JP7339870B2 - Multilayer structure, manufacturing method thereof, packaging material and product using same, and protective sheet for electronic device - Google Patents

Description

TECHNICAL FIELD The present invention relates to a multilayer structure, a method for producing the same, packaging materials and products using the same, and protective sheets for electronic devices.

A multi-layered structure in which a gas barrier layer composed of aluminum or aluminum oxide is formed on a plastic film has been well known for a long time, and is used as a packaging material to protect articles that are easily deteriorated by oxygen (for example, food). It is These gas barrier layers are formed on plastic films by dry processes such as physical vapor deposition (PVD) and chemical vapor deposition (CVD), and the reaction products of aluminum oxide particles and phosphorus compounds are In some cases, it is formed by coating on plastic. Moreover, such a multilayer structure is also used as a constituent member of a protective sheet for an electronic device that requires gas barrier properties and water vapor barrier properties for the purpose of protecting the features of the electronic device.

Patent Document 1 describes a composite structure having a transparent gas barrier layer composed of a reaction product of aluminum oxide particles and a phosphorus compound. describes a method in which a coating liquid containing aluminum oxide particles and a phosphorus compound is applied to the substrate, followed by drying and heat treatment.

On the other hand, in Patent Document 2, an anchor coat using a coating agent whose main component is a mixture of a water-based dispersion liquid having polyurethane as a main chain and a solvent-based isocyanate curing agent between a base material layer and a vapor deposition layer. It is described that the provision of a layer suppresses the deterioration of barrier properties after storage under high temperature and high humidity conditions.

WO2011/122036 JP 2013-199066 A

However, when the above conventional multilayer structure is used as a packaging material and autoclaved under conditions exceeding 130° C. (for example, 135° C.) (hereinafter referred to as “severe conditions”), the interlayer between the substrate and the gas barrier layer may peel off, resulting in deterioration of gas barrier properties and poor appearance. Therefore, there is a demand for a gas barrier multi-layer structure having good properties even after autoclave treatment under severe conditions.

An object of the present invention is to provide a novel multilayer structure which is excellent in gas barrier properties and water vapor barrier properties, can maintain the barrier properties even after autoclave treatment under severe conditions, and does not cause appearance defects such as delamination, and the like. It is to provide packaging materials and products used. Another object of the present invention is to use a novel multilayer structure that not only has excellent gas barrier properties and water vapor barrier properties, but also can maintain excellent gas barrier properties and water vapor barrier properties even after a dump heat test. To provide a protective sheet for an electronic device. The ability to maintain its barrier properties even after autoclave treatment under severe conditions and the fact that appearance defects such as delamination do not occur even after autoclave treatment under severe conditions are hereinafter referred to as "severe autoclave treatment resistance". is sometimes expressed as

That is, the present invention
[1] A substrate (X), a layer (Z) laminated on the substrate (X), and a layer (Y) laminated on the layer (Z), wherein the layer (Y) contains aluminum a multilayer structure comprising a reaction product (D) of a metal oxide (A) and an inorganic phosphorus compound (BI), wherein the layer (Z) comprises a hydroxyl group-containing resin (C);
[2] The multilayer structure of [1], wherein the hydroxyl-containing resin (C) accounts for more than 50% by mass of the layer (Z);
[3] The hydroxyl-containing resin (C) has hydroxyl-containing monomer units, and the content of the hydroxyl-containing monomer units in the hydroxyl-containing resin (C) constitutes the hydroxyl-containing resin (C). The multilayer structure of [1] or [2], which is 30 mol% or more with respect to all monomer units;
[4] Viscosity of 4% by mass aqueous solution of hydroxyl group-containing resin (C) is 1 mPa s or more and 100 mPa s or less, measured according to JIS K 6726 (1994) [1] to [3] ] any multilayer structure;
[5] The multilayer structure of any one of [1] to [4], wherein the hydroxyl-containing resin (C) contains a vinyl alcohol-based resin;
[6] The multilayer structure of [5], wherein the vinyl alcohol resin has a degree of saponification of 40 to 99.9 mol%;
[7] The multilayer structure of any one of [1] to [6], wherein the layer (Z) has a thickness in the range of 1 to 100 nm;
[8] Step (I) of applying a coating liquid (R) containing a hydroxyl group-containing resin (C) and a solvent onto a substrate (X) and then removing the solvent to form a layer (Z); A step of applying a coating liquid (S) containing a metal oxide (A) containing a metal oxide (A), an inorganic phosphorus compound (BI), and a solvent onto the layer (Z), and then removing the solvent to form a layer (Y) precursor. The method for producing a multilayer structure according to any one of [1] to [7], comprising (II) and step (III) of forming the layer (Y) by heat-treating the layer (Y) precursor;
[9] A packaging material comprising the multilayer structure of any one of [1] to [7];
[10] The packaging material of [9], which is a vertical form-fill-seal bag, a vacuum packaging bag, a pouch, a laminate tube container, an infusion bag, a lid material for a container, a paper container, a strip tape, or an in-mold label container;
[11] A product at least partially using the packaging material of [9] or [10];
[12] The product of [11], wherein the product includes a content, the content is a core material, the interior of the product is decompressed, and functions as a vacuum insulator;
[13] A protective sheet for an electronic device, comprising the multilayer structure of any one of [1] to [7];
[14] The electronic device protection sheet of [13], which is a protection sheet for protecting the surface of a photoelectric conversion device, an information display device, or a lighting device;
[15] An electronic device having a protective sheet of [13] or [14];
This is achieved by providing

