JP2023118619A - Barrier substrate, barrier laminate, lid material and package - Google Patents

Abstract

To provide a barrier substrate having a vapor-deposition film on a stretched resin layer primarily composed of polyolefin, the barrier substrate having excellent gas barrier properties.SOLUTION: A barrier substrate has at least a stretched resin layer primarily composed of polyolefin, and a vapor-deposition film. The barrier substrate further has a primer layer containing an aqueous polyhydroxy urethane resin between the stretched resin layer and the vapor-deposition film.SELECTED DRAWING: None

Description

The present disclosure relates to barrier substrates, barrier laminates, lids, and packaging containers.

Base materials made of polyester such as polyethylene terephthalate (PET) (hereinafter also referred to as "polyester base materials") are excellent in mechanical properties, chemical stability, heat resistance and transparency, and are inexpensive. Therefore, polyester base materials have conventionally been used as base materials for constructing laminates used to produce packaging containers.

Depending on the contents filled in the packaging container, the packaging container is required to have gas barrier properties such as oxygen barrier properties and water vapor barrier properties. In order to meet this demand, a deposited film containing alumina, silica, or the like is formed on the surface of a polyester base material (see, for example, Patent Document 1).

In recent years, along with the increasing demand for building a recycling-oriented society, there is a demand for packaging containers with high recyclability. However, in conventional packaging containers, the base material and the sealant film are made of different resin materials, and it is difficult to separate each resin material, so it is currently not recycled.

JP-A-2005-053223

From the standpoint of single materialization (monomaterialization) that is easy to recycle, the present inventors have studied single materialization using polyolefin. Specifically, the present inventors used a stretched base material containing polyolefin as a main component instead of a conventional polyester base material, and replaced the stretched base material with a sealant film containing polyolefin as a main component. I considered combining them. With such a configuration, since both the base material and the sealant film are made of polyolefin, the recyclability of the packaging container can be improved.

As a result of investigation, the present inventors found that when a vapor deposition film is provided on the surface of a stretched base material (stretched resin layer) containing polyolefin as a main component, gas barrier properties are not sufficient.

One of the problems to be solved by the present disclosure is to provide a barrier substrate having a vapor deposition film on a stretched resin layer containing polyolefin as a main component and having excellent gas barrier properties.

The barrier base material of the present disclosure includes at least a stretched resin layer containing polyolefin as a main component and a deposited film, and a primer layer containing a water-based polyhydroxyurethane resin is provided between the stretched resin layer and the deposited film. Prepare more.

According to the present disclosure, it is possible to provide a barrier substrate having a vapor deposition film on a stretched resin layer containing polyolefin as a main component, and having excellent gas barrier properties.

FIG. 1 is a schematic cross-sectional view showing one embodiment of a barrier substrate. FIG. 2 is a schematic cross-sectional view showing one embodiment of the barrier substrate. FIG. 3 is a schematic cross-sectional view showing one embodiment of the barrier laminate. FIG. 4 is a schematic cross-sectional view showing one embodiment of the barrier laminate. FIG. 5 is a schematic cross-sectional view showing one embodiment of the barrier laminate. FIG. 6 is a schematic cross-sectional view showing one embodiment of the barrier laminate. FIG. 7 is a schematic cross-sectional view showing one embodiment of the barrier laminate. FIG. 8 is a schematic cross-sectional view showing one embodiment of the barrier laminate. FIG. 9 is a schematic front view showing one embodiment of the packaging container. FIG. 10 is a schematic perspective view showing one embodiment of the packaging container.

Hereinafter, embodiments of the present disclosure will be described in detail. This disclosure may be embodied in many different forms and should not be construed as limited to the description of the exemplary embodiments set forth below. In order to make the description clearer, the drawings may schematically represent the width, thickness, shape, etc. of each layer compared to the embodiment, but this is only an example and does not limit the interpretation of the present disclosure. . In this specification and each figure, elements similar to those already described with respect to previous figures may be denoted by the same reference numerals, and detailed description thereof may be omitted as appropriate.

In the following description, each component that appears (e.g., polyolefins such as polypropylene and polyethylene, α-olefins, resin materials, polyhydroxyurethane resins, additives, inorganic oxides, and gas barrier resins) is used one type each. may be used, or two or more may be used.

[Barrier substrate]
The barrier substrate of the present disclosure has at least
A stretched resin layer containing polyolefin as a main component;
A primer layer containing a water-based polyhydroxyurethane resin,
A vapor deposition film is provided in this order in the thickness direction.
In the present disclosure, the “stretched resin layer” means a resin layer that has been stretched.
The barrier substrate may further comprise a layer, which will be described later.

1 and 2 are schematic cross-sectional views showing one embodiment of the barrier substrate.
The barrier substrate 1 shown in FIG. 1 includes a stretched resin layer 10, a primer layer 12, and a deposited film 14 in this order in the thickness direction. The barrier substrate 1 shown in FIG. 2 includes a stretched resin layer 10, a primer layer 12, a deposited film 14, and a barrier coat layer 16 in this order in the thickness direction.

<Stretched resin layer>
The stretched resin layer contains polyolefin as a main component, that is, the polyolefin content preferably exceeds 50% by mass. Polyolefins include, for example, polypropylene, polyethylene and polymethylpentene. As the stretched resin layer, a polypropylene layer containing polypropylene as a main component and a polyethylene layer containing polyethylene as a main component are preferable.

The melt flow rate (MFR) of the polyolefin is preferably 0.1 g/10 min or more and 50 g/10 min or less, more preferably 0.3 g/10 min or more and 30 g/10 min or less, from the viewpoint of film formability and processability. , more preferably 0.5 g/10 min or more and 10 g/10 min or less. In the present disclosure, the MFR of polyolefin is measured by A method under the condition of a load of 2.16 kg according to JIS K7210. The MFR measurement temperature is set according to the melting point of the polyolefin, etc. For example, it is 190° C. for polyethylene and 230° C. for polypropylene.

The polyolefin content in the stretched resin layer is preferably more than 50% by mass, more preferably 80% by mass or more, still more preferably 85% by mass or more, even more preferably 90% by mass or more, and particularly preferably 95% by mass. That's it.

The stretched resin layer may contain a resin material other than polyolefin. Examples of such resin materials include (meth)acrylic resins, vinyl resins, cellulose resins, polyamides, polyesters and ionomer resins.

The stretched resin layer may contain additives. Examples of additives include cross-linking agents, antioxidants, anti-blocking agents, slip agents, UV absorbers, light stabilizers, fillers, reinforcing agents, antistatic agents, compatibilizers, pigments and modifiers. resins for

The stretched resin layer is a polyolefin layer that has been stretched. Thereby, for example, the heat resistance, impact resistance, water resistance and dimensional stability of the barrier substrate can be improved. A barrier base material having such a stretched resin layer is suitable, for example, as a base material constituting packaging containers subjected to boiling treatment or retorting treatment.

The stretching treatment may be uniaxial stretching or biaxial stretching.
The stretching ratio in the case of stretching in the longitudinal direction (flow direction of the base material, MD direction) is preferably 2 times or more and 15 times or less, more preferably 5 times or more and 13 times or less. The draw ratio in the case of stretching in the transverse direction (direction perpendicular to the MD direction, TD direction) is preferably 2 to 15 times, more preferably 5 to 13 times. By setting the draw ratio to 2 times or more, for example, the strength and heat resistance of the polyolefin layer can be further improved, and the printability of the polyolefin layer can be improved. From the viewpoint of the breaking limit of the polyolefin layer, the draw ratio is preferably 15 times or less.

The stretched resin layer may be surface-treated in one embodiment. Thereby, for example, the adhesion between the stretched resin layer and other layers can be improved. Examples of surface treatment methods include physical treatments such as corona discharge treatment, ozone treatment, low-temperature plasma treatment using oxygen gas and/or nitrogen gas, glow discharge treatment; and oxidation treatment using chemicals. Chemical treatment can be mentioned.
An easy-adhesion layer may be provided on the surface of the stretched resin layer.

The stretched resin layer may have a single layer structure or a multilayer structure. When the stretched resin layer has a multilayer structure, the number of layers of the stretched resin layer is, for example, 2 to 7, preferably 3 to 5.

The thickness of the stretched resin layer is preferably 5 μm or more and 100 μm or less, more preferably 10 μm or more and 50 μm or less. When the stretched resin layer has a multilayer structure, the total thickness is preferably within the above range. When the thickness is at least the lower limit, for example, the strength, heat resistance and recyclability of the barrier substrate can be improved. When the thickness is equal to or less than the upper limit, for example, the processability of the barrier substrate can be improved.

(polypropylene layer)
The polypropylene layer as the stretched resin layer contains polypropylene as a main component, that is, the polypropylene content preferably exceeds 50% by mass. By providing the barrier substrate of the present disclosure with a polypropylene layer, for example, the oil resistance of packaging containers produced using the barrier substrate can be improved.

The polypropylene may be a propylene homopolymer (homopolypropylene), a propylene random copolymer (random polypropylene) or a propylene block copolymer (block polypropylene), or a mixture of two or more selected from these. As the polypropylene, biomass-derived polypropylene, mechanically recycled or chemically recycled polypropylene may be used from the viewpoint of reducing the environmental load.

A propylene homopolymer is a polymer of propylene only. A propylene random copolymer is a random copolymer of propylene and an α-olefin other than propylene. A propylene block copolymer is a copolymer having a polymer block composed of propylene and a polymer block composed of an α-olefin other than propylene.

Examples of α-olefins other than propylene include α-olefins having 2 to 20 carbon atoms, specifically ethylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1- Decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, 3-methyl-1-butene, 4-methyl-1-pentene and 6-methyl-1-heptene.

Among polypropylenes, random copolymers are preferable from the viewpoint of transparency. A homopolymer is preferable when importance is placed on the rigidity and heat resistance of the packaging container. Block copolymers are preferred when the impact resistance of the packaging container is important. The stretched resin layer WHEREIN: A homopolymer is preferable from a heat resistant viewpoint.

Density of polypropylene is, for example, 0.88 g/cm ³ or more and 0.92 g/cm ³ or less. In the present disclosure, the density is measured according to JIS K7112, particularly D method (density gradient tube method, 23°C).

From the viewpoint of heat resistance, the melting point (Tm) of polypropylene is, for example, 120° C. or higher and 170° C. or lower, preferably 125° C. or higher and 170° C. or lower, more preferably 140° C. or higher and 170° C. or lower. In the present disclosure, Tm is obtained by differential scanning calorimetry (DSC) according to JIS K7121.

The content of polypropylene in the polypropylene layer is preferably more than 50% by mass, more preferably 80% by mass or more, still more preferably 85% by mass or more, even more preferably 90% by mass or more, particularly preferably 95% by mass or more. is.

The polypropylene layer may have a single layer structure or a multilayer structure. When the polypropylene layer has a multilayer structure, the number of layers of the polypropylene layer is, for example, 2 to 7 layers, preferably 3 to 5 layers.

(polyethylene layer)
The polyethylene layer as the stretched resin layer contains polyethylene as a main component, that is, preferably contains polyethylene in an amount exceeding 50% by mass. In the present disclosure, polyethylene refers to a polymer containing 50 mol % or more of ethylene-derived structural units in all repeating structural units. In this polymer, the content of ethylene-derived structural units is preferably 70 mol % or more, more preferably 80 mol % or more, still more preferably 90 mol % or more, and particularly preferably 95 mol % or more. The content ratio can be measured by the NMR method.

Polyethylene may be an ethylene homopolymer or a copolymer of ethylene and an ethylenically unsaturated monomer other than ethylene. Examples of ethylenically unsaturated monomers other than ethylene include propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, and 1-octadecene. , 1-eicosene, 3-methyl-1-butene, 4-methyl-1-pentene and 6-methyl-1-heptene, α-olefins having 2 to 20 carbon atoms; vinyls such as vinyl acetate and vinyl propionate monomers; and (meth)acrylic acid esters such as methyl (meth)acrylate and ethyl (meth)acrylate.

Polyethylene includes, for example, high density polyethylene, medium density polyethylene, low density polyethylene, linear low density polyethylene and ultra low density polyethylene. From the viewpoint of the strength and heat resistance of the barrier substrate, high-density polyethylene and medium-density polyethylene are preferred. As the polyethylene, biomass-derived polyethylene, or mechanically recycled or chemically recycled polyethylene may be used from the viewpoint of reducing the environmental load.

In the present disclosure, the density of the polyethylene is as follows.
The density of high density polyethylene is preferably greater than 0.945 g/ ^cm3 . The upper density limit of high-density polyethylene is, for example, 0.965 g/cm ³ . The density of medium density polyethylene is preferably greater than 0.930 g/cm ³ and less than or equal to 0.945 g/cm ³ . The density of the low density polyethylene is preferably greater than 0.900 g/cm ³ and less than or equal to 0.930 g/cm ³ . The density of the linear low-density polyethylene is preferably greater than 0.900 g/cm ³ and less than or equal to 0.930 g/cm ³ . The density of the ultra-low density polyethylene is preferably 0.900 g/cm ³ or less. The lower limit of the density of ultra-low density polyethylene is, for example, 0.860 g/cm ³ . In the present disclosure, the density is measured according to JIS K7112, particularly D method (density gradient tube method, 23°C).

Low-density polyethylene is usually polyethylene obtained by polymerizing ethylene by a high-pressure polymerization method (high-pressure low-density polyethylene). Linear low-density polyethylene is usually polyethylene obtained by polymerizing ethylene and a small amount of α-olefin by a polymerization method using a multi-site catalyst such as a Ziegler-Natta catalyst or a single-site catalyst such as a metallocene catalyst.

From the viewpoint of heat resistance, the melting point (Tm) of polyethylene is preferably 100° C. or higher and 140° C. or lower, more preferably 105° C. or higher and 140° C. or lower, still more preferably 110° C. or higher and 140° C. or lower. In the present disclosure, Tm is obtained by differential scanning calorimetry (DSC) according to JIS K7121.

Polyethylenes with different densities or branches can be obtained by appropriately selecting the polymerization method. For example, using a multi-site catalyst such as a Ziegler-Natta catalyst or a single-site catalyst such as a metallocene catalyst as a polymerization catalyst, one-stage polymerization is performed by any of gas phase polymerization, slurry polymerization, solution polymerization and high-pressure ion polymerization. Alternatively, it is preferable to carry out the polymerization in two or more stages.

The content of polyethylene in the polyethylene layer is preferably more than 50% by mass, more preferably 80% by mass or more, still more preferably 85% by mass or more, even more preferably 90% by mass or more, and particularly preferably 95% by mass or more. is.

The polyethylene layer may have a single layer structure or a multilayer structure. When the polyethylene layer has a multilayer structure, the number of layers of the polyethylene layer is, for example, 2 to 7 layers, preferably 3 to 5 layers.

<Primer layer>
The barrier base material of the present disclosure includes a primer layer containing a water-based polyhydroxyurethane resin between the stretched resin layer and the deposited film. By providing such a primer layer, for example, it is possible to improve the flatness of the surface on which the vapor deposition film is formed and to reduce the heat shrinkage of the stretched resin layer, and the adhesion and adhesion of the vapor deposition film formed on the surface of the primer layer. Uniformity can be improved, and gas barrier properties can be improved.

The barrier base material of the present disclosure includes a stretched resin layer, a primer layer, and a deposited film in this order in the thickness direction. In one embodiment, the primer layer is a coat layer provided on one surface of the stretched resin layer.

The water-based polyhydroxyurethane resin will be described below.
Conventional polyurethane resins are obtained using polyol and polyisocyanate as raw materials, whereas polyhydroxyurethane resins have a chemical structure with urethane bonds and hydroxyl groups in the main chain. The polyhydroxyurethane resin is obtained, for example, from a cyclic carbonate compound and an amine compound, where the cyclic carbonate compound is preferably a compound obtained by reacting an epoxy compound and carbon dioxide. That is, the polyhydroxyurethane resin is preferably a resin produced by using, for example, an epoxy compound, carbon dioxide and an amine compound as raw materials and combining these raw materials. Carbon dioxide used as a raw material is incorporated as a -CO-O- bond in the chemical structure of polyhydroxyurethane resin, so polyhydroxyurethane resin is a greenhouse gas from the viewpoint of effective utilization of carbon dioxide. preferable.

The acid value of the aqueous polyhydroxyurethane resin is preferably 10 mgKOH/g or more and 100 mgKOH/g or less, more preferably 15 mgKOH/g or more and 50 mgKOH/g or less, from the viewpoint of water dispersibility of the resin particles.

The hydroxyl value of the aqueous polyhydroxyurethane resin is preferably 150 mgKOH/g or more and 300 mgKOH/g or less, more preferably 175 mgKOH/g or more and 250 mgKOH/g or less, from the viewpoint of gas barrier properties and adhesion.

Both the acid value and hydroxyl value of the aqueous polyhydroxyurethane resin are measured for each resin by a titration method based on JIS K1557, and the content of each functional group per 1 g of resin is represented by mg equivalent of KOH.

The weight average molecular weight (Mw) of the aqueous polyhydroxyurethane resin in terms of polystyrene is preferably 10,000 or more and 100,000 or less, more preferably 20,000 or more and 90,000 or less, and still more preferably 30,000 or more and 80,000. It is below. Mw is measured by gel permeation chromatography (GPC) using N,N-dimethylformamide (DMF) as a mobile phase. GPC measurement is performed using, for example, GPC-8220 (trade name) manufactured by Tosoh Corporation with columns Super AW2500+AW3000+AW4000+AW5000.

The waterborne polyhydroxyurethane resin, in one embodiment, is a water-dispersed polyhydroxyurethane resin. A water-based polyhydroxyurethane resin usually has a carboxy group. This enables self-emulsification of the aqueous polyhydroxyurethane resin. The waterborne polyhydroxyurethane resin, in one embodiment, has a group represented by >NC(=O)-V-COOH. V in the formula has the same meaning as V in formula (6) described later.

The water-based polyhydroxyurethane resin has a particle diameter in water of, for example, 0.001 μm or more and 100 μm or less, preferably 0.001 μm or more and 10 μm or less, more preferably 0.001 μm or more and 2 μm or less, and still more preferably 0.01 μm or more and 2 μm or less. It is possible to constitute an aqueous dispersion obtained by dispersing in.

The median diameter (d50) of the aqueous polyhydroxyurethane resin in the aqueous dispersion is, for example, 0.005 μm or more and 0.5 μm or less. d50 can be measured on an aqueous dispersion using a dynamic light scattering Nanotrac particle size analyzer.

The content of the aqueous polyhydroxyurethane resin in the aqueous dispersion (for example, the primer layer coating solution) may be, for example, 5% by mass or more and 50% by mass or less, 10% by mass or more and 45% by mass or less, or 15% by mass. 40 mass % or less may be sufficient. The content of the dispersion medium such as water in the aqueous dispersion may be, for example, 50% by mass or more and 95% by mass or less, 55% by mass or more and 90% by mass or less, or 60% by mass or more and 85% by mass or less.

Examples of water-based polyhydroxyurethane resins include resins having a repeating structural unit represented by formula (1) (hereinafter also referred to as "structural unit (1)"). The water-based polyhydroxyurethane resin may have two or more types of structural units (1).

The meaning of each symbol in formula (1) is as follows.
X is a direct bond or an optionally substituted divalent hydrocarbon group. In the present disclosure, optionally substituted hydrocarbon groups include unsubstituted hydrocarbon groups and substituted hydrocarbon groups (hereinafter also referred to as "substituted hydrocarbon groups").

Examples of hydrocarbon groups include aliphatic hydrocarbon groups having 1 to 30 carbon atoms, alicyclic hydrocarbon groups having 4 to 40 carbon atoms and aromatic hydrocarbon groups having 6 to 40 carbon atoms. A substituted hydrocarbon group may have an ether bond, an amino bond, a sulfonyl bond or an ester bond, and may have a substituent such as a hydroxyl group, a halogen atom and a polyalkylene glycol chain. The group bonded to Z ₁ in the substituted hydrocarbon group may be an ether bond, amino bond, sulfonyl bond or ester bond. The group bonded to Z ₂ in the substituted hydrocarbon group may be an ether bond, amino bond, sulfonyl bond or ester bond. Such embodiments are also included in substituted hydrocarbon groups.

Y is an optionally substituted divalent hydrocarbon group. Examples of hydrocarbon groups include aliphatic hydrocarbon groups having 1 to 15 carbon atoms, alicyclic hydrocarbon groups having 4 to 15 carbon atoms and aromatic hydrocarbon groups having 6 to 15 carbon atoms. The substituted hydrocarbon group may have an ether bond or a sulfonyl bond, and may have a substituent such as a hydroxyl group and a halogen atom.

Y may be a divalent organic group having a carboxy group. As the organic group, for example, in a divalent group derived from a compound having at least two primary amino groups and at least one secondary amino group, at least one of the secondary amino groups (—NH—) is -N(CO-V-COOH)- includes a group substituted (in terms of notation) for the group represented by -. V is an optionally substituted divalent hydrocarbon group. Examples of hydrocarbon groups include aliphatic hydrocarbon groups having 1 to 10 carbon atoms and aromatic hydrocarbon groups having 6 to 10 carbon atoms. A substituted hydrocarbon group may have an oxygen atom or a nitrogen atom.

Z ₁ and Z ₂ each independently represent at least one structure selected from formula (2), formula (3), formula (4) and formula (5).

In Formula (4) and Formula (5), R is a hydrogen atom or a methyl group.

The water-based polyhydroxyurethane resin preferably has a carboxy group-containing chemical structure represented by formula (6) (hereinafter also referred to as "chemical structure (6)"). The water-based polyhydroxyurethane resin may have two or more chemical structures (6). In addition, when the structural unit (1) has a divalent organic group having a carboxyl group as Y, the water-based polyhydroxyurethane resin does not have to have the chemical structure (6).

The meaning of each symbol in formula (6) is as follows.
W is an optionally substituted divalent hydrocarbon group. Examples of hydrocarbon groups include aliphatic hydrocarbon groups having 1 to 30 carbon atoms, alicyclic hydrocarbon groups having 4 to 40 carbon atoms and aromatic hydrocarbon groups having 6 to 40 carbon atoms. A substituted hydrocarbon group may have an ether bond, an amino bond, a sulfonyl bond or an ester bond, and may have a substituent such as a hydroxyl group, a halogen atom and a polyalkylene glycol chain.

Y is a moiety that binds to the urethane structure having a bond in formula (1), and can be selected from groups that can be selected as Y in formula (1). Y in formula (1) and Y in formula (6) may be the same or different.

V is an optionally substituted divalent hydrocarbon group. Examples of hydrocarbon groups include aliphatic hydrocarbon groups having 1 to 10 carbon atoms and aromatic hydrocarbon groups having 6 to 10 carbon atoms. A substituted hydrocarbon group may have an oxygen atom or a nitrogen atom.

The water-based polyhydroxyurethane resin may have a chemical structure represented by formula (7) (hereinafter also referred to as "chemical structure (7)"). The water-based polyhydroxyurethane resin may have two or more chemical structures (7).

In formula (7), W and Y are synonymous with the same symbols in formula (6).

The water-based polyhydroxyurethane resin may have an --O--CO--bond in which carbon dioxide is immobilized in its structure. The water-based polyhydroxyurethane resin may have -O-CO- bonds derived from carbon dioxide (immobilized amount of carbon dioxide) in the range of 1% by mass or more and 30% by mass or less, and 5% by mass or more and 25% by mass. You may have in the following ranges, and you may have in the range of 10 mass % or more and 20 mass % or less.

The structural unit (1) in the aqueous polyhydroxyurethane resin includes, for example, a compound having at least two five-membered cyclic carbonate structures (also referred to simply as a "cyclic carbonate compound") and a compound having at least two primary amino groups ( It is composed of a polyaddition reaction product with (also simply referred to as "amine compound"). The cyclic carbonate compound can be synthesized, for example, by using carbon dioxide as raw materials for at least a part thereof, and specifically, by using a compound having at least two epoxy groups and carbon dioxide as raw materials.

The water-based polyhydroxyurethane resin can be produced, for example, as follows. First, a compound having at least two primary amino groups is polyaddition-reacted with a compound having at least two epoxy groups and a compound having at least two five-membered cyclic carbonate structures to obtain a secondary amino group. to obtain a polyhydroxyurethane resin having Next, the secondary amino groups of the polyhydroxyurethane resin are reacted with a cyclic acid anhydride to obtain a polyhydroxyurethane resin having a carboxyl group.

In the above polyaddition reaction, a compound having at least two epoxy groups is added to a compound having at least two primary amino groups so that the equivalent ratio of amino groups to epoxy groups is primary amino group/epoxy group=4/ The reaction may be carried out under conditions in which one or more primary amino groups are in excess. The compound thus obtained has primary amino groups at both ends and a secondary amino group inside. In this case, it is known that the internal secondary amino group does not react with the cyclic carbonate compound. Then, a compound having at least two five-membered cyclic carbonate structures may be polyaddition-reacted with the obtained compound. As a result, a polyhydroxyurethane resin having secondary amino groups is obtained.

A compound having at least two primary amino groups, a compound having at least two epoxy groups, and a compound having at least two five-membered cyclic carbonate structures are reacted at once to have a secondary amino group. A polyhydroxyurethane resin may be obtained.

The water-based polyhydroxyurethane resin may be produced, for example, as follows. First, a compound having at least two five-membered cyclic carbonate structures and a compound having at least two primary amino groups and at least one secondary amino group are subjected to a polyaddition reaction to obtain a polyhydroxy compound having a secondary amino group. A urethane resin is obtained. Next, the secondary amino groups of the polyhydroxyurethane resin are reacted with a cyclic acid anhydride to obtain a polyhydroxyurethane resin having a carboxyl group.

An aqueous dispersion of a water-based polyhydroxyurethane resin can be formed, for example, by neutralizing the carboxy groups in the polyhydroxyurethane resin and then adding water for phase inversion emulsification. Since the water-based polyhydroxyurethane resin has a carboxy group-containing structure, water can be added for phase inversion emulsification.

The divalent group represented by -C(=O)OZ ₁ -XZ ₂ -OC(=O)- in formula (1) includes, for example, the following divalent groups derived from cyclic carbonate compounds group.

R in the above formula is a hydrogen atom or a methyl group.

Examples of the divalent group represented by -NH-Y-NH- in formula (1) include divalent groups derived from compounds having at least two primary amino groups. Examples of such compounds include ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane, 1,8-diaminooctane, 1,10-diaminodecane, 1,12-diamino linear aliphatic polyamines such as dodecane; cycloaliphatic polyamines such as isophoronediamine, norbornanediamine, 1,6-cyclohexanediamine, piperazine and 2,5-diaminopyridine; aliphatic polyamines having aromatic rings such as xylylenediamine; Aromatic polyamines such as metaphenylenediamine and diaminodiphenylmethane are included.

Compounds having at least two primary amino groups and at least one secondary amino group include, for example, diethylenetriamine, triethylenetetramine, iminobispropylamine, tetraethylenepentamine, N,N'-bis(3-aminopropyl )-1,3-propylenediamine and linear aliphatic polyamines such as N,N'-bis(3-aminopropyl)-1,4-butylenediamine.

As the divalent group represented by —CH ₂ —CH(OH)—CH ₂ —O—W—O—CH ₂ —CH(OH)—CH ₂ — in formulas (6) and (7), Examples thereof include divalent groups derived from compounds having at least two epoxy groups. Examples of the above compounds include bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, novolac type epoxy compounds, alicyclic epoxy compounds, glycidyl ethers, glycidyl esters and resorcin type epoxy compounds.

Examples of the group represented by -C(=O)-V-COOH in formula (6) include groups derived from cyclic acid anhydrides. As the cyclic acid anhydride, for example, an anhydride obtained by intramolecular dehydration condensation of the carboxy groups of a compound having a plurality of carboxy groups is preferable. Specifically, succinic anhydride, itaconic anhydride, and maleic anhydride are preferable. , caronic anhydride, citraconic anhydride, glutaric anhydride, diglycolic anhydride and 1,2,3,4-butanetetracarboxylic dianhydride; phthalic acid, trimellit Aromatic anhydrides such as acid anhydrides, 1,2-naphthalic anhydride and pyromellitic anhydride; 1,1-cyclohexanediacetic anhydride, 1-cyclohexene-1,2-dicarboxylic anhydride, 1 , 1-cyclopentane diacetic anhydride and 5-norbornene-2,3-dicarboxylic anhydride.

The carboxyl groups present in the structure of the water-based polyhydroxyurethane resin may remain as they are when water is added to form an aqueous dispersion by phase inversion emulsification, but they promote ionization in water. To do so, some, preferably all, of the carboxy groups may be neutralized to form a neutralized salt.

Basic compounds that can be used for neutralization include, for example, ammonia, ethylamine, trimethylamine, triethylamine, triisopropylamine, tributylamine, triethanolamine, N-methyldiethanolamine, N-phenyldiethanolamine, monoethanolamine, dimethylethanolamine, Organic amines such as diethylethanolamine, morpholine, N-methylmorpholine, 2-amino-2-ethyl-1-propanol, trimethylamine, triethylamine, tripropylamine, tributylamine, N-methyldiethanolamine and triethanolamine; lithium, potassium and alkali metals such as sodium; inorganic bases such as sodium hydroxide, potassium hydroxide, calcium hydroxide, potassium hydroxide and ammonia.

Water-based polyhydroxyurethane resins can be produced, for example, by the methods described in Japanese Patent No. 6298421, Japanese Patent No. 6563242 and Japanese Patent No. 6813337.

The content of the water-based polyhydroxyurethane resin in the primer layer is preferably 70% by mass or more, more preferably 80% by mass or more, and still more preferably 90% by mass or more.
The primer layer may contain a resin material other than the water-based polyhydroxyurethane resin.
The primer layer may contain the above additives.

The ratio of the thickness of the primer layer to the total thickness of the barrier substrate is preferably 1% or more and 20% or less, more preferably 1% or more and 15% or less, still more preferably 2% or more and 10% or less, and particularly preferably It is 3% or more and 8% or less. When the above ratio is at least the lower limit, for example, the adhesion of the deposited film can be further improved, the gas barrier property can be further improved, and the lamination strength of the packaging container can be further improved. When the above ratio is equal to or less than the upper limit, for example, the processability of the base material and the recyclability of the packaging container can be further improved.

The thickness of the primer layer is preferably 0.1 μm or more and 10 μm or less, more preferably 0.2 μm or more and 8 μm or less, still more preferably 0.3 μm or more and 6 μm or less, and particularly preferably 0.5 μm or more and 4 μm or less. When the thickness is at least the lower limit, for example, the adhesion of the deposited film can be further improved, the gas barrier property can be further improved, and the lamination strength of the packaging container can be further improved. When the thickness is equal to or less than the upper limit, for example, the processability of the base material and the recyclability of the packaging container can be further improved.

The arithmetic mean roughness Ra of the primer layer surface is preferably 2.0 nm or less, more preferably 1.5 nm or less, even more preferably 1.0 nm or less, and particularly preferably 0.5 nm or less. As a result, for example, it is possible to improve the formability of the vapor deposition film and therefore the gas barrier properties. For example, by using a water-based polyhydroxyurethane resin, such a primer layer having excellent surface smoothness can be formed. Ra is measured using an atomic force microscope (AFM) under the condition that the radius of curvature of the tip of the stylus is 2 μm, and the specific measurement conditions are as follows.
・Measuring device: Dimension icon made by Bruker
・Measurement range: 2 μm×2 μm

For the primer layer, for example, a water-based coating liquid containing a water-based polyhydroxyurethane resin is applied using, for example, a gravure coater, a knife coater, a reverse coater, a bar coater, a spray coater, a slit coater, etc., and water and the remaining It can be formed by evaporating an organic solvent. The water-based coating liquid is, for example, an aqueous dispersion of a water-based polyhydroxyurethane resin.

The primer layer can be formed off-line. Specifically, after obtaining a resin film by forming a polyolefin or a resin composition containing a polyolefin using a T-die method or an inflation method, the resin film is stretched, and the resin film after stretching is obtained. A primer layer coating solution may be applied thereon and dried.

The primer layer can also be formed in-line. Specifically, after obtaining a resin film by forming a polyolefin or a resin composition containing a polyolefin using a T-die method or an inflation method, the resin film is stretched in the longitudinal direction (MD direction). Then, the resin film may be coated with a primer layer coating solution, dried, and then stretched in the transverse direction (TD direction). In addition, you may perform extending|stretching to a horizontal direction first. Thus, the primer layer can be formed in-line.

A conventional primer layer is mainly formed using a coating liquid containing a resin material and an organic solvent. That is, conventional primer layers are mainly organic solvent-based coating layers. Therefore, in-line processing is difficult in the production of barrier substrates, resulting in high production costs, high energy consumption, and problems from the viewpoint of volatile organic compounds (VOC).

In the present disclosure, the primer layer is formed using a water-based polyhydroxyurethane resin. For example, the primer layer is a coat layer formed using an aqueous dispersion containing a water-based polyhydroxyurethane resin. Therefore, in-line processing is possible in the production of the barrier substrate, and volatile organic compound (VOC) emissions can be suppressed.

<Deposited film>
The barrier substrate has a deposited film provided on the surface of the primer layer. Thereby, the gas barrier property of the barrier substrate, specifically, the oxygen barrier property and the water vapor barrier property can be improved. A packaging container produced using a barrier base material can suppress a decrease in mass of contents filled in the packaging container.

The deposited film, in one embodiment, is composed of an inorganic oxide.
Examples of inorganic oxides include aluminum oxide (alumina), silicon oxide (silica), magnesium oxide, calcium oxide, zirconium oxide, titanium oxide, boron oxide, hafnium oxide, barium oxide, and silicon oxide carbide (carbon-containing silicon oxide). is mentioned. Among these, silica, silicon carbide oxide and alumina are preferred.

In one embodiment, silica is more preferable as the inorganic oxide because it does not require an aging treatment after deposition film formation. In one embodiment, carbon-containing silicon oxide is more preferable as the inorganic oxide, since it is possible to suppress deterioration of the gas barrier property even when the barrier substrate is bent.

The thickness of the deposited film is preferably 1 nm or more and 150 nm or less, more preferably 5 nm or more and 60 nm or less, and still more preferably 10 nm or more and 40 nm or less. When the thickness is at least the lower limit, for example, the oxygen barrier properties and water vapor barrier properties of the barrier substrate can be further improved. When the thickness is equal to or less than the upper limit, for example, the occurrence of cracks in the deposited film can be suppressed, and the recyclability of the packaging container can be improved.

The surface of the deposited film is preferably subjected to the surface treatment described above. This can improve the adhesion between the deposited film and the adjacent layer.

Examples of methods for forming a deposited film include physical vapor deposition methods (physical vapor deposition methods, PVD methods) such as vacuum deposition methods, sputtering methods and ion plating methods, plasma chemical vapor deposition methods, and thermal chemical vapor deposition methods. A chemical vapor deposition method (Chemical Vapor Deposition method, CVD method) such as a growth method and a photochemical vapor deposition method can be used.

The vapor deposition film may be a single layer formed by one vapor deposition process, or may be a multilayer film formed by multiple vapor deposition processes. When the deposited film is multilayered, each layer may be composed of the same inorganic oxide, or may be composed of different inorganic oxides. Each layer may be formed by the same method or by different methods.

The vapor-deposited film on the barrier substrate is preferably a vapor-deposited film formed by a CVD method, and more preferably a carbon-containing silicon oxide vapor-deposited film formed by a CVD method. Thereby, even if the barrier substrate is bent, deterioration of the gas barrier properties can be suppressed.

The carbon-containing silicon oxide deposited film contains silicon, oxygen and carbon.
In one embodiment of the carbon-containing silicon oxide deposited film, the proportion C of carbon is preferably 3% or more and 50% or less, more preferably 5% or more and 40% with respect to the total 100% of the three elements of silicon, oxygen and carbon. % or less, more preferably 10% or more and 35% or less. By setting the ratio C of carbon within the above range, for example, deterioration of the gas barrier property can be suppressed even when the barrier substrate is bent. In this specification, the ratio of each element is on a molar basis.

In one embodiment of the carbon-containing silicon oxide deposited film, the ratio Si of silicon is preferably 1% or more and 45% or less, more preferably 3% or more and 38% with respect to a total of 100% of the three elements of silicon, oxygen and carbon. % or less, more preferably 8% or more and 33% or less. The oxygen ratio O is preferably 10% or more and 70% or less, more preferably 20% or more and 65% or less, and still more preferably 25% or more and 60% or less with respect to 100% in total of the three elements of silicon, oxygen, and carbon. is. By setting the ratio Si of silicon and the ratio O of oxygen within the above range, for example, even if the barrier substrate is bent, deterioration of the gas barrier properties can be further suppressed.

In one embodiment of the carbon-containing silicon oxide deposited film, the oxygen proportion O is preferably higher than the carbon proportion C, the silicon proportion Si is preferably lower than the carbon proportion C, and the oxygen proportion O is preferably higher than the silicon fraction Si. In other words, it is preferable that each ratio decreases in the order of ratio O, ratio C, and ratio Si. As a result, for example, even if the barrier substrate is bent, deterioration of the gas barrier property can be further suppressed.

The proportion C, the proportion Si and the proportion O in the carbon-containing silicon oxide deposited film can be measured by narrow scan analysis under the following measurement conditions by X-ray photoelectron spectroscopy (XPS).

(Measurement condition)
Equipment used: “ESCA-3400” (manufactured by Kratos)
[1] Spectrum collection conditions Incident X-ray: MgKα (monochromatic X-ray, hν = 1253.6 eV)
X-ray output: 150W (10kV/15mA)
X-ray scanning area (measurement area): about 6mmφ
Photoelectron capture angle: 90 degrees [2] Ion sputtering conditions Ion species: Ar ⁺
Acceleration voltage: 0.2 (kV)
Emission current: 20 (mA)
Etching range: 10mmφ
Ion sputtering time: 30 seconds, spectrum collected

<Barrier coat layer>
In one embodiment, the barrier substrate can further include a barrier coat layer on the deposited film. That is, the barrier substrate may further include a barrier coat layer on the surface of the deposited film opposite to the stretched resin layer side. Thereby, for example, the oxygen barrier property and water vapor barrier property of the barrier substrate can be improved.

In one embodiment, the barrier coat layer contains a gas barrier resin. Gas barrier resins include, for example, ethylene-vinyl alcohol copolymer, polyvinyl alcohol, polyacrylonitrile, polyester, polyamides such as nylon 6, nylon 6,6 and poly-metaxylylene adipamide, polyurethanes, and (meth)acrylic resins. is mentioned.

The content of the gas barrier resin in the barrier coat layer is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 70% by mass or more. With such a configuration, for example, the gas barrier properties of the barrier coat layer can be improved.
The barrier coat layer may contain the above additives.

The thickness of the barrier coat layer containing the gas barrier resin is preferably 0.01 μm or more and 10 μm or less, more preferably 0.1 μm or more and 5 μm or less. By setting the thickness of the barrier coat layer to 0.01 μm or more, for example, gas barrier properties can be further improved. By setting the thickness of the barrier coat layer to 10 μm or less, for example, the processability of the barrier substrate and the recyclability of the packaging container can be improved.

The barrier coat layer can be formed, for example, by applying and drying a coating liquid obtained by dissolving or dispersing a material such as a gas barrier resin in water or a suitable organic solvent.

In another embodiment, the barrier coat layer is prepared by mixing a metal alkoxide, a water-soluble polymer, and optionally a silane coupling agent, and optionally adding water, an organic solvent, and a sol-gel catalyst. It is a gas barrier coating film formed by applying the obtained gas barrier composition on a deposited film and drying it. The gas barrier coating film contains a hydrolyzed polycondensate obtained by hydrolyzing and polycondensing the metal alkoxide or the like by a sol-gel method. By providing such a barrier coat layer on the vapor deposition film, it is possible to effectively suppress the occurrence of cracks in the vapor deposition film.

A metal alkoxide is represented by Formula (1), for example.
^{R1nM (} _OR2 ) _m (1)
In formula (1), R ¹ and R ² each independently represent an organic group having 1 to 8 carbon atoms, M represents a metal atom, n represents an integer of 0 or more, and m is an integer of 1 or more. and n+m represents the valence of M.

Examples of organic groups for R ¹ and R ² include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, n-hexyl group and Examples thereof include alkyl groups having 1 to 8 carbon atoms such as n-octyl group.
Metal atom M is, for example, silicon, zirconium, titanium or aluminum.

Examples of metal alkoxides include alkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetrabutoxysilane.

Examples of water-soluble polymers include hydroxyl group-containing polymers such as polyvinyl alcohol and ethylene-vinyl alcohol copolymers. Either one of polyvinyl alcohol and ethylene-vinyl alcohol copolymer may be used, or both may be used in combination, depending on desired physical properties such as oxygen barrier properties, water vapor barrier properties, water resistance, and weather resistance. Alternatively, a gas barrier coating film obtained using polyvinyl alcohol and a gas barrier coating film obtained using an ethylene-vinyl alcohol copolymer may be laminated. The amount of the water-soluble polymer used is preferably 3 parts by mass or more and 500 parts by mass or less with respect to 100 parts by mass of the metal alkoxide.

As the silane coupling agent, known organic reactive group-containing organoalkoxysilanes can be used, and organoalkoxysilanes having an epoxy group are preferred, such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxy Propylmethyldiethoxysilane and β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane are included. The amount of the silane coupling agent used is preferably 1 part by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the metal alkoxide.

The gas barrier composition may contain water in a proportion of preferably 0.1 mol or more and 100 mol or less, more preferably 0.5 mol or more and 60 mol or less, relative to 1 mol of the metal alkoxide. By making the water content equal to or higher than the lower limit, for example, the oxygen barrier properties and water vapor barrier properties of the barrier substrate can be improved. By making the water content equal to or less than the upper limit, for example, the hydrolysis reaction can be carried out quickly.

The gas barrier composition may contain an organic solvent. Organic solvents include, for example, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol and n-butyl alcohol.

As the sol-gel process catalyst, an acid or amine compound is preferable.
Acids include, for example, mineral acids such as sulfuric acid, hydrochloric acid and nitric acid; and organic acids such as acetic acid and tartaric acid. The amount of the acid to be used is preferably 0.001 mol or more and 0.05 mol or less per 1 mol of the total molar amount of the metal alkoxide and the alkoxide portion (for example, silicate portion) of the silane coupling agent.

As the amine compound, tertiary amines that are substantially insoluble in water and soluble in organic solvents are suitable, such as N,N-dimethylbenzylamine, tripropylamine, tributylamine and tripentylamine. Amines are mentioned. The amount of the amine compound used is preferably 0.01 parts by mass or more and 1.0 parts by mass or less, more preferably 0.03 parts by mass or more, relative to 100 parts by mass of the total amount of the metal alkoxide and the silane coupling agent. It is 0.3 parts by mass or less.

Examples of the method of applying the gas barrier composition include application means such as roll coating such as gravure roll coater, spray coating, spin coating, dipping, brush, bar coating and applicator.

An embodiment of a method for forming a gas barrier coating film will be described below.
A gas barrier composition is prepared by mixing a metal alkoxide, a water-soluble polymer, a sol-gel catalyst, water, an organic solvent, and optionally a silane coupling agent. A polycondensation reaction proceeds gradually in the composition. The above composition is applied onto the vapor-deposited film by a conventional method and dried. This drying further promotes polycondensation of the metal alkoxide and the water-soluble polymer (and the silane coupling agent if the composition contains a silane coupling agent) to form a composite polymer layer. The above operation may be repeated to laminate a plurality of composite polymer layers. For example, the applied composition is heated at a temperature of preferably 20° C. to 150° C., more preferably 50° C. to 120° C., still more preferably 70° C. to 100° C. for 1 second to 10 minutes. Thereby, a gas barrier coating film can be formed.

The thickness of the gas barrier coating film is preferably 0.01 μm or more and 100 μm or less, more preferably 0.1 μm or more and 50 μm or less, and still more preferably 0.1 μm or more and 5 μm or less. As a result, for example, the gas barrier property can be improved, the occurrence of cracks in the deposited film can be suppressed, and the recyclability of the packaging container can be improved.

<Print layer>
The barrier substrate of the present disclosure may have a printed layer on the surface of the stretched resin layer. The image formed on the printed layer is not particularly limited, and may be letters, patterns, symbols, combinations thereof, or the like. The printing layer can also be formed using a biomass-derived ink. As a result, the environmental load can be further reduced.

Examples of methods for forming the printed layer include conventionally known printing methods such as gravure printing, offset printing, and flexographic printing. Among these, the flexographic printing method is preferable from the viewpoint of reducing the environmental load.

The thickness of the printed layer is, for example, 0.5 μm or more and 3 μm or less.

[Base material for vapor deposition film formation]
The substrate for forming a deposited film of the present disclosure includes at least a stretched resin layer containing polyolefin as a main component, and a primer layer formed on the stretched resin layer. The primer layer contains a water-based polyhydroxyurethane resin. The arithmetic mean roughness Ra on the surface of the primer layer is preferably 2.0 nm or less. Details of the stretched resin layer, the primer layer, each component, and the physical properties (Ra) are as described above, so the description in this section is omitted.

[Barrier laminate]
The barrier laminate of the present disclosure includes at least the above-described barrier substrate and a sealant layer.
The sealant layer is a resin layer containing polyolefin as a main component,
The barrier laminate of the present disclosure is suitable for use as a packaging material.

In the barrier laminate of the present disclosure, the barrier substrate may be arranged such that the deposited film faces the sealant layer side and the stretched resin layer faces the side opposite to the sealant layer. As a result, deterioration of the deposited film can be suppressed.

In one embodiment, the barrier laminate of the present disclosure includes a first base material, a second base material (intermediate base material), and a sealant layer in this order in the thickness direction. and at least one of the second substrate is the barrier substrate.

The barrier laminate of the present disclosure may comprise a stretched substrate containing polyolefin as a main component as the first substrate or the second substrate. The stretched base material containing polyolefin as a main component includes a base material composed of a stretched resin layer containing polyolefin as a main component.

For example, the barrier laminate of the present disclosure includes a stretched base material containing polyolefin as a main component as a first base material, a barrier base material as a second base material, and a sealant layer. Directions may be provided in this order. In this case, the barrier substrate is arranged such that the deposited film faces the first substrate side and the stretched resin layer faces the sealant layer side, or the deposited film faces the sealant layer side and the stretched resin The barrier substrate is arranged so that the layer faces the first substrate side. Among these, the barrier substrate is arranged so that the vapor deposited film faces the first substrate side and the stretched resin layer faces the sealant layer side, from the viewpoint of further suppressing the deterioration of the deposited film. is preferred.

For example, the barrier laminate of the present disclosure includes a barrier substrate as a first substrate, a stretched substrate containing polyolefin as a main component, and a sealant layer as a second substrate. Directions may be provided in this order. In this case, it is preferable that the barrier substrate be arranged so that the deposited film faces the sealant layer side and the stretched resin layer faces the side opposite to the sealant layer.

3 to 8 are schematic cross-sectional views showing one embodiment of the barrier laminate.
The barrier laminate 2 shown in FIG. 3 includes a barrier substrate 1, an adhesive layer 30, and a sealant layer 20 in this order in the thickness direction. The barrier substrate 1 includes a stretched resin layer 10, a primer layer 12, and a deposited film . In this example, the stretched resin layer 10 constitutes the outermost layer of the barrier laminate 2 , and the deposited film 14 is in contact with the adhesive layer 30 .

FIG. 4 is the same as FIG. 3 except that the barrier substrate 1 comprises a stretched resin layer 10, a primer layer 12, a deposited film 14, and a barrier coat layer 16 in this order in the thickness direction. In this example, barrier coat layer 16 is in contact with adhesive layer 30 .

The barrier laminate 2 shown in FIG. 5 includes an oriented polyolefin substrate 3, an adhesive layer 30A, a barrier substrate 1, an adhesive layer 30B, and a sealant layer 20 in this order in the thickness direction. The barrier substrate 1 includes a stretched resin layer 10, a primer layer 12, and a deposited film . In this example, the stretched resin layer 10 is in contact with the adhesive layer 30B, and the deposited film 14 is in contact with the adhesive layer 30A.

FIG. 6 is the same as FIG. 5 except that the barrier substrate 1 comprises a stretched resin layer 10, a primer layer 12, a deposited film 14, and a barrier coat layer 16 in this order in the thickness direction. In this example, the barrier coat layer 16 is in contact with the adhesive layer 30A.

The barrier laminate 2 shown in FIG. 7 includes a barrier substrate 1, an adhesive layer 30A, a polyolefin stretched substrate 3, an adhesive layer 30B, and a sealant layer 20 in this order in the thickness direction. The barrier substrate 1 includes a stretched resin layer 10, a primer layer 12, and a deposited film . In this example, the stretched resin layer 10 constitutes the outermost layer of the barrier laminate 2, and the deposited film 14 is in contact with the adhesive layer 30A.

FIG. 8 is the same as FIG. 7 except that the barrier substrate 1 comprises a stretched resin layer 10, a primer layer 12, a deposited film 14, and a barrier coat layer 16 in this order in the thickness direction. In this example, the barrier coat layer 16 is in contact with the adhesive layer 30A.

Specific examples of the laminate structure of the barrier laminate of the present disclosure are shown below. "/" represents the boundary between layers. "OPP film" refers to a polypropylene substrate that has been stretched.
(1) Barrier substrate/printing layer/adhesive layer/sealant layer (2) OPP film/printing layer/adhesive layer/barrier substrate/adhesive layer/sealant layer (3) Barrier substrate/printing layer/adhesion Layer/OPP film/adhesive layer/sealant layer (4) Barrier substrate/printing layer/adhesive layer/barrier substrate/adhesive layer/sealant layer

The polyolefin content (hereinafter also referred to as "monomaterial ratio") in the barrier laminate of the present disclosure, and in one embodiment, the content of polypropylene or polyethylene is preferably 80% by mass or more, more preferably 85% by mass or more. , more preferably 88% by mass or more, and particularly preferably 90% by mass or more. As a result, for example, a monomaterial packaging container can be produced using the barrier laminate, and the recyclability of the packaging container can be improved. A higher monomaterialization rate is more preferable, but the upper limit may be, for example, 99% by mass or 98% by mass.

In the present disclosure, the monomaterial ratio means the content ratio of polyolefin with respect to the total mass of the barrier laminate. However, when the layer contains polyolefin as a main component (that is, more than 50% by mass), the monomaterial ratio may be calculated assuming that 100% by mass of the layer is composed of polyolefin. For example, in the case of a sealant layer composed of 80% by mass of polypropylene and 20% by mass of another resin material, the above monomaterialization rate is calculated assuming that the sealant layer is composed of 100% by mass of polypropylene. good too.

<Sealant layer>
The barrier laminate of the present disclosure comprises a sealant layer.
The sealant layer is a resin layer containing polyolefin as a main component. In one embodiment, the sealant layer is made of the same resin material as the stretched resin layer in the barrier base material, that is, polyolefin. As a result, the packaging container can be made of a monomaterial. After recovering the used packaging container, there is no need to separate the base material and the sealant layer, and the recyclability of the packaging container can be improved.

Among polyolefins, polypropylene and polyethylene are preferred.

The MFR of the polyolefin constituting the sealant layer is preferably 0.1 g/10 min or more and 50 g/10 min or less, more preferably 0.3 g/10 min or more and 30 g/10 min or less, from the viewpoint of film formability and processability. , more preferably 0.5 g/10 minutes or more and 20 g/10 minutes or less.

When the sealant layer is produced by the T-die method, the MFR of the polyolefin is preferably 5.0 g/10 minutes or more and 20 g/10 minutes or less. When the MFR is at least the lower limit, for example, the workability of the sealant layer can be improved. When the MFR is equal to or less than the upper limit, for example, breakage of the sealant layer can be suppressed.

When the sealant layer is produced by the inflation method, the MFR of the polyolefin is preferably 0.5 g/10 minutes or more and 5.0 g/10 minutes or less. When the MFR is at least the lower limit, for example, the workability of the sealant layer can be improved. When the MFR is equal to or lower than the upper limit, for example, film formability can be improved.

The content of polyolefin in the sealant layer is preferably 70% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, and even more preferably 95% by mass or more. Thereby, for example, the recyclability of the packaging container can be improved.

The sealant layer may contain the above additives.

The sealant layer may have a single layer structure or a multilayer structure.

The thickness of the sealant layer is preferably 10 μm or more and 200 μm or less, more preferably 20 μm or more and 150 μm or less. When the sealant layer has a multilayer structure, the total thickness is preferably within the above range. When the thickness is at least the lower limit, for example, the heat sealability of the sealant layer and the recyclability of the packaging container can be improved. When the thickness is equal to or less than the upper limit, for example, the processability of the barrier laminate can be improved. When a pouch (particularly a pouch for retort pouches) is produced from the barrier laminate, the thickness of the sealant layer is preferably 30 µm to 100 µm, more preferably 40 µm to 100 µm, still more preferably 60 µm to 100 µm.

From the viewpoint of heat sealability, the sealant layer is preferably an unstretched resin film, more preferably an unstretched coextruded resin film, and each layer constituting the sealant layer is a coextruded resin layer. The resin film can be produced by using, for example, a casting method, a T-die method, an inflation method, or the like.
The sealant layer may be subjected to the surface treatment described above.

For example, an unstretched resin film corresponding to the sealant layer may optionally be laminated on the barrier substrate via an adhesive layer, and the polyolefin or its resin composition is melt-extruded onto the barrier substrate. A sealant layer may be formed thereby. Examples of the adhesive layer include an adhesive layer to be described later.

For example, an unstretched resin film corresponding to the sealant layer may be laminated on the first base material or the second base material via an adhesive layer as necessary, and polypropylene or its resin composition may be laminated on the first base material. The sealant layer may be formed by melt extrusion onto the substrate or a second substrate. Examples of the adhesive layer include the following adhesive layers.

The sealant layer, in one embodiment, is a resin layer containing polypropylene as a main component, that is, preferably in a range of more than 50% by mass. By configuring the sealant layer with polypropylene, the oil resistance of the packaging container produced using the laminate can also be improved.

Polypropylene includes, for example, propylene homopolymers, propylene random copolymers such as propylene-α-olefin random copolymers, and propylene block copolymers such as propylene-α-olefin block copolymers. Details of the α-olefin are as described above. From the viewpoint of reducing environmental load, biomass-derived polypropylene and/or recycled polypropylene may be used.

The density of polypropylene is, for example, 0.88 g/cm ³ or more and 0.92 g/cm ³ or less from the viewpoint of heat sealability. In the present disclosure, the density is measured according to JIS K7112, particularly D method (density gradient tube method, 23°C).

The melting point (Tm) of the polypropylene constituting the sealant layer is, for example, 120° C. or higher and 160° C. or lower, preferably 125° C. or higher and 155° C. or lower, more preferably 130° C. or higher and 150° C. or lower, from the viewpoint of the balance between heat resistance and heat sealability. It is below.

In one embodiment, the content of polypropylene in the sealant layer is preferably 70% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, and even more preferably 95% by mass or more. Thereby, for example, the recyclability of the packaging container can be improved.

In one embodiment, the sealant layer is a resin layer containing polyethylene as a main component, that is, preferably containing polyethylene in an amount exceeding 50% by mass. Examples of polyethylene include high-density polyethylene, medium-density polyethylene, low-density polyethylene, linear low-density polyethylene, and ultra-low-density polyethylene. and ultra low density polyethylene are preferred. From the viewpoint of reducing environmental load, biomass-derived polyethylene and/or recycled polyethylene may be used.

The melting point (Tm) of polyethylene constituting the sealant layer is preferably 90° C. or higher and 140° C. or lower, more preferably 90° C. or higher and 130° C. or lower, from the viewpoint of the balance between heat resistance and heat sealability.

In one embodiment, the content of polyethylene in the sealant layer is preferably over 50% by mass, more preferably 80% by mass or more, even more preferably 90% by mass or more, and even more preferably 95% by mass or more. Thereby, for example, the recyclability of the packaging container can be improved.

A sealant film as a sealant layer can be produced, for example, by a conventionally known method. The sealant film is obtained by mixing the above-mentioned materials by a usual method and forming the obtained mixture into a film by a usual method. The sealant film is preferably a film obtained by extrusion. Extrusion is preferably performed by a T-die method or an inflation method. Specifically, after drying the material constituting the sealant film as necessary, it is supplied to a melt extruder heated to a temperature equal to or higher than the melting point of the material to melt the material, for example, a T die or the like. A sealant film can be formed by extruding a film from a die and rapidly cooling and solidifying the extruded film with a rotating cooling drum or the like.

As the melt extruder, a single-screw extruder, a twin-screw extruder, a vent extruder, a tandem extruder, or the like can be used depending on the purpose. The temperature of the molten polymer when extruded from the melt extruder may be, for example, 200° C. or higher and 300° C. or lower, or 220° C. or higher and 270° C. or lower.

<Adhesive layer>
The barrier laminate of the present disclosure, in one embodiment, comprises an adhesive layer between the barrier substrate and the sealant layer. The barrier laminate, in one embodiment, comprises a first adhesive layer between the first substrate and the second substrate. The barrier laminate, in one embodiment, comprises a second adhesive layer between the second substrate and the sealant layer. Thereby, the adhesion between the barrier substrate and the sealant layer, the adhesion between the first substrate and the second substrate, and the adhesion between the second substrate and the sealant layer can be improved.

The adhesive layer is composed of an adhesive. The adhesive may be a one-component curing adhesive, a two-component curing adhesive, or a non-curing adhesive. The adhesive may be a non-solvent type adhesive or a solvent type adhesive.

Solvent-free adhesives, ie, non-solvent laminate adhesives, include, for example, polyether-based adhesives, polyester-based adhesives, silicone-based adhesives, epoxy-based adhesives, and polyurethane-based adhesives. Among these, polyurethane-based adhesives are preferable, and two-liquid curing polyurethane-based adhesives are more preferable.

Examples of solvent-based adhesives include rubber-based adhesives, vinyl-based adhesives, olefin-based adhesives, silicone-based adhesives, epoxy-based adhesives, phenol-based adhesives, and polyurethane-based adhesives. Among these, polyurethane-based adhesives are preferred, and two-liquid curing polyurethane-based adhesives are more preferred.

The thickness of the adhesive layer is preferably 0.1 μm or more and 10 μm or less, more preferably 0.2 μm or more and 8 μm or less, and still more preferably 0.5 μm or more and 6 μm or less.

The method for producing the barrier laminate of the present disclosure is not particularly limited, and it can be produced using a conventionally known method such as a dry lamination method, a melt extrusion lamination method, a sand lamination method, or the like. For example, the laminate of the present disclosure, in one embodiment, comprises a barrier substrate and a sealant film, or a first substrate, a second substrate and a sealant film, using a solvent-free adhesive. It may be produced by laminating by a non-solvent lamination method, or by a dry lamination method using a solvent-based adhesive.

[Packaging container]
The barrier laminate of the present disclosure (hereinafter also simply referred to as "laminate") can be suitably used for packaging materials. Packaging materials are used to make packaging containers. A packaging material comprises the laminate of the present disclosure. A packaging container can be produced by using at least a packaging material comprising the laminate of the present disclosure.

The packaging container of the present disclosure comprises the laminate of the present disclosure. In the packaging container, the sealant layer of the laminate is usually located on the inner surface side. Packaging containers include, for example, packaging bags, tube containers, and containers with lids. A lidded container includes a container body having an accommodating portion, and a lid member joined (heat-sealed) to the container body so as to seal the accommodating portion.

In one embodiment, the packaging container of the present disclosure maintains gas barrier properties even when subjected to high-temperature treatment, and is less deformable, and is therefore suitable as a microwave oven container, or a boil or retort container. The packaging container of the present disclosure is also suitable as a microwave boiler or retort container. The packaging container of the present disclosure is particularly suitable as a boil or retort pouch.

Methods of heat sealing include, for example, bar sealing, rotary roll sealing, belt sealing, impulse sealing, high frequency sealing and ultrasonic sealing.

As packaging bags, for example, standing pouch type, side seal type, two side seal type, three side seal type, four side seal type, envelope pasted seal type, palm pasted seal type (pillow seal type), plaited seal type, flat bottom seal. There are various types of packaging bags such as type, square bottom seal type and gusset type.

The packaging container may be provided with an easy-open part. The easy-to-open portion includes, for example, a notch portion that serves as a starting point for tearing the packaging container, and a half-cut line formed by laser processing, a cutter, or the like as a path for tearing the packaging container.

The packaging container may be provided with a steam release mechanism. When the steam pressure inside the packaging container exceeds a predetermined value, the steam venting mechanism allows the inside of the packaging container to communicate with the outside to release the steam, and also prevents the steam from escaping at locations other than the steam venting mechanism. is configured as

The steam release mechanism includes, for example, a steam release seal portion protruding toward the inside of the packaging container from the side seal portion, and a non-sealed portion separated from the contents accommodating portion by the steam release seal portion. The unsealed portion communicates with the outside of the packaging container. The packaging container filled with contents and heat-sealed at the opening is heated using a microwave oven or the like. As a result, the internal pressure increases and the steam release seal portion is peeled off. The steam escapes to the outside of the packaging container through the peeled portion of the steam releasing seal portion and the non-sealed portion.

In one embodiment, the laminate of the present disclosure is folded in half so that the barrier substrate is positioned on the outside and the sealant layer is positioned on the inside, and the ends and the like are heat-sealed to form a packaging bag. can be made. In another embodiment, a packaging bag can be produced by stacking a plurality of laminates of the present disclosure such that the sealant layers face each other and heat-sealing the ends and the like. The entire packaging bag may be composed of the laminate, or part of the packaging bag may be composed of the laminate.

In one embodiment, the laminate of the present disclosure is used as a lid material in a lidded container. A lidded container includes a container body having an accommodating portion, and a lid member joined (heat-sealed) to the container body so as to seal the accommodating portion. Here, the lid material, that is, the sealant layer of the laminate and the container body are heat-sealed. Examples of the shape of the container body include a cup shape and a bottomed cylindrical shape. The container body is made of, for example, polystyrene, polypropylene, polyethylene, or paper.

Contents contained in packaging containers include, for example, liquids, solids, powders, and gels. The contents may be food or drink, or may be non-food or drink such as chemicals, cosmetics, and pharmaceuticals. After containing the contents in the packaging container, the packaging container can be sealed by heat-sealing the opening of the packaging container.

As specific examples of packaging bags, small bags and standing pouches will be described below.
A sachet is a small packaging bag, and is used to contain, for example, 1 g or more and 200 g or less of contents. Contents contained in the sachet include, for example, sauces, soy sauce, dressings, ketchup, syrups, cooking liquors, other liquid or viscous seasonings; liquid soups, powdered soups, fruit juices; spices; Beverages, jellied beverages, ready-to-eat foods, and other food and drink.

Standing pouches are used, for example, to contain contents of 50 g or more and 2000 g or less. Contents contained in the standing pouch include, for example, shampoo, rinse, conditioner, hand soap, body soap, fragrance, deodorant, deodorant, insect repellent, detergent; dressing, edible oil, mayonnaise, and others. Liquid or viscous seasonings; liquid beverages, jelly-like beverages, instant foods, other foods and drinks; and creams.

FIG. 9 shows a packaging bag 50 obtained by bonding two laminates together. The shaded area indicates the heat-sealed portion. The packaging bag 50 may include an easy-open portion 51 . The easy-to-open portion 51 includes, for example, a notch portion 52 that is a starting point for tearing, and a half-cut line 53 that is formed by laser processing, a cutter, or the like as a path for tearing.

FIG. 10 schematically shows an example of the configuration of a standing pouch. The shaded area indicates the heat-sealed portion. Standing pouch 60 , in one embodiment, comprises a body 61 and a bottom 62 . The trunk portion 61 and the bottom portion 62 may be configured by the same member, or may be configured by separate members. Since the bottom portion 62 retains the shape of the body portion 61, the pouch can be made self-supporting and can be a standing pouch. A storage space for storing contents is formed in a region surrounded by the body portion 61 and the bottom portion 62 .

The standing pouch 60 may be provided with a steam release mechanism 63 . The steam release mechanism 63 includes a steam release seal portion 63a protruding toward the inside of the packaging container from the side seal portion, and a non-sealed portion 63b separated from the contents accommodating portion by the steam release seal portion 63a. The unsealed portion 63b communicates with the outside of the packaging container.

In the standing pouch, only the body may be composed of the laminate of the present disclosure, only the bottom may be composed of the laminate of the present disclosure, or both the body and the bottom may be composed of the laminate of the present disclosure. may

In one embodiment, the body can be formed by making a bag so that the sealant layer included in the laminate of the present disclosure is the innermost layer. In one embodiment, the body can be formed by preparing two laminates of the present disclosure, stacking them so that the sealant layers face each other, and heat-sealing the side edges on both sides to form a bag. .

In another embodiment, the body is prepared by preparing two laminates of the present disclosure, overlapping them with the sealant layers facing each other, and separating the laminates at both side edges of the overlapped laminate. , two laminates folded in a V shape with the sealant layer on the outside are inserted and heat-sealed. Such a method of manufacture results in a standing pouch having a body with side gussets.

In one embodiment, the bottom can be formed by inserting the laminate of the present disclosure between the formed bag lower body and heat sealing. More specifically, the bottom portion can be formed by inserting a laminated body folded in a V shape so that the sealant layer is on the outside, and heat-sealing it between the lower parts of the bag body.

In one embodiment, two laminates are prepared, these are superimposed so that the sealant layers face each other, and then another laminate is folded in a V shape so that the sealant layer is on the outside. , is sandwiched between the lower portions of the laminates facing each other and heat-sealed to form a bottom portion. The body is then formed by heat sealing the two sides adjacent to the bottom. In this manner, an embodiment standing pouch can be formed.

The present disclosure relates to, for example, the following [1] to [15].
[1] A barrier substrate comprising at least a stretched resin layer containing polyolefin as a main component and a vapor deposited film, wherein the barrier substrate comprises a water-based polyhydroxyurethane between the stretched resin layer and the vapor deposited film. A barrier substrate, further comprising a primer layer containing a resin.
[2] The barrier according to [1] above, wherein the water-based polyhydroxyurethane resin has an acid value of 10 mgKOH/g or more and 100 mgKOH/g or less and a hydroxyl value of 150 mgKOH/g or more and 300 mgKOH/g or less. base material.
[3] The barrier substrate according to [1] or [2] above, wherein the ratio of the thickness of the primer layer to the total thickness of the barrier substrate is 1% or more and 20% or less.
[4] The barrier substrate according to any one of [1] to [3] above, wherein the primer layer surface has an arithmetic mean roughness Ra of 2.0 nm or less.
[5] The barrier substrate according to any one of [1] to [4] above, wherein the polyolefin is polypropylene or polyethylene.
[6] The barrier substrate according to any one of [1] to [5] above, wherein the deposited film is a deposited film composed of an inorganic oxide.
[7] The barrier substrate according to any one of [1] to [6] above, further comprising a barrier coat layer on the deposited film.
[8] A barrier laminate comprising at least a substrate and a sealant layer, wherein the substrate is the barrier substrate according to any one of [1] to [7] above, and the sealant layer is polyolefin A barrier laminate, which is a resin layer containing as a main component.
[9] The stretched resin layer contains polypropylene as a main component, and the sealant layer contains polypropylene as a main component, or the stretched resin layer contains polyethylene as a main component, and the sealant layer contains polyethylene as a main component. The barrier laminate according to [8] above, containing as a main component.
[10] The barrier laminate according to [8] or [9] above, wherein the polyolefin content is 80% by mass or more.
[11] A packaging container comprising the barrier laminate according to any one of [8] to [10] above.
[12] The packaging container according to [11] above, which is a boil or retort pouch.
[13] A lid material comprising the barrier laminate according to any one of [8] to [10] above.
[14] A packaging container comprising a container body having an accommodating portion, and the lid member according to the above [13] joined to the container body so as to seal the accommodating portion.
[15] A vapor deposition film forming substrate comprising at least a stretched resin layer containing polyolefin as a main component and a primer layer formed on the stretched resin layer, wherein the primer layer contains a water-based polyhydroxyurethane resin and an arithmetic mean roughness Ra of the surface of the primer layer of 2.0 nm or less.

The barrier substrate of the present disclosure will be specifically described below based on examples.

[Example 1]
Water containing 20% by mass of water-based polyhydroxy urethane resin (weight average molecular weight: 72,000, acid value: 20 mgKOH/g, hydroxyl value: 195 mgKOH/g, _CO2 content: 20% by mass, d50: 0.02 µm) A dispersion was prepared. This aqueous dispersion was used as a primer layer coating solution.

A biaxially oriented polypropylene film (ME-1, Mitsui Chemicals Tohcello, Inc.) having a thickness of 20 μm and having one side subjected to corona treatment was prepared. The above coating solution for primer layer was applied to the corona-treated surface of the film and dried to form a primer layer having a thickness of 1.0 μm.

On the primer layer, a carbon-containing silicon oxide (silica) deposition film with a thickness of 12 nm is formed by the CVD method while applying tension to the film by Roll to Roll using a low-temperature plasma chemical vapor deposition apparatus, which is an actual machine. did.

The deposition film formation conditions were as follows.
(Formation conditions)
・ Hexamethyldisiloxane: oxygen gas: helium = 1:10:10 (unit: slm)
・Power supplied to cooling/electrode drum: 22 kW
・Line speed: 100m/min

After that, the carbon ratio C, the silicon ratio Si, and the oxygen ratio O in the carbon-containing silicon oxide deposited film were measured by X-ray photoelectron spectroscopy (XPS) by narrow scan analysis under the above-described measurement conditions. The ratio C of carbon, the ratio Si of silicon, and the ratio O of oxygen were 32.7%, 29.8%, and 37.5%, respectively, with respect to the total 100% of the three elements of silicon, oxygen, and carbon. Ta.

As described above, a transparent barrier substrate (1) comprising a biaxially stretched polypropylene film, a primer layer, and a carbon-containing silicon oxide deposition film was obtained.

385 g of water, 67 g of isopropyl alcohol, and 9.1 g of 0.5N hydrochloric acid were mixed to obtain a solution of pH 2.2. To this solution, 175 g of tetraethoxysilane as a metal alkoxide and 9.2 g of glycidoxypropyltrimethoxysilane as a silane coupling agent were mixed while cooling to 10° C. to obtain a solution A. A solution B was obtained by mixing 14.7 g of polyvinyl alcohol having a saponification degree of 99% or more and a degree of polymerization of 2400 as a water-soluble polymer, 324 g of water, and 17 g of isopropyl alcohol. Solution A and solution B were mixed so that the ratio by mass (solution A:solution B) was 6.5:3.5 to obtain a barrier coating agent. A barrier coating agent was coated on the carbon-containing silicon oxide deposition film by spin coating, and heat-treated in an oven at 80° C. for 60 seconds to form a barrier coating layer with a thickness of 300 nm.

As described above, a transparent barrier substrate (2) comprising a biaxially stretched polypropylene film, a primer layer, a carbon-containing silicon oxide deposition film, and a barrier coat layer was obtained.

[Comparative Example 1]
The procedure was the same as in Example 1, except that no primer layer was provided.

[Comparative Example 2]
As a coating solution for the primer layer, a 2-component curing type resin of polyester polyol and polyisocyanate (solid content 10% by mass, organic solvent solution) was applied and dried to form a primer layer with a thickness of 1.0 μm. Except for this, the same procedure as in Example 1 was carried out.

[evaluation]
[Oxygen permeability]
Using an oxygen permeability measuring device (OX-TRAN2/20, manufactured by MOCON), the biaxially stretched polypropylene film surface of the transparent barrier substrate is set to the oxygen supply side, and is measured in accordance with JIS K7126. , a temperature of 23° C. and a relative humidity of 90% RH (unit: cc/m ² ·day·atm).

[Water vapor permeability]
Using a water vapor transmission rate measuring device (PERMATRAN-w 3/33, manufactured by MOCON), the biaxially oriented polypropylene film surface of the transparent barrier substrate is set to the water vapor supply side, and is measured in accordance with JIS K7129. Then, the water vapor transmission rate (g/m ² ·day) was measured under an environment of a temperature of 40°C and a relative humidity of 90% RH.

[Arithmetic mean roughness]
At the stage of forming the primer layer on the biaxially stretched polypropylene film, the arithmetic mean roughness Ra (nm) of the primer layer was measured using an atomic force microscope (AFM) under the condition of a stylus tip curvature radius of 2 μm. In Comparative Example 1, the arithmetic mean roughness Ra (nm) of the biaxially stretched polypropylene film was measured.

1: barrier substrate, 2: barrier laminate, 3: stretched polyolefin substrate, 10: stretched resin layer, 12: primer layer, 14: deposited film, 16: barrier coat layer, 20: sealant layer, 30, 30A, 30B: adhesive layer,
50: packaging bag, 51: easy-to-open portion, 52: notch portion, 53: half-cut line,
60: standing pouch, 61: body portion, 62: bottom portion, 63: vapor release mechanism, 63a: vapor release seal portion, 63b: non-seal portion

Claims (15)

A stretched resin layer containing polyolefin as a main component;
A barrier substrate comprising at least a vapor deposited film,
The barrier substrate further comprises a primer layer containing a water-based polyhydroxyurethane resin between the stretched resin layer and the deposited film.
Barrier substrate. 2. The barrier substrate according to claim 1, wherein the water-based polyhydroxyurethane resin has an acid value of 10 mgKOH/g or more and 100 mgKOH/g or less and a hydroxyl value of 150 mgKOH/g or more and 300 mgKOH/g or less. . 3. The barrier substrate according to claim 1, wherein the ratio of the thickness of the primer layer to the total thickness of the barrier substrate is 1% or more and 20% or less. The barrier substrate according to any one of claims 1 to 3, wherein the primer layer surface has an arithmetic mean roughness Ra of 2.0 nm or less. The barrier substrate according to any one of claims 1 to 4, wherein the polyolefin is polypropylene or polyethylene. The barrier substrate according to any one of claims 1 to 5, wherein the vapor deposited film is a vapor deposited film composed of an inorganic oxide. The barrier substrate according to any one of claims 1 to 6, further comprising a barrier coat layer on the deposited film. A barrier laminate comprising at least a substrate and a sealant layer,
The base material is the barrier base material according to any one of claims 1 to 7,
The sealant layer is a resin layer containing polyolefin as a main component,
Barrier laminate. The stretched resin layer contains polypropylene as a main component, and the sealant layer contains polypropylene as a main component, or
The stretched resin layer contains polyethylene as a main component, and the sealant layer contains polyethylene as a main component,
The barrier laminate according to claim 8. 10. The barrier laminate according to claim 8, wherein the polyolefin content is 80% by mass or more. A packaging container comprising the barrier laminate according to any one of claims 8 to 10. The packaging container according to claim 11, which is a boil or retort pouch. A lid material comprising the barrier laminate according to any one of claims 8 to 10. a container body having an accommodating portion;
A packaging container comprising the lid member according to claim 13 joined to the container body so as to seal the accommodating portion. A stretched resin layer containing polyolefin as a main component;
A base material for forming a deposited film comprising at least a primer layer formed on the stretched resin layer,
The primer layer contains a water-based polyhydroxyurethane resin,
The arithmetic average roughness Ra on the surface of the primer layer is 2.0 nm or less,
Substrate for deposition film formation.