12))
A gas barrier layer coating liquid is applied to the surface of the intermediate layer 103 formed in the step (α11), and the gas barrier layer 102 is removed by drying to remove water (or an organic solvent if an organic solvent is included) in the gas barrier layer coating liquid. Is formed.
The coating method of the gas barrier layer coating liquid is not particularly limited. For example, casting method, dipping method, roll coating method, gravure coating method, screen printing method, reverse coating method, spray coating method, kit coating method, die coating method. , Metal ring bar coating method, chamber doctor combined coating method, curtain coating method and the like.

The drying method is not particularly limited, and examples thereof include a hot air drying method, a hot roll contact method, an infrared heating method, and a microwave heating method, and these methods may be performed alone or in combination. The drying temperature is not particularly limited, but when the above-mentioned water or a mixed solvent of water and an organic solvent is used as a solvent, it is usually preferably 50 to 160 ° C. The pressure during drying is usually preferably normal pressure or reduced pressure, and preferably normal pressure from the viewpoint of facility simplicity.

For the purpose of increasing the proportion of the condensate in the silicon compound (i) contained in the gas barrier layer 102, heat treatment may be performed when the drying is completed (or almost completed). The heat treatment is usually carried out at a temperature of 120 to 240 ° C., preferably 150 to 230 ° C., usually 10 seconds to 30 minutes, preferably 20 seconds to 20 minutes.
The drying and heat treatment have portions where conditions such as temperature overlap, but these do not need to be clearly distinguished and may be performed continuously.

[Use]
The packaging material precursor 110 is useful as a packaging material precursor as shown below, or for the production of a package in which an article to be packaged is packaged with a packaging material.

<Packaging materials>
The packaging material 111 of this embodiment is the same as the packaging material precursor 110 except that the gas barrier layer 104 is provided instead of the gas barrier layer 102, and the support 101, the intermediate layer 103, and the gas barrier layer 104 are adjacent in this order. And a laminated structure laminated.

Gas barrier layer 104 of the packaging material 111, the ^1490cm -1 ~ ^1659cm maximum peak height absorbance in the range of ^-1 and (alpha), the maximum peak height in absorbance within the range of the ^{1660 cm} -1 ~ 1750 cm ^-1 Except that the ratio (α / β) to (β) is 7 or more, it is the same as the gas barrier layer 102 of the packaging material precursor 110.

The packaging material 111 can be obtained by subjecting the packaging material precursor 110 to hot water treatment.
Examples of the hot water treatment include retort treatment and boil treatment. The retort process and the boil process will be described in detail in the subsequent manufacturing method of the package.
When the packaging material precursor 110 is subjected to hydrothermal treatment, moisture is supplied to the gas barrier layer 102 and the intermediate layer 103, and ionic crosslinking with polyvalent metal ions of the carboxyl group of the polycarboxylic acid polymer contained in the gas barrier layer 102 proceeds. The ratio (α / β) increases from 1 to less than 7 to 7 or more, and the gas barrier layer 102 becomes the gas barrier layer 104. Thereby, the packaging material 111 is obtained.

If the ratio (α / β) of the gas barrier layer 102 before the hot water treatment is 1 or more and less than 7, the gas barrier layer 102 is difficult to expand due to moisture supplied via the support 101. If the ratio (α / β) after the hydrothermal treatment is 7 or more, the ionic crosslinking degree of the carboxyl group of the polycarboxylic acid polymer is sufficiently high. Therefore, the crosslink density of the gas barrier layer 104 after the hot water treatment is sufficiently high, and the gas barrier layer 104 exhibits excellent gas barrier properties even under high humidity conditions.

The oxygen permeability of the packaging material 111, that is, the packaging material precursor 110 after the hot water treatment is preferably 50 cm ³ (STP) / (m ² · day · MPa) or less, and 20 cm ³ (STP). ) / (M ² · day · MPa) or less, more preferably 10 cm ³ (STP) / (m ² · day · MPa) or less. The lower the oxygen permeability, the better. The lower limit is not particularly limited, but it is usually 0.1 cm ³ / (m ² · day · MPa) or more.
The oxygen permeability is a value measured under conditions of a temperature of 30 ° C. and a relative humidity (RH) of 70% in accordance with ASTM F1927-98 (2004). (STP) means standard conditions (0 ° C., 1 atm) for defining the volume of oxygen.

<Manufacturing method of package>
Using the same method as the manufacturing method of the packaging body of the first embodiment, the packaging material is packaged using the packaging material precursor 110 and subjected to hot water treatment, so that the packaging material is packaged with the packaging material 111. Can be obtained.

«Fifth embodiment»
FIG. 9 is a schematic cross-sectional view of a packaging material precursor 120 according to a fifth embodiment of the present invention. FIG. 10 is a schematic cross-sectional view of the packaging material 121 obtained from the packaging material precursor 120. In the embodiment described below, the same reference numerals are given to the components corresponding to the previous embodiment, and the detailed description thereof is omitted.
The packaging material precursor 120 of the present embodiment has a laminated structure in which the support 107, the intermediate layer 103, and the gas barrier layer 102 are laminated adjacently in this order. That is, in the packaging material precursor 120 of this embodiment, the intermediate layer 103 is directly provided on the support 107 and the gas barrier layer 102 is directly provided on the intermediate layer 103.
The support 107 includes a base material 105 and an anchor coat layer 106 provided adjacent to one surface (on the intermediate layer 103 side) of the base material 105.
The packaging material 121 is the same as the packaging material precursor 120 except that the gas barrier layer 102 is the gas barrier layer 104.

<Precursor for packaging materials>
(Support)
Similarly to the water vapor permeability of the support 101, the water vapor permeability of the support 107 is 100 g / m ² or more, and more preferably 120 g / m ² or more.

Examples of the base material 105 constituting the support 107 include the same materials as those of the support 101 of the fourth embodiment. However, the water vapor transmission rate in a state where the anchor coat layer 106 is laminated needs to be 100 g / m ² or more.

The anchor coat layer 106 is provided to improve the adhesion between the base material 105 and the intermediate layer 103.
The anchor coat layer 106 can have the same configuration as the anchor coat layer 6 of the second embodiment.

[Method for producing precursor for packaging material]
The packaging material precursor 120 can be manufactured, for example, by a manufacturing method including the following steps (β11), (β12), and (β13).
(Β11): A step of forming the anchor coat layer 106 on one surface of the substrate 105 to obtain the support 107.
(Β12): A step of forming the intermediate layer 103 by applying the intermediate layer coating liquid to the surface of the support 107 on the anchor coat layer 106 side and drying it.
(Β13): A step of forming the gas barrier layer 102 by applying a gas barrier layer coating solution on the surface of the gas barrier layer 102 and drying it.
The intermediate layer coating solution and the gas barrier layer coating solution are the same as those in the fourth embodiment.

(Process (β11))
The formation method of the anchor coat layer 106 is not particularly limited, and a known method can be appropriately selected. For example, the anchor coat layer 106 can be formed by applying and drying an anchor coat layer coating solution.
Examples of the coating liquid for the anchor coat layer include those containing the above-mentioned resin or its precursor, a solvent, and additives as necessary. The resin or its precursor is preferably a polyurethane-based, polyester-based or acrylic-based polymer material. Among them, a two-component solution comprising a main component containing a polyester-based polyol, which is a polyurethane-based polymer material, and a curing agent containing an isocyanate. A type anchor coating agent is preferred.

(Process (β12))
The step (β12) can be performed in the same manner as the step (α11) in the fourth embodiment.

(Process (β13))
The step (β13) can be performed in the same manner as the step (α12) in the fourth embodiment.

After forming the anchor coat layer 106 on the substrate 105 in the step (β11), after forming the intermediate layer 103 in the step (β12), or after forming the gas barrier layer 102 in the step (β13), An aging treatment may be performed. Examples of the aging treatment include a treatment of holding at a temperature of usually 30 to 200 ° C., preferably 30 to 150 ° C. for 0.5 to 10 days, preferably 1 to 7 days.

For the purpose of increasing the ratio of the condensate in the silicon compound (i) contained in the gas barrier layer 102, when the drying in the step (β13) is completed (or almost completed) or after the step (β13) A heat treatment may be performed when the treatment is performed and the aging treatment is completed. The heat treatment is usually carried out at a temperature of 120 to 240 ° C., preferably 150 to 230 ° C., usually 10 seconds to 30 minutes, preferably 20 seconds to 20 minutes.
Note that the drying, heat treatment, and aging treatment have portions where conditions such as temperature overlap, but these do not need to be clearly distinguished and may be performed continuously.

[Use]
The packaging material precursor 120 is useful as a precursor for the packaging material 121 or for producing a package in which an object to be packaged is packaged with the packaging material 121.

<Packaging materials>
The packaging material 121 is the same as the packaging material precursor 120 except that it has the gas barrier layer 104 instead of the gas barrier layer 102, and the support 107, the intermediate layer 103, and the gas barrier layer 104 are laminated adjacently in this order. A laminated structure is provided.

The packaging material 121 can be obtained by subjecting the packaging material precursor 120 to hot water treatment.
The hot water treatment is the same as described above.
The preferable oxygen permeability of the packaging material 121, that is, the packaging material precursor 120 after the hot water treatment is the same as in the fourth embodiment.

<Manufacturing method of package>
A package body in which the package object is packaged with the package material 121 can be obtained by packaging the package object using the packaging material precursor 120 and performing hot water treatment.
Packaging of the package and hot water treatment can be performed in the same manner as in the fourth embodiment.

<< Sixth Embodiment >>
FIG. 11 is a schematic cross-sectional view of a packaging material precursor 130 according to a sixth embodiment of the present invention. FIG. 12 is a schematic cross-sectional view of the packaging material 131 obtained from the packaging material precursor 130.
The packaging material precursor 130 of this embodiment includes a laminated structure in which a support 101, an intermediate layer 103, and a gas barrier layer 102 are laminated adjacently in this order, and an adhesive layer 109 on the surface of the laminated structure on the gas barrier layer 102 side. And the other base material 108 laminated via. That is, in the packaging material precursor 130 of this embodiment, the intermediate layer 103 is directly provided on the support 101 and the gas barrier layer 102 is directly provided on the intermediate layer 103.
The packaging material 131 is the same as the packaging material precursor 130 except that the gas barrier layer 102 is the gas barrier layer 104.

<Precursor for packaging materials>
(Other base materials)
The other base material 108 is used for imparting arbitrary physical properties to the packaging material precursor 130 and the packaging material 131. Specifically, the other base material 108 can provide strength, sealability, easy-opening property at the time of sealing, design property, light blocking property, moisture resistance, and the like. Furthermore, when performing a retort process, a boil process, etc., the gas barrier layer 102 is not directly exposed to a hot water or a vapor | steam, and an external appearance becomes favorable.

The other substrate 108 is appropriately selected depending on the purpose, but plastic films are preferable. The other base material 108 may be a laminate having two or more layers.
Examples of the material of the other base material 108 include polyolefin, nylon, and inorganic vapor-deposited nylon.
The thickness of the other substrate 108 is preferably 1 to 1000 μm, and more preferably 5 to 500 μm.

(Adhesive layer)
The adhesive layer is a layer that adheres the intermediate layer 103 and another substrate 108.
The material of the adhesive layer 109 is not particularly limited. For example, when another substrate 108 is laminated by a dry laminating method, the adhesive layer 109 can be formed using a one-component or two-component polyurethane adhesive or an acrylic adhesive. In the case of laminating another base material 108 by an extrusion laminating method, an adhesive resin such as an ethylene-vinyl acetate copolymer, an ethylene-acrylic acid copolymer, an ethylene-methacrylic acid copolymer, or an ionomer resin is used. The adhesive layer 109 can be formed.

[Method for producing precursor for packaging material]
The packaging material precursor 130 can be manufactured, for example, by a manufacturing method including the following steps (γ11), (γ12), and (γ13).
(Γ11): A step of forming the intermediate layer 3 by applying the following intermediate layer coating solution on one surface of the support 101 and drying it.
(Γ12): A step of forming the gas barrier layer 102 by applying the following gas barrier layer coating liquid on the surface of the gas barrier layer 102 and drying it.
(Γ13): A process of laminating another base material 108 on the gas barrier layer 102 via the adhesive layer 109.

(Process (γ11))
The step (γ11) can be performed in the same manner as the step (α11) in the fourth embodiment.

(Process (γ12))
The step (γ12) can be performed in the same manner as the step (α12) in the fourth embodiment.

(Process (γ13))
The method for laminating the other base material 108 is not particularly limited, and examples thereof include a dry laminating method and an extrusion laminating method.
The method for applying the adhesive in the dry laminating method is not particularly limited, and examples thereof include a gravure coating method.

[Use]
The packaging material precursor 130 is useful as a precursor for the packaging material 131 or for producing a package in which an object to be packaged is packaged with the packaging material 131.

<Packaging materials>
The packaging material 131 is the same as the packaging material precursor 130 except that it has the gas barrier layer 104 instead of the gas barrier layer 102, and the support 101, the intermediate layer 103, and the gas barrier layer 104 are laminated adjacently in this order. A laminated structure and another base material 108 laminated with an adhesive layer 109 on the surface of the laminated structure on the intermediate layer 103 side are provided.

The packaging material 131 can be obtained by subjecting the packaging material precursor 130 to hot water treatment.
The hot water treatment is the same as described above.
The preferable oxygen permeability of the packaging material 131, that is, the packaging material precursor 130 after the hot water treatment is the same as in the fourth embodiment.

<Manufacturing method of package>
A package body in which the package object is packaged with the package material 131 can be obtained by packaging the package object using the packaging material precursor 130 and performing hot water treatment.
Packaging of the package and hot water treatment can be performed in the same manner as in the fourth embodiment.
When the other base material 108 functions as a sealant layer, it can be formed into a bag shape by heat-sealing the outer edge portion with the other base material 108 side surfaces of the packaging material precursor 130 facing each other. Examples of the form of the bag include a three-side seal, a four-side seal, a standing pouch, and pillow packaging.

While the present invention has been described with reference to the first to sixth embodiments, the present invention is not limited to these embodiments. Each configuration in the above embodiment, a combination thereof, and the like are examples, and the addition, omission, replacement, and other modifications of the configuration can be made without departing from the spirit of the present invention.
For example, in the third embodiment, the support 7 may be used instead of the support 1. Moreover, printing or vapor deposition may be given to the other base material 8 from viewpoints, such as designability provision, light-blocking provision, moisture-proof provision.
Further, in the sixth embodiment, a support 107 may be used instead of the support 101. From the viewpoints of providing design properties, providing light blocking properties, and providing moisture resistance, printing or vapor deposition may be performed on the other base material 108.

Hereinafter, the present invention will be described in detail with reference to examples. However, the present invention is not limited to these examples.
The evaluation method used below is shown below.

<Evaluation method>
[Lamination]
CPP (polypropylene film) was used on the protective layer side surface of the packaging material precursors obtained in Examples 1 to 9 and Comparative Examples 1 to 7 using a multicoater TM-MC made by HIRANO TECSEED. And pasted together. Further, an adhesive was used on the protective layer side surface of the packaging material precursors obtained in Examples 10 to 18 and Comparative Examples 8 to 15, and CPP (polypropylene) was used with a multicoater TM-MC manufactured by HIRANO TECSEED. Film). Thus, it was set as the laminated film of the structure of the precursor for packaging materials / adhesion layer / CPP. As the adhesive, a two-component curable adhesive Takelac (registered trademark) A620 (main agent) / Takenate (registered trademark) A65 (curing agent) manufactured by Mitsui Chemicals Polyurethane was used. As the CPP, Toray Film processed polypropylene film Treffan (registered trademark) ZK93KM (thickness 60 μm) was used. The obtained laminated film was cured at 40 ° C. for 3 days after being bonded.

[Abuse examination by bending]
The laminate film obtained by the above lamination was bent 50 times with a gelbo flex tester manufactured by Tester Sangyo.

[Bag making and water filling]
A three-sided pouch having a size of 100 mm × 140 mm was prepared by pasting together the CPP surfaces of the obtained laminate film obtained by the lamination or the laminate film after the abuse test with an impulse sealer. The three-way pouch was filled with 100 g of water.

[Retort processing]
For a three-way pouch filled with water, a hot water storage retort kettle manufactured by Nisaka Manufacturing Co., Ltd .: RCS-60 / 10TG, treatment temperature 120 ° C, treatment time 30 minutes, treatment tank pressure 2 kg (0.2 MPa) The retort treatment was carried out. Thereafter, water was removed from the three-way pouch, and the oxygen permeability of the laminate film constituting the three-way pouch was measured.

[Measurement of oxygen permeability (OTR)]
The oxygen permeability of the laminate film was measured under the conditions of a temperature of 30 ° C. and a relative humidity of 70% using an oxygen permeation tester OXTRAN (registered trademark) 2/20 manufactured by Modern Control. The measuring method was based on ASTM F1927-98 (2004), and the measured value was expressed in the unit cm ³ (STP) / (m ² · day · MPa). (STP) means standard conditions (0 ° C., 1 atm) for defining the volume of oxygen.
The OTR of the laminate film that has not been subjected to the abuse test is also referred to as “post-retort OTR”, and the OTR of the laminate film that has been subjected to the abuse test is also referred to as “retort OTR after abuse”.

[Measurement of water vapor permeability]
The water vapor permeability of the precursors for packaging materials obtained in the examples and comparative examples (configuration in which CPP is not laminated) was determined by using PERMATRAN-W 3/31 manufactured by Modern Control, temperature of 40 ° C., and relative humidity. The moisture permeability (WVTR) at 90% was measured.
The measuring method was based on ASTM F1249-01, and the measured value was expressed in units of g / (m ² · day).

[Measurement of infrared absorption spectrum]
The infrared absorption spectrum of the gas barrier layer of the obtained laminate film obtained by the lamination was measured by the following procedure before and after the retort treatment. The ratio of 1490cm ^-1 ~ 1659cm maximum peak height absorbance in the range of ^-1 and ^(alpha), the maximum peak height in absorbance in the range of 1660 cm -1 ~ 1750 cm ^-1 and (β) (α / β) Asked.
For Examples 1 to 9 and Comparative Examples 1 to 7, first, the CPP film of the laminate film was peeled off. Thereafter, the adhesive was dissolved using an organic solvent such as toluene, and the protective layer was removed using alcohols such as 2-propanol to expose the gas barrier layer. Next, the infrared absorption spectrum of the exposed gas barrier layer was measured by ATR method using FT-JR1710 manufactured by Perkin-Elmer.
For Examples 10 to 18 and Comparative Examples 8 to 15, first, the CPP film of the laminate film was peeled off. Thereafter, the adhesive was dissolved using an organic solvent such as toluene to expose the gas barrier layer. Next, the infrared absorption spectrum of the exposed gas barrier layer was measured by ATR method using FT-JR1710 manufactured by Perkin-Elmer.

<Preparation of coating liquid A for anchor coat layer>
[Preparation of coating liquid A-1]
Polyol, Si agent, curing agent and ethyl acetate were mixed in the formulation shown in Table 1 to prepare coating liquid A-1.
As the polyol, Mitsubishi Rayon Dianal LR209 (acrylic polyol) was used. As the Si agent, Shin-Etsu Silicone KBE9007 (3-isocyanatepropyltriethoxysilane) was used. As a curing agent, Takenate A56 (isophorone diisocyanate (IPDI) / xylylene diisocyanate (XDI)) made by Mitsui Chemicals Polyurethane was used. As ethyl acetate, Tokyo Chemical Industry ethyl acetate was used.
In Table 1, “%” of the solid content concentration is “mass%”, and the same applies to the following.

[Preparation of coating liquid A-2]
A polyol, a curing agent and ethyl acetate were mixed in the formulation shown in Table 2 to prepare a coating liquid A-2.
As a polyol, Mitsui Chemicals Polyurethane Takelac A525 (polyester polyol) was used. As a curing agent, Takenate A52 (diisocyanate) made by Mitsui Chemicals Polyurethane was used. As ethyl acetate, Tokyo Chemical Industry ethyl acetate was used.

<Preparation of coating liquid B for gas barrier layer>
A polycarboxylic acid-based polymer, a polyvalent metal compound, a Si agent, distilled water and 2-propanol are mixed in the formulation shown in Table 3, and coating liquid B (B-1, B-2, B-3, B-4) is mixed. , B′-1, B′-2, B′-3, B′-4) were prepared.
As a polycarboxylic acid polymer, Toronsei Aron A10-H (polyacrylic acid, neutralization degree 0 mol%) was used. As the polyvalent metal compound, zinc oxide (zinc oxide) manufactured by Tokyo Chemical Industry was used. As the silicon compound, KBM403 (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Silicone was used. As 2-propanol, 2-propanol produced by Tokyo Chemical Industry was used.
In Table 3, the degree of neutralization was determined as the ratio (mol%) of the number of moles in terms of polyvalent metal atom of the polyvalent metal compound to the number of moles of the carboxyl group of the polycarboxylic acid polymer. The amount of Si agent is the ratio (mass%) of the Si agent with respect to the polycarboxylic acid polymer.

<Preparation of coating liquid T for protective layer and intermediate layer>
A polyvalent metal compound, a dispersant and water were mixed in the formulation shown in Table 4 to prepare a coating liquid Ta.
As a polyvalent metal compound, FINEX50 (Zinc oxide ultrafine particles, average primary particle diameter 20 nm) manufactured by Sakai Chemical Industry was used. As a dispersant, ARON (registered trademark) T-50 (sodium polyacrylate, average molecular weight 6000) manufactured by Toagosei Co., Ltd. was used. For the stirring, T. K fill mix (high speed stirrer) was used.
The obtained coating liquid Ta, polyester resin, isocyanate compound, water and 2-propanol as a solvent were mixed in the formulation shown in Table 4, and coating liquids T (T-1 to T-3, T′-1, T′— 2) was prepared.
Unitika Elitel KT-8803 (polyester resin) was used as the polyester resin. As the isocyanate compound, Liofol Hardener UR5889-21 (hexamethylene diisocyanate polymer) manufactured by Henkel was used. As 2-propanol, 2-propanol produced by Tokyo Chemical Industry was used.
In Table 4, the polyvalent metal compound ratio is the ratio (mass%) of the polyvalent metal compound to the total solid content of the coating liquid T, and the dispersant ratio is the ratio (mass%) of the dispersant to the polyvalent metal component. It is.

<Example 1: Ny / B-1 / T-1>
On one side of a stretched nylon (Ny) film, the coating liquids B-1 and T-1 were sequentially applied using a bar coater so that the thickness after drying was 0.3 μm and 0.3 μm, respectively. Dried. Thus, a precursor for packaging material having a structure of Ny / gas barrier layer / protective layer was obtained. As a stretched Ny film, Unitika stretched nylon film emblem ONBC (thickness 15 μm) was used. The stretched Ny film had a water vapor permeability of 150 g / m ² .
The above-described evaluation ([Lamination] to [Measurement of water vapor permeability]) was performed on the obtained packaging material precursor. The results are shown in Table 5.

<Example 2: Ny / A-1 / B-1 / T-1>
On one side of the stretched Ny film, the coating solution A-1 was applied and dried using a bar coater so that the thickness after drying was 0.2 μm, thereby forming an anchor coat layer. Thus, a support having a configuration of Ny / A-1 was obtained. As the stretched Ny film, a united nylon stretched nylon film, Emblem ONBC (thickness 15 μm) was used. The water vapor permeability of the support was 150 g / m ² .
On the anchor coat layer of the support, the coating liquids B-1 and T-1 are sequentially applied and dried using a bar coater so that the thickness after drying becomes 0.3 μm and 0.3 μm, respectively. I let you. In this way, a packaging material precursor having a structure of Ny / anchor coat layer / gas barrier layer / protective layer was obtained. The above-mentioned evaluation was performed about the obtained precursor for packaging materials. The results are shown in Table 5.

<Example 3: Ny / B-1 / T-2>
A precursor for a packaging material was obtained and evaluated in the same manner as in Example 1 except that the coating liquid T-2 was used instead of the coating liquid T-1. The results are shown in Table 5.

<Example 4: Ny / B-1 / T-3>
A packaging material precursor was obtained and evaluated in the same manner as in Example 1 except that the coating liquid T-3 was used instead of the coating liquid T-1. The results are shown in Table 5.

<Example 5: Ny / B-2 / T-1>
A packaging material precursor was obtained and evaluated in the same manner as in Example 1 except that the coating liquid B-2 was used instead of the coating liquid B-1. The results are shown in Table 5.

<Example 6: Ny / A-2 / B-1 / T-1>
A packaging material precursor was obtained and evaluated in the same manner as in Example 2 except that the coating liquid A-2 was used in place of the coating liquid A-1. The results are shown in Table 5. The water vapor permeability of the support was 150 g / m ² .

<Example 7>
Coating was performed in the same manner as described above except that AQUALIC DL40S manufactured by Nippon Shokubai (sodium polyacrylate, solid content (solute) concentration 40%, average molecular weight 3500) was used instead of the dispersant in the coating liquid T-1. Liquid T-4 was prepared.
A packaging material precursor was obtained and evaluated in the same manner as in Example 1 except that the coating liquid T-4 was used instead of the coating liquid T-1. The results are shown in Table 5.

<Example 8>
Other than using Aaron A-6330 manufactured by Toagosei Co., Ltd. (sodium acrylate-maleic acid copolymer, solid content (solute) concentration 40%, average molecular weight 10,000) instead of the dispersant in the coating liquid T-1. A coating solution T-5 was prepared in the same manner as described above.
A packaging material precursor was obtained and evaluated in the same manner as in Example 1 except that the coating liquid T-5 was used instead of the coating liquid T-1. The results are shown in Table 5.

<Example 9>
The same as above except that Kao's Poise 520 (acrylic acid-maleic acid copolymer sodium, solid (solute) concentration 40%, average molecular weight 4000) was used instead of the dispersant in the coating liquid T-1. Coating liquid T-6 was prepared as described above.
A packaging material precursor was obtained and evaluated in the same manner as in Example 1 except that the coating liquid T-6 was used instead of the coating liquid T-1. The results are shown in Table 5.

<Example 10: Ny / T-1 / B-3>
On one side of a stretched nylon (Ny) film, the coating liquids T-1 and B-3 were sequentially applied using a bar coater so that the thickness after drying was 0.3 μm and 0.3 μm, respectively. Dried. In this way, a precursor for packaging material having a structure of Ny / intermediate layer / gas barrier layer was obtained. As the stretched Ny film, a stretched nylon film emblem ONBC (thickness 15 μm) manufactured by Unitika was used. The stretched Ny film had a water vapor permeability of 150 g / m ² .
The above-described evaluation ([Lamination] to [Measurement of water vapor permeability]) was performed on the obtained packaging material precursor. The results are shown in Table 5.

<Example 11: Ny / A-1 / T-1 / B-3>
On one side of the stretched Ny film, the coating liquid A-1 was applied using a bar coater so that the thickness after drying was 0.2 μm and dried to form an anchor coat layer, and Ny / A− A support having the structure of 1 was obtained. As the stretched Ny film, a stretched nylon film manufactured by Unitika, Emblem ONBC (thickness 15 μm) was used. The water vapor permeability of the support was 150 g / m ² .
On the anchor coat layer of the support, the coating liquids T-1 and B-3 are sequentially applied and dried using a bar coater so that the thickness after drying becomes 0.3 μm and 0.3 μm, respectively. Thus, a packaging material precursor having a structure of Ny / anchor coat layer / intermediate layer / gas barrier layer was obtained. The above-mentioned evaluation was performed about the obtained precursor for packaging materials. The results are shown in Table 5.

<Example 12: Ny / T-2 / B-3>
A packaging material precursor was obtained and evaluated in the same manner as in Example 10 except that the coating liquid T-2 was used instead of the coating liquid T-1. The results are shown in Table 5.

<Example 13: Ny / T-3 / B-3>
A packaging material precursor was obtained and evaluated in the same manner as in Example 10 except that the coating liquid T-3 was used instead of the coating liquid T-1. The results are shown in Table 5.

<Example 14: Ny / T-1 / B-4>
A packaging material precursor was obtained and evaluated in the same manner as in Example 10 except that the coating liquid B-4 was used instead of the coating liquid B-3. The results are shown in Table 5.

<Example 15: Ny / A-2 / T-1 / B-3>
A precursor for a packaging material was obtained and evaluated in the same manner as in Example 11 except that the coating liquid A-2 was used instead of the coating liquid A-1. The results are shown in Table 5. The water vapor permeability of the support was 150 g / m ² .

<Example 16>
Coating was performed in the same manner as described above except that AQUALIC DL40S manufactured by Nippon Shokubai (sodium polyacrylate, solid content (solute) concentration 40%, average molecular weight 3500) was used instead of the dispersant in the coating liquid T-1. Liquid T-4 was prepared.
A precursor for packaging material was obtained and evaluated in the same manner as in Example 10 except that the coating liquid T-4 was used instead of the coating liquid T-1. The results are shown in Table 5.

<Example 17>
Other than using Aaron A-6330 manufactured by Toagosei Co., Ltd. (sodium acrylate-maleic acid copolymer, solid content (solute) concentration 40%, average molecular weight 10,000) instead of the dispersant in the coating liquid T-1. A coating solution T-5 was prepared in the same manner as described above.
A precursor for packaging material was obtained and evaluated in the same manner as in Example 10 except that the coating liquid T-5 was used instead of the coating liquid T-1. The results are shown in Table 5.

<Example 18>
The same as above except that Kao's Poise 520 (acrylic acid-maleic acid copolymer sodium, solid (solute) concentration 40%, average molecular weight 4000) was used instead of the dispersant in the coating liquid T-1. Coating liquid T-6 was prepared as described above.
A packaging material precursor was obtained and evaluated in the same manner as in Example 10 except that the coating liquid T-6 was used instead of the coating liquid T-1. The results are shown in Table 5.

<Comparative Example 1: PET / B-1 / T-1>
A precursor for packaging material was obtained and evaluated in the same manner as in Example 1 except that Toray polyethylene terephthalate (PET) film mirror P60 (thickness 12 μm) was used instead of the stretched Ny film. The results are shown in Table 5. The water vapor permeability of this PET film was 50 g / m ² .

<Comparative Example 2: Ny / B'-1 / T-1>
A precursor for a packaging material was obtained and evaluated in the same manner as in Example 1 except that the coating liquid B′-1 was used instead of the coating liquid B-1. The results are shown in Table 5.

<Comparative Example 3: Ny / B'-2 / T-1>
A precursor for a packaging material was obtained and evaluated in the same manner as in Example 1 except that the coating liquid B′-2 was used instead of the coating liquid B-1. The results are shown in Table 5.

<Comparative Example 4: Ny / B-1 / T'-1>
A packaging material precursor was obtained and evaluated in the same manner as in Example 1 except that the coating liquid T′-1 was used instead of the coating liquid T-1. The results are shown in Table 5.

<Comparative Example 5: Ny / B-1 / T'-2>
A packaging material precursor was obtained and evaluated in the same manner as in Example 1 except that the coating liquid T′-2 was used instead of the coating liquid T-1. The results are shown in Table 5.

<Comparative Example 6: Ny / A-1 / inorganic vapor deposition layer / B-1 / T-1>
On one side of the stretched Ny film, the coating solution A-1 was applied and dried using a bar coater so that the thickness after drying was 0.2 μm, thereby forming an anchor coat layer. As the stretched Ny film, a united nylon stretched nylon film, Emblem ONBC (thickness 15 μm) was used.
The metal aluminum was evaporated by an electron beam heating vacuum deposition apparatus, oxygen gas was introduced therein, and aluminum oxide was deposited on the anchor coat layer. By forming an inorganic vapor deposition layer having a thickness of 20 nm, a support having a configuration of Ny / anchor coat layer / inorganic vapor deposition layer was obtained. The water vapor permeability of this support was 1 g / m ² .
On the inorganic vapor deposition layer of the support, the coating liquids B-1 and T-1 are sequentially applied and dried using a bar coater so that the thickness after drying becomes 0.3 μm and 0.3 μm, respectively. I let you. Thus, a precursor for packaging material having a structure of Ny / anchor coat layer / inorganic vapor deposition layer / gas barrier layer / protective layer was obtained. The above-mentioned evaluation was performed about the obtained precursor for packaging materials. The results are shown in Table 5.

<Comparative Example 7: Ny / inorganic vapor deposition layer / B-1 / T-1>
The metal aluminum was evaporated by an electron beam heating vacuum deposition apparatus, oxygen gas was introduced therein, and aluminum oxide was deposited on one side of the stretched Ny film to form an inorganic deposited layer having a thickness of 20 nm. This obtained the support body of the structure of Ny / inorganic vapor deposition layer. As the stretched Ny film, a stretched nylon film manufactured by Unitika, Emblem ONBC (thickness 15 μm) was used. The water vapor permeability of this support was 1 g / m ² .
On the inorganic vapor deposition layer of the support, the coating liquids B-1 and T-1 are sequentially applied and dried using a bar coater so that the thickness after drying becomes 0.3 μm and 0.3 μm, respectively. Thus, a packaging material precursor having a structure of Ny / inorganic vapor deposition layer / gas barrier layer / protective layer was obtained. The above-mentioned evaluation was performed about the obtained precursor for packaging materials. The results are shown in Table 5.

<Comparative Example 8: PET / T-1 / B-3>
A precursor for packaging material was obtained and evaluated in the same manner as in Example 10 except that Toray polyethylene terephthalate (PET) film mirror P60 (thickness 12 μm) was used instead of the stretched Ny film. The results are shown in Table 5. The water vapor permeability of this PET film was 50 g / m ² .

<Comparative Example 9: Ny / T-1 / B'-3>
A packaging material precursor was obtained and evaluated in the same manner as in Example 10 except that the coating liquid B′-3 was used instead of the coating liquid B-3. The results are shown in Table 5.

<Comparative Example 10: Ny / T-1 / B'-4>
A packaging material precursor was obtained and evaluated in the same manner as in Example 10 except that the coating liquid B′-4 was used instead of the coating liquid B-3. The results are shown in Table 5.

<Comparative Example 11: Ny / T'-1 / B-3>
A packaging material precursor was obtained and evaluated in the same manner as in Example 10 except that the coating liquid T′-1 was used instead of the coating liquid T-1. The results are shown in Table 5.

<Comparative Example 12: Ny / T'-2 / B-3>
A packaging material precursor was obtained and evaluated in the same manner as in Example 10 except that the coating liquid T′-2 was used instead of the coating liquid T-1. The results are shown in Table 5.

<Comparative Example 13: Ny / A-1 / inorganic vapor deposition layer / T-1 / B-3>
On one side of the stretched Ny film, the coating solution A-1 was applied and dried using a bar coater so that the thickness after drying was 0.2 μm, thereby forming an anchor coat layer. As the stretched Ny film, a stretched nylon film manufactured by Unitika, Emblem ONBC (thickness 15 μm) was used.
On the anchor coat layer, an aluminum vapor is evaporated by an electron beam heating type vacuum deposition apparatus, oxygen gas is introduced therein, and aluminum oxide is deposited to form an inorganic vapor deposition layer having a thickness of 20 nm. A support having a structure of / anchor coat layer / inorganic vapor deposition layer was obtained. The water vapor permeability of this support was 1 g / m ² .
The coating liquids T-1 and B-3 are sequentially applied onto the inorganic vapor-deposited layer of the support using a bar coater so that the thickness after drying is 0.3 μm and 0.3 μm, respectively, and dried. Thus, a precursor for a packaging material having a structure of Ny / anchor coat layer / inorganic vapor deposition layer / intermediate layer / gas barrier layer was obtained. The above-mentioned evaluation was performed about the obtained precursor for packaging materials. The results are shown in Table 5.

<Comparative Example 14: Ny / inorganic vapor deposition layer / T-1 / B-3>
On one side of the stretched Ny film, by evaporating metal aluminum by introducing a vacuum vapor deposition apparatus using an electron beam heating method, oxygen gas is vaporized therein, and aluminum oxide is vapor deposited to form an inorganic vapor deposition layer having a thickness of 20 nm. A support having a structure of Ny / inorganic vapor deposition layer was obtained. As the stretched Ny film, a stretched nylon film manufactured by Unitika, Emblem ONBC (thickness 15 μm) was used. The water vapor permeability of this support was 1 g / m ² .
The coating liquids T-1 and B-3 are sequentially applied onto the inorganic vapor-deposited layer of the support using a bar coater so that the thickness after drying is 0.3 μm and 0.3 μm, respectively, and dried. Thus, a packaging material precursor having a structure of Ny / inorganic vapor deposition layer / intermediate layer / gas barrier layer was obtained. The above-mentioned evaluation was performed about the obtained precursor for packaging materials. The results are shown in Table 5.

<Comparative Example 15: Ny / B-3 / T-1>
On one side of a stretched nylon (Ny) film, the coating liquids B-3 and T-1 were sequentially applied using a bar coater so that the thickness after drying was 0.3 μm and 0.3 μm, respectively. It dried and obtained the precursor for packaging materials of the structure of Ny / gas barrier layer / intermediate layer. As the stretched Ny film, a stretched nylon film emblem ONBC (thickness 15 μm) manufactured by Unitika was used.
The above-mentioned evaluation was performed about the obtained precursor for packaging materials. The results are shown in Table 5.

As shown in the above results, when the packaging material precursors of Examples 1 to 9 were retorted, excellent oxygen gas barrier properties were exhibited. Even when abused before retort treatment, the oxygen gas barrier property was not deteriorated.
On the other hand, Comparative Examples 1 and 6 to 7 in which the water vapor permeability of the support is less than 100 g / m ² and Comparative Examples 2 to 3 in which the degree of neutralization of the polycarboxylic acid polymer in the gas barrier layer coating liquid is greater than 0%. Comparative Example 4 in which the content of the dispersant in the coating liquid for the protective layer is less than 2% by mass relative to the polyvalent metal component, and the content of the polyvalent metal component in the coating liquid for the protective layer is the total solid content. On the other hand, the packaging material precursor of Comparative Example 5, which is less than 40% by mass, was inferior to Examples 1 to 9 in oxygen gas barrier properties after retorting. Moreover, when it abused before the retort process, oxygen gas barrier property deteriorated.

Further, as shown in the above results, when the packaging material precursors of Examples 10 to 18 were retorted, excellent oxygen gas barrier properties were exhibited. Even when abused before retort treatment, the oxygen gas barrier property was not deteriorated.
On the other hand, Comparative Examples 8 and 13 to 14 in which the water vapor permeability of the support is less than 100 g / m ² and Comparative Examples 9 to 10 in which the neutralization degree of the polycarboxylic acid polymer in the gas barrier layer coating solution is 0%. Comparative Example 11 in which the content of the dispersant in the intermediate layer coating liquid is less than 2% by mass with respect to the polyvalent metal component, and the content of the polyvalent metal component in the intermediate layer coating liquid is the total solid content. On the other hand, the precursor for packaging material of Comparative Example 12 in which the stacking order of the gas barrier layer and the intermediate layer is reversed is less than 40% by mass, and the oxygen gas barrier property after retorting is greater than that of Examples 10-18. Was also inferior. Particularly in Comparative Examples 8 to 14, the oxygen gas barrier properties deteriorated when abused before the retort treatment.

Since the precursor for a gas barrier packaging material of the present invention has the above characteristics, it is easily deteriorated by the influence of oxygen, water vapor, etc., for example, an article such as a precision metal part such as a food, a beverage, a pharmaceutical, and an electronic part. It is useful as a precursor of a packaging material that wraps the product or for producing a package in which the article is packaged with a packaging material.
For example, the above-mentioned article (package) is packaged with a precursor for gas barrier packaging material, and subjected to hot water treatment such as boil treatment and retort treatment, whereby the precursor for gas barrier packaging material is used as a gas barrier packaging material. At the same time, a package in which an article to be packaged is wrapped with a gas barrier packaging material can be obtained.

DESCRIPTION OF SYMBOLS 1,101 Support body 2,102 Gas barrier layer 3,103 Protective layer 4,104 Gas barrier layer 5,105 Base material 6,106 Anchor coat layer 7,107 Support body 8,108 Other base materials 9,109

Adhesive layer

10, 110 precursors for

packaging materials

11, 111

packaging materials

20, 120 precursors for

packaging materials

21, 121

packaging materials

30, 130 precursors for

packaging materials

31, 131 packaging materials

Claims

A support;
Directly provided on the support, comprising a polycarboxylic acid polymer and at least one silicon compound selected from the group consisting of hydrolyzable silane compounds, hydrolysates thereof, and condensates thereof. A gas barrier layer;
A protective layer provided directly on the gas barrier layer and comprising a polyvalent metal component, a polyester resin, and a dispersant;
The water vapor permeability at 40 ° C. and 90% relative humidity of the support is 100 g / m 2 or more,
The content of the polyvalent metal component is 40 to 90% by mass with respect to the total mass of the protective layer,
The content of the dispersant is 2 to 20% by mass with respect to the polyvalent metal component,
The content of the silicon compound is 2 to 25% by mass with respect to the polycarboxylic acid polymer,
Wherein when measuring the infrared absorption spectrum of the gas barrier layer, the maximum peak height in absorbance in the range of wave number 1490cm -1 ~ 1659cm -1 and (alpha), the absorbance in the wave number range of 1660 cm -1 ~ 1750 cm -1 A precursor for a gas barrier packaging material having a ratio (α / β) of 1 to 7 with respect to the maximum peak height (β).
A support;
Directly provided on the support, comprising a polycarboxylic acid polymer and at least one silicon compound selected from the group consisting of hydrolyzable silane compounds, hydrolysates thereof, and condensates thereof. A gas barrier layer;
A protective layer provided directly on the gas barrier layer and comprising a polyvalent metal component, a polyester resin, and a dispersant;
The water vapor permeability at 40 ° C. and 90% relative humidity of the support is 100 g / m 2 or more,
The content of the polyvalent metal component is 40 to 90% by mass with respect to the total mass of the protective layer,
The content of the dispersant is 2 to 20% by mass with respect to the polyvalent metal component,
The content of the silicon compound is 2 to 25% by mass with respect to the polycarboxylic acid polymer,
Wherein when measuring the infrared absorption spectrum of the gas barrier layer, the maximum peak height in absorbance in the range of wave number 1490cm -1 ~ 1659cm -1 and (alpha), the absorbance in the wave number range of 1660 cm -1 ~ 1750 cm -1 A gas barrier packaging material having a ratio (α / β) of 7 or more to the maximum peak height (β).
A gas barrier comprising a polycarboxylic acid polymer, a hydrolyzable silane compound, a hydrolyzate thereof, a hydrolyzate thereof, and at least one silicon compound selected from the group consisting of these condensates and a liquid medium on the surface of the support Apply the layer coating liquid and dry to form a gas barrier layer,
Forming a protective layer by applying a coating liquid for a protective layer containing a polyvalent metal component, a polyester resin, a dispersant, and water on the surface of the gas barrier layer and drying the coating;
The water vapor permeability at 40 ° C. and 90% relative humidity of the support is 100 g / m 2 or more,
The content of the polyvalent metal component is 40 to 90% by mass with respect to the total solid content of the protective layer coating solution,
The content of the dispersant is 2 to 20% by mass with respect to the polyvalent metal component,
The content of the silicon compound is 2 to 25% by mass with respect to the polycarboxylic acid polymer,
The manufacturing method of the precursor for gas barrier packaging materials whose neutralization degree by the polyvalent metal of the carboxyl group of the said polycarboxylic acid-type polymer is 0 mol%.
A method for producing a package body, which comprises packaging a package using the precursor for a gas barrier packaging material according to claim 1 and treating it with hot water to obtain a package body.
A support;
An intermediate layer provided directly on the support and comprising a polyvalent metal component, a polyester resin, and a dispersant;
Directly provided on the intermediate layer, comprising a polycarboxylic acid polymer and at least one silicon compound selected from the group consisting of hydrolyzable silane compounds, hydrolysates thereof, and condensates thereof. A gas barrier layer,
The water vapor permeability at 40 ° C. and 90% relative humidity of the support is 100 g / m 2 or more,
The content of the polyvalent metal component is 40 to 90% by mass with respect to the total mass of the intermediate layer,
The content of the dispersant is 2 to 20% by mass with respect to the polyvalent metal component, and the content of the silicon compound is 2 to 25% by mass with respect to the polycarboxylic acid polymer,
Wherein when measuring the infrared absorption spectrum of the gas barrier layer, the maximum peak height in absorbance in the range of wave number 1490cm -1 ~ 1659cm -1 and (alpha), the absorbance in the wave number range of 1660 cm -1 ~ 1750 cm -1 A precursor for a gas barrier packaging material having a ratio (α / β) of 1 to 7 with respect to the maximum peak height (β).
A support;
An intermediate layer provided directly on the support and comprising a polyvalent metal component, a polyester resin, and a dispersant;
Directly provided on the intermediate layer, comprising a polycarboxylic acid polymer and at least one silicon compound selected from the group consisting of hydrolyzable silane compounds, hydrolysates thereof, and condensates thereof. A gas barrier layer,
The water vapor permeability at 40 ° C. and 90% relative humidity of the support is 100 g / m 2 or more,
The content of the polyvalent metal component is 40 to 90% by mass with respect to the total mass of the intermediate layer,
The content of the dispersant is 2 to 20% by mass with respect to the polyvalent metal component,
The content of the silicon compound is 2 to 25% by mass with respect to the polycarboxylic acid polymer,
Wherein when the infrared absorption spectrum of the gas barrier layer were measured, 1490cm -1 ~ 1659cm maximum peak height absorbance in the range of -1 and (alpha), the maximum peak absorbance in the range of 1660 cm -1 ~ 1750 cm -1 A gas barrier packaging material having a ratio (α / β) of 7 or more to the height (β).
On the surface of the support, an intermediate layer coating solution containing a polyvalent metal component, a polyester resin, a dispersant, and a liquid medium is applied and dried to form an intermediate layer.
A gas barrier containing, on the surface of the intermediate layer, at least one silicon compound selected from the group consisting of a polycarboxylic acid polymer, a hydrolyzable silane compound, a hydrolyzate thereof, and a condensate thereof, and water. Applying a layer coating solution and drying to form a gas barrier layer;
The water vapor permeability at 40 ° C. and 90% relative humidity of the support is 100 g / m 2 or more,
The content of the polyvalent metal component is 40 to 90% by mass with respect to the total solid content of the intermediate layer coating solution,
The content of the dispersant is 2 to 20% by mass with respect to the polyvalent metal component,
The content of the silicon compound is 2 to 25% by mass with respect to the polycarboxylic acid polymer,
A method for producing a precursor for a gas barrier packaging material, wherein the degree of neutralization of a carboxyl group of the polycarboxylic acid polymer by a polyvalent metal is 20 to 50 mol%.
A method for producing a packaged body obtained by packaging a packaged article using the gas barrier packaging material precursor according to claim 5 and treating it with hot water to obtain a packaged body.