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to obtain a novel multilayer structure that is excellent in gas barrier properties, water vapor barrier properties, resistance to severe autoclave treatment, and does not cause appearance defects such as delamination, and packaging materials and products using the same. In addition, a protective sheet for electronic devices using a novel multilayer structure that not only has excellent gas barrier properties and water vapor barrier properties but can maintain excellent gas barrier properties and water vapor barrier properties even after a dump heat test can be obtained.

The multilayer structure of the present invention includes a substrate (X), a layer (Z) laminated on the substrate (X), and a layer (Y) laminated on the layer (Z), and a layer ( Y) contains a reaction product (D) of a metal oxide containing aluminum (A) and an inorganic phosphorus compound (BI), and layer (Z) contains a hydroxyl-containing resin (C).

[Base material (X)]
The material of the substrate (X) is not particularly limited, and substrates made of various materials can be used. Examples of materials for the substrate (X) include resins such as thermoplastic resins and thermosetting resins; fiber aggregates such as fabrics and papers; wood; glass; metals; Among them, it preferably contains a thermoplastic resin and a fiber assembly, and more preferably contains a thermoplastic resin. The form of the substrate (X) is not particularly limited, and may be a layered form such as a film or sheet. The substrate (X) preferably contains at least one selected from the group consisting of a thermoplastic resin film, a paper layer and an inorganic deposition layer (X′), more preferably a thermoplastic resin film, More preferably, it is a plastic resin film.

Thermoplastic resins used for the substrate (X) include, for example, polyolefin resins such as polyethylene and polypropylene; polyethylene terephthalate (PET), polyethylene-2,6-naphthalate, polybutylene terephthalate, and copolymers thereof; Polyamide resins such as nylon-6, nylon-66, and nylon-12; hydroxyl group-containing polymers such as polyvinyl alcohol and ethylene-vinyl alcohol copolymer; polystyrene; poly(meth)acrylic acid ester; polyacrylonitrile; polyvinyl acetate; polycarbonate; polyarylate; regenerated cellulose; polyimide; The thermoplastic resin used for the substrate (X) is preferably at least one selected from the group consisting of polyethylene, polypropylene, polyethylene terephthalate, nylon-6, and nylon-66, more preferably polyethylene terephthalate.

When the thermoplastic resin film is used as the substrate (X), the substrate (X) may be a stretched film or a non-stretched film. A stretched film, particularly a biaxially stretched film, is preferred because the processability (printing, lamination, etc.) of the obtained multilayer structure is excellent. The biaxially stretched film may be a biaxially stretched film produced by any one of a simultaneous biaxial stretching method, a sequential biaxial stretching method and a tubular stretching method.

Examples of paper used for the base material (X) include kraft paper, fine paper, imitation paper, glassine paper, parchment paper, synthetic paper, white paperboard, manila ball, milk carton base paper, cup base paper, ivory paper, and the like. be done. By using paper as the substrate (X), a multilayer structure for a paper container can be obtained.

When the substrate (X) is layered, its thickness is preferably 1 to 1,000 μm, more preferably 5 to 500 μm, from the viewpoint of improving the mechanical strength and workability of the resulting multilayer structure. ~200 μm is even more preferred.

[Inorganic deposition layer (X')]
The inorganic deposition layer (X') is usually a layer having barrier properties against oxygen and water vapor, and preferably has transparency. The inorganic deposition layer (X') can be formed by depositing an inorganic material. Inorganic substances include metals (e.g., aluminum), metal oxides (e.g., silicon oxide, aluminum oxide), metal nitrides (e.g., silicon nitride), metal oxynitrides (e.g., silicon oxynitride), or metal carbonitrides. substances (for example, silicon carbonitride) and the like. Among them, an inorganic deposition layer (X′) formed of aluminum oxide, silicon oxide, magnesium oxide, or silicon nitride is preferable from the viewpoint of excellent barrier properties.

The method for forming the inorganic vapor deposition layer (X′) is not particularly limited, and physical vapor deposition methods such as vacuum vapor deposition (e.g., resistance heating vapor deposition, electron beam vapor deposition, molecular beam epitaxy, etc.), sputtering methods, ion plating methods, etc. Growth method; thermal chemical vapor deposition method (e.g., catalytic chemical vapor deposition method), photochemical vapor deposition method, plasma chemical vapor deposition method (e.g., capacitively coupled plasma, inductively coupled plasma, surface wave plasma, electron cyclotron resonance , dual magnetron, atomic layer deposition, etc.), chemical vapor deposition such as metal-organic vapor deposition.

The thickness of the inorganic vapor deposited layer (X′) varies depending on the type of component constituting the inorganic vapor deposited layer, but is preferably 0.002 to 0.5 μm, more preferably 0.005 to 0.2 μm, and 0.01 to 0.01 μm. 0.1 μm is more preferred. The thickness may be selected within this range so that the multilayer structure has good barrier properties and mechanical strength. When the thickness of the inorganic vapor deposition layer (X') is 0.002 µm or more, the barrier property of the inorganic vapor deposition layer (X') against oxygen and water vapor tends to be improved. Further, when the thickness of the inorganic vapor deposition layer (X') is 0.5 µm or less, the barrier property of the inorganic vapor deposition layer (X') after bending tends to be maintained.

[Layer (Z)]
The layer (Z) is a layer laminated on the substrate (X) and contains the hydroxyl group-containing resin (C). By providing the layer (Z) between the base material (X) and the layer (Y), the interlayer adhesion of the multilayer structure of the present invention is improved, and the severe autoclave treatment resistance is improved. From the viewpoint of adhesion, the layer (Z) is preferably laminated directly with the substrate (X).

[Hydroxyl group-containing resin (C)]
The resin (C) is a resin containing a hydroxyl group, and good adhesion between the substrate (X) and the layer (Y) is exhibited when the resin (C) is used. The resin (C) is preferably a hydrophilic resin, more preferably a water-soluble or water-dispersible resin. The resin (C) preferably has a monomer unit having a hydroxyl group from the viewpoint of increasing hydrophilicity, and the content of the monomer units having such a hydroxyl group is equal to the total monomer units constituting the resin (C). is preferably 30 mol % or more, more preferably 50 mol % or more, still more preferably 65 mol % or more, and particularly preferably 90 mol % or more. In addition, in the resin (C), the content of the monomer unit having a hydroxyl group may be 100% by mass or less, or 99.9% by mass, relative to the total monomer units constituting the resin (C). It may be below. When the content of the monomer unit having a hydroxyl group in the resin (C) is within the above range, the adhesion between the substrate (X) and the layer (Y) will be better, and the severe autoclave treatment resistance will be better. become a trend.

Examples of the resin (C) include hydroxyl group-containing epoxy resins, hydroxyl group-containing polyester resins, hydroxyl group-containing (meth)acrylic resins, hydroxyl group-containing polyurethane resins, vinyl alcohol resins, and polysaccharides. It preferably contains saccharides, more preferably contains a vinyl alcohol-based resin, more preferably a vinyl alcohol-based resin, from the viewpoint of being more excellent in resistance to severe autoclave treatment.

Examples of vinyl alcohol resins include polyvinyl alcohol (hereinafter sometimes abbreviated as "PVA") resins and ethylene-vinyl alcohol copolymer (hereinafter sometimes abbreviated as "EVOH") resins. Among them, the resin (C) is preferably a PVA resin from the viewpoint of good adhesion between the substrate (X) and the layer (Y). The PVA resin includes, for example, a PVA resin obtained by homopolymerizing a vinyl ester and saponifying it, and a modified PVA resin having other modifying groups. The modified PVA resin may be copolymer-modified or post-modified. EVOH resins include, for example, EVOH resins obtained by copolymerizing vinyl ester and ethylene and saponifying them, and modified EVOH resins having other modifying groups. The modified EVOH resin may be copolymer-modified or post-modified. These vinyl alcohol-based resins may be used alone or in combination of two or more. In this specification, an ethylene unit content of 20 mol % or more is defined as an EVOH resin, and an ethylene unit content of less than 20 mol % is defined as a PVA resin.

The degree of saponification of the PVA resin is preferably 40 mol% or more, more preferably 50 mol% or more, even more preferably 70 mol% or more. The degree of saponification of the PVA resin is preferably 99.9 mol% or less, may be 99.0 mol% or less, or may be 98 mol% or less. When the degree of saponification is 40 mol % or more, the adhesion to the layer (Y) tends to be better. Further, when the degree of saponification is 99.9 mol % or less, preparation of the coating liquid (R) described later tends to be facilitated.

The degree of saponification of the EVOH resin is preferably 70 mol% or more, more preferably 80 mol% or more, even more preferably 90 mol% or more. Further, the degree of saponification of the EVOH resin may be 99.9 mol% or less. By adjusting the degree of saponification to the above range, the adhesion to the layer (Y) tends to be better. The ethylene unit content of the EVOH resin may be 20 mol % or more and 60 mol % or less, preferably 40 mol % or less, and more preferably 30 mol % or less. When the ethylene unit content of the EVOH resin is 60 mol % or less, the hydrophilicity tends to be improved and the adhesion between the substrate (X) and the layer (Y) is improved.

When the vinyl alcohol resin has a modifying group, the modifying group includes a silanol group, a thiol group, an aldehyde group, a carboxyl group, a sulfonic acid group, a nitrile group, an amino group, etc., and preferably has a silanol group. By having a modifying group, adhesion may be improved by chemical bonding with the substrate (X) and the layer (Y).

When the vinyl alcohol resin is copolymerized and modified, other monomers to be copolymerized with the vinyl ester include, for example, ethylene, propylene, isobutylene, α-octene, α-dodecene, α-octadecene, and the like. olefins; hydroxy group-containing α-olefins such as 3-buten-1-ol, 4-penten-1-ol, 5-hexene-1-ol and derivatives such as acylated products thereof; acrylic acid, methacrylic acid, Unsaturated acids such as crotonic acid, maleic acid, maleic anhydride, itaconic acid, and undecylenic acid, their salts, monoesters, or dialkyl esters; acrylonitrile, methacrylonitrile, and other nitriles; diacetone acrylamide, acrylamide, methacrylamide, etc. amides; ethylenesulfonic acid, allylsulfonic acid, olefinsulfonic acids such as methallylsulfonic acid or salts thereof; Vinyl compounds such as dialkyl-4-vinyl-1,3-dioquinane, glycerin monoallyl ether, 3,4-diacetoxy-1-butene; substituted vinyl acetates such as isopropenyl acetate and 1-methoxyvinyl acetate; vinylidene chloride ; 1,4-diacetoxy-2-butene; and vinylene carbonate. When the vinyl alcohol resin contains the other monomer, the content thereof may be 10 mol % or less, 5 mol % or less, or 3 mol % or less.

As polysaccharides, those having a molecular weight of 2000 or more are preferable, and examples thereof include starch, cellulose, dextrin, etc. Among them, dextrin is preferable from the viewpoint of easy preparation of the coating liquid (R) described later. As the starch, known starch can be used, and examples thereof include amylose, amylopectin and the like. As the cellulose, known cellulose can be used, but since it is usually insoluble in water, it is preferably dispersed in the coating liquid (R) described later.

The viscosity at 20° C. of the 4% by mass aqueous solution of the resin (C), measured according to JIS K 6726 (1994), is preferably 1 mPa s or more and 100 mPa s or less, and 3 mPa s or more and 90 mPa s. The following is more preferable, and 5 mPa·s or more and 80 mPa·s or less is particularly preferable. Within the above range, the layer (Z) can be easily adjusted to have a uniform thickness, and the adhesiveness of the obtained multilayer structure tends to be stably reproduced.

The layer (Z) may contain other components as long as the effects of the present invention are not impaired. Other components that can be contained in the layer (Z) include, for example, inorganic acid metal salts such as carbonates, hydrochlorides, nitrates, hydrogencarbonates, sulfates, hydrogensulfates, borates, oxalates, acetic acid salts, organic acid metal salts such as tartrates and stearates, metal complexes such as cyclopentadienyl metal complexes (e.g. titanocene), cyano metal complexes (e.g. Prussian blue), layered clay compounds, cross-linking agents, resins ( Polymer compounds other than C), plasticizers, antioxidants, ultraviolet absorbers, flame retardants, and the like can be mentioned. The content of the other components in the layer (Z) is preferably less than 50% by mass, more preferably less than 20% by mass, even more preferably less than 10% by mass, particularly preferably less than 5% by mass, and 0% by mass (other ) may be used.

The proportion of the resin (C) in the layer (Z) is preferably more than 50% by mass, more preferably 80% by mass or more, still more preferably 90% by mass or more, particularly preferably 95% by mass or more, and 99% by mass or more. may be 100% by mass. When the resin (C) in the layer (Z) exceeds 50% by mass, the resistance to severe autoclave treatment tends to be more excellent.

As a method for forming the layer (Z), for example, known printing methods such as offset printing, gravure printing and silk screen printing; and known coating methods such as roll coating, knife edge coating and gravure coating can be used. Drying conditions may be conditions generally used.

The thickness of the layer (Z) is preferably 1 nm or more, more preferably 5 nm or more, even more preferably 10 nm or more. Also, the thickness of the layer (Z) is preferably 100 nm or less, more preferably 70 nm or less, and even more preferably 30 nm or less. When the thickness of the layer (Z) is 1 nm or more and 100 nm or less, there is a tendency that a film with good appearance after autoclave treatment under severe conditions and high transparency can be obtained. The thickness of (Z) can be measured by the method described in Examples below.

[Layer (Y)]
The layer (Y) is a layer laminated on the layer (Z) and contains the reaction product (D) of the metal oxide containing aluminum (A) and the inorganic phosphorus compound (BI). From the viewpoint of adhesion, the layer (Y) is preferably laminated directly on the layer (Z).

[Metal oxide containing aluminum (A)]
The metal atoms constituting the metal oxide (A) (they may be collectively referred to as "metal atoms (M)") are at least one metal selected from metal atoms belonging to groups 2 to 14 of the periodic table. Atoms include at least aluminum atoms. The metal atom (M) may be an aluminum atom alone, or may include an aluminum atom and other metal atoms. In addition, you may mix and use 2 or more types of metal oxides (A) as a metal oxide (A). Metal atoms other than aluminum atoms include, for example, metals of group 2 of the periodic table such as magnesium and calcium; metals of group 12 of the periodic table such as zinc; metals of group 13 of the periodic table; metals of group 13 of the periodic table such as silicon; group metals; transition metals such as titanium and zirconium; Although silicon is sometimes classified as a semimetal, silicon is included in metals in this specification. The metal atom (M) that can be used in combination with aluminum is preferably at least one selected from the group consisting of titanium and zirconium from the viewpoint of excellent handleability and gas barrier properties of the resulting multilayer structure.

The proportion of aluminum atoms in the metal atoms (M) is preferably 50 mol% or more, more preferably 70 mol% or more, still more preferably 90 mol% or more, even if it is 95 mol% or more, it is 100 mol% or more. good too. Examples of the metal oxide (A) include metal oxides produced by methods such as a liquid phase synthesis method, a gas phase synthesis method, and a solid pulverization method.

The metal oxide (A) may be a hydrolytic condensate of a compound (E) containing a metal atom (M) to which a hydrolyzable characteristic group is attached. Examples of the characteristic group include halogen atoms, NO ₃ , optionally substituted alkoxy groups having 1 to 9 carbon atoms, and optionally substituted aryloxy groups having 6 to 9 carbon atoms. , an optionally substituted C 2-9 acyloxy group, an optionally substituted C 3-9 alkenyloxy group, an optionally substituted C 5 A β-diketonato group of up to 15, or a diacylmethyl group having an optionally substituted acyl group of 1 to 9 carbon atoms. A hydrolytic condensate of compound (E) can be substantially regarded as metal oxide (A). Therefore, in this specification, the hydrolytic condensate of compound (E) may be referred to as "metal oxide (A)". That is, in the present specification, "metal oxide (A)" can be read as "hydrolysis condensate of compound (E)", and "hydrolysis condensate of compound (E)" can be read as "metal oxidation It can also be read as "thing (A)".

[Compound (E) Containing Metal Atom (M) to which Hydrolyzable Specific Group is Bonded]
The compound (E) preferably contains an aluminum-containing compound (Ea), which will be described later, because the reaction with the inorganic phosphorus compound (BI) can be easily controlled and the resulting multilayer structure has excellent gas barrier properties.

Examples of the compound (Ea) include aluminum chloride, aluminum nitrate, aluminum acetate, tris(2,4-pentanedionato)aluminum, trimethoxyaluminum, triethoxyaluminum, tri-n-propoxyaluminum, triisopropoxyaluminum, tri-n-butoxyaluminum, tri-sec-butoxyaluminum, tri-tert-butoxyaluminum, etc., among which triisopropoxyaluminum and tri-sec-butoxyaluminum are preferred. As the compound (E), two or more compounds (Ea) may be used in combination.

The compound (E) may also contain a compound (Eb) containing a metal atom (M) other than aluminum. Examples of the compound (Eb) include tetrakis(2,4-pentanedionato)titanium, tetra Titanium compounds such as methoxytitanium, tetraethoxytitanium, tetraisopropoxytitanium, tetra-n-butoxytitanium, tetrakis(2-ethylhexoxy)titanium; tetrakis(2,4-pentanedionato)zirconium, tetra-n-propoxyzirconium, and zirconium compounds such as tetra-n-butoxyzirconium. These may be used individually by 1 type, or may use 2 or more types of compounds (Eb) together.

The ratio of the compound (Ea) to the compound (E) is not particularly limited, and is preferably 80 mol% or more, more preferably 90 mol% or more, further preferably 95 mol% or more, and may be 100 mol%. .

By hydrolyzing the compound (E), at least part of the hydrolyzable characteristic groups of the compound (E) are converted to hydroxyl groups. Furthermore, the hydrolyzate is condensed to form a compound in which the metal atom (M) is bonded via the oxygen atom (O). When this condensation is repeated, compounds are formed which can be regarded as substantially metal oxides. Incidentally, hydroxyl groups are usually present on the surface of the metal oxide (A) thus formed.

In this specification, a compound in which the ratio of [number of moles of oxygen atoms (O) bonded only to metal atoms (M)]/[number of moles of metal atoms (M)] is 0.8 or more is defined as a metal shall be included in oxide (A). Here, the oxygen atom (O) bonded only to the metal atom (M) is the oxygen atom (O) in the structure represented by MOM, and the structure represented by MOH Oxygen atoms bonded to metal atoms (M) and hydrogen atoms (H) such as oxygen atoms (O) in are excluded. The ratio in the metal oxide (A) is preferably 0.9 or higher, more preferably 1.0 or higher, and even more preferably 1.1 or higher. Although the upper limit of this ratio is not particularly limited, it is usually represented by n/2, where n is the valence of the metal atom (M).

In order for the hydrolytic condensation to occur, it is important that the compound (E) has a hydrolyzable characteristic group. If these groups are not bonded, the hydrolytic condensation reaction does not occur or becomes extremely slow, making it difficult to prepare the desired metal oxide (A).

A hydrolytic condensate of compound (E) may be produced from a specific raw material by, for example, a technique employed in a known sol-gel method. The raw materials include compound (E), a partial hydrolyzate of compound (E), a complete hydrolyzate of compound (E), a compound obtained by partially hydrolyzing and condensing compound (E), and compound (E ) can be used at least one selected from the group consisting of compounds obtained by condensing a part of the complete hydrolyzate.

The metal oxide (A) to be mixed with the inorganic phosphorus compound (BI)-containing material (the inorganic phosphorus compound (BI) or the composition containing the inorganic phosphorus compound (BI)) described below contains substantially phosphorus atoms. It is preferable not to contain

[Inorganic phosphorus compound (BI)]
The inorganic phosphorus compound (BI) contains sites capable of reacting with the metal oxide (A), and typically contains a plurality of such sites, preferably 2 to 20 sites. Such sites include functional groups (e.g., hydroxyl groups) present on the surface of the metal oxide (A) and sites capable of condensation reactions, e.g., halogen atoms directly bonded to phosphorus atoms, phosphorus atoms directly bonded to An oxygen atom etc. are mentioned. Functional groups (eg, hydroxyl groups) present on the surface of the metal oxide (A) are usually bonded to metal atoms (M) constituting the metal oxide (A).

Examples of inorganic phosphorus compounds (BI) include phosphoric acid, diphosphoric acid, triphosphoric acid, polyphosphoric acid in which four or more molecules of phosphoric acid are condensed, phosphorous acid, phosphonic acid, phosphonous acid, phosphinic acid, and phosphine. Phosphorus oxoacids such as acids, salts thereof (e.g., sodium phosphate), and derivatives thereof (e.g., halides (e.g., phosphoryl chloride), dehydrates (e.g., diphosphorus pentoxide)), etc. and may be used singly or in combination of two or more. Among them, from the viewpoint of improving the stability of the coating liquid (S) described below and the gas barrier properties of the obtained multilayer structure, phosphoric acid is used alone, or phosphoric acid is used in combination with another inorganic phosphorus compound (BI). preferably. When phosphoric acid and another inorganic phosphorus compound (BI) are used in combination, it is preferable that 50 mol % or more of the inorganic phosphorus compound (BI) is phosphoric acid.

[Reaction product (D)]
The reaction product (D) is obtained by reacting the metal oxide (A) with the inorganic phosphorus compound (BI). The reaction product (D) also includes compounds produced by reacting the metal oxide (A), the inorganic phosphorus compound (BI), and other compounds.

In the infrared absorption spectrum of the layer (Y), the maximum absorption wave number in the region of 800-1400 cm ^-1 is preferably in the range of 1080-1130 cm ^-1 . For example, in the process where the metal oxide (A) and the inorganic phosphorus compound (BI) react to form the reaction product (D), the metal atom (M) derived from the metal oxide (A) and the inorganic phosphorus compound ( BI) and a phosphorus atom (P) originating from BI) form a bond represented by M--O--P via an oxygen atom (O). As a result, a characteristic absorption band derived from the bond is generated in the infrared absorption spectrum of the reaction product (D). When the characteristic absorption band based on MOP bonds is found in the region of 1080 to 1130 cm ^-1 , the obtained multilayer structure exhibits excellent gas barrier properties. In particular, when the characteristic absorption band is the strongest absorption in the region of 800 to 1400 cm ⁻¹ where absorption originating from bonding between various atoms and oxygen atoms is generally observed, the obtained multilayer structure further Exhibits excellent gas barrier properties.

On the other hand, when a metal compound such as a metal alkoxide or a metal salt and the inorganic phosphorus compound (BI) are mixed in advance and then hydrolytically condensed, the metal atoms derived from the metal compound and the inorganic phosphorus compound (BI) A composite is obtained in which the originating phosphorus atoms are almost uniformly mixed and reacted. In that case, in the infrared absorption spectrum, the maximum absorption wave number in the region of 800 to 1400 cm ^-1 is outside the range of 1080 to 1130 cm ^-1 .

In the infrared absorption spectrum of the layer (Y), the half width of the maximum absorption band in the region of 800 to 1400 cm ^-1 is preferably 200 cm ^-1 or less, and 150 cm ^-1 or less from the viewpoint of the gas barrier properties of the resulting multilayer structure. It is more preferably 100 cm ^-1 or less, and particularly preferably 50 cm ^-1 or less.

The infrared absorption spectrum of the layer (Y) can be measured by an attenuated total reflection method using a Fourier transform infrared spectrophotometer (Spectrum One manufactured by PerkinElmer Co., Ltd.) with a measurement range of 800 to 1400 cm ⁻¹ . However, when the measurement cannot be performed by the above methods, reflection measurements such as the reflection absorption method, external reflection method, and attenuated total reflection method, and transmission measurements such as the Nujol method and the tablet method after scraping the layer (Y) from the multilayer structure. , but is not limited to these.

Moreover, the layer (Y) may partially contain the metal oxide (A) and/or the inorganic phosphorus compound (BI) that are not involved in the reaction.

In the layer (Y), the molar ratio between the metal atoms constituting the metal oxide (A) and the phosphorus atoms derived from the inorganic phosphorus compound (BI) is [metal atoms constituting the metal oxide (A)]:[ Phosphorus atom derived from inorganic phosphorus compound (BI)] is preferably in the range of 1.0:1.0 to 3.6:1.0, preferably 1.1:1.0 to 3.0:1. It is more preferably in the range of 0. Within this range, excellent gas barrier properties can be obtained. The molar ratio in the layer (Y) can be adjusted by adjusting the mixing ratio of the metal oxide (A) and the inorganic phosphorus compound (BI) in the coating liquid (S) for forming the layer (Y). The molar ratio in layer (Y) is usually the same as in coating liquid (S).

The thickness of the layer (Y) (when the multilayer structure has two or more layers (Y), the total thickness of each layer (Y)) is preferably 0.05 to 4.0 μm, and 0.1 ~2.0 μm is more preferred. By making the layer (Y) thinner, it is possible to suppress the dimensional change of the multilayer structure during processing such as printing and lamination. Moreover, since the flexibility of the multilayer structure is increased, its mechanical properties can be brought closer to those of the base material itself. When the multilayer structure of the present invention has two or more layers (Y), the thickness of each layer (Y) is preferably 0.05 μm or more from the viewpoint of gas barrier properties. The thickness of the layer (Y) can be controlled by the concentration of the coating liquid (S) used for forming the layer (Y), which will be described later, or the coating method thereof. The thickness of layer (Y) can be measured by observing the cross section of the multilayer structure with a scanning electron microscope or a transmission electron microscope.

The layer (Y) may contain at least one selected from the group consisting of organic phosphorus compounds (BO) and polymers (F) in addition to the components described above.

[Organic phosphorus compound (BO)]
The organophosphorus compound (BO) is preferably a polymer (BOa) having a plurality of phosphorus atoms or an organophosphorus compound (BOb) described below.

[Polymer having a plurality of phosphorus atoms (BOa)]
The functional group containing a phosphorus atom possessed by the polymer (BOa) includes, for example, a phosphoric acid group, a phosphorous acid group, a phosphonic acid group, a phosphonous acid group, a phosphinic acid group, a phosphinic acid group, and derivatives thereof. functional groups (eg, salts, (partial) ester compounds, halides (eg, chlorides), dehydrates), etc., among which phosphate groups and phosphonic acid groups are preferred, and phosphonic acid groups are more preferred.

Examples of the polymer (BOa) include 6-[(2-phosphonoacetyl)oxy]hexyl acrylate, 2-phosphonooxyethyl methacrylate, phosphonomethyl methacrylate, 11-phosphonoundecyl methacrylate, methacrylic acid 1 , Polymers of phosphono (meth) acrylic acid esters such as 1-diphosphonoethyl; Polymers; polymers of vinylphosphinic acids such as vinylphosphinic acid and 4-vinylbenzylphosphinic acid; and starch phosphates. The polymer (BOa) may be a homopolymer of a monomer having a functional group containing at least one phosphorus atom, or may be a copolymer of two or more monomers. Further, as the polymer (BOa), two or more types of polymers composed of a single monomer may be used in combination. Among them, phosphono(meth)acrylic acid ester polymers and vinylphosphonic acid polymers are preferred, and vinylphosphonic acid polymers are more preferred. That is, poly(vinylphosphonic acid) is preferable as the polymer (BOa). The polymer (BOa) can also be obtained by homopolymerizing or copolymerizing a vinylphosphonic acid derivative such as a vinylphosphonic acid halide or a vinylphosphonic acid ester, followed by hydrolysis.

The polymer (BOa) may also be a copolymer of a monomer having at least one functional group containing a phosphorus atom and another vinyl monomer. Other vinyl monomers that can be copolymerized with a monomer having a functional group containing a phosphorus atom include, for example, (meth)acrylic acid, (meth)acrylates, acrylonitrile, methacrylonitrile, styrene, nuclear substitution styrenes, alkyl vinyl ethers, alkyl vinyl esters, perfluoroalkyl vinyl ethers, perfluoroalkyl vinyl esters, maleic acid, maleic anhydride, fumaric acid, itaconic acid, maleimide, phenylmaleimide, etc.; ) acrylic esters, acrylonitrile, styrene, maleimide and phenylmaleimide are preferred.

In order to obtain a multilayer structure having superior bending resistance, the ratio of structural units derived from a monomer having a functional group containing a phosphorus atom to the total structural units of the polymer (BOa) is 10 mol%. 20 mol % or more is more preferable, 40 mol % or more is even more preferable, 70 mol % or more is particularly preferable, and 100 mol % may be acceptable.

Although the molecular weight of the polymer (BOa) is not particularly limited, the number average molecular weight is preferably in the range of 1,000 to 100,000. When the number average molecular weight is in this range, the effect of improving the bending resistance by laminating the layer (Y) and the viscosity stability of the coating liquid (S) when using the coating liquid (S) described later are improved. , compatible at a high level.

When the layer (Y) of the multilayer structure contains the inorganic phosphorus compound (BI) and the polymer (BOa), the weight W _BI of the inorganic phosphorus compound (BI) and the weight of the polymer (BOa) in the layer (Y) The W _BOa ratio W _BOa /W _BI preferably satisfies the relationship of 0.01/99.99≦W _BOa /W _BI <6.00/94.00. More preferably, the relationship of 99.90≦W _BOa /W _BI <4.50/95.50 is satisfied, and the relationship of 0.20/99.80≦W _BOa /W _BI <4.00/96.00 is satisfied. Those satisfying the relationship of 0.50/99.50≦W _BOa /W _BI <3.50/96.50 are particularly preferable. That is, W _BOa is a very small amount of 0.01 or more and less than 6.00, whereas W _BI is preferably used in a large amount of 94.00 or more and 99.99 or less. Note that even when the inorganic phosphorus compound (BI) and/or the organic phosphorus compound (BOa) react in the layer (Y), the inorganic phosphorus compound (BI) and/or the organic phosphorus compound (BOa) constituting the reaction product ) are considered inorganic phosphorus compounds (BI) and/or organic phosphorus compounds (BOa). In this case, the mass of the inorganic phosphorus compound (BI) and/or the organic phosphorus compound (BOa) used to form the reaction product (the mass of the inorganic phosphorus compound (BI) and/or the organic phosphorus compound (BOa) before the reaction ), is included in the weight of inorganic phosphorus compound (BI) and/or organic phosphorus compound (BOa) in layer (Y).

[Organic phosphorus compound (BOb)]
In the organophosphorus compound (BOb), a phosphorus atom to which at least one hydroxyl group is bonded and a polar group are bonded via an alkylene or polyoxyalkylene chain having 3 to 20 carbon atoms. The organic phosphorus compound (BOb) has a lower surface free energy than the metal oxide (A), the inorganic phosphorus compound (BI), and their reaction products (D), and in the process of forming the precursor of the layer (Y), Segregate on the surface side. The organic phosphorus compound (BOb) contains a phosphorus atom to which at least one hydroxyl group capable of reacting with the component contained in the layer (Y) is bonded, and other members (e.g., adhesive layer (I), other layer (J) ( For example, since it has a polar group capable of reacting with the ink layer)), the adhesiveness is improved, and the interlayer adhesion can be maintained even after autoclave treatment under severe conditions, thereby suppressing appearance defects such as delamination. becomes possible.

Organic phosphorus compounds (BOb) include, for example, 3-hydroxypropylphosphonic acid, 4-hydroxybutylphosphonic acid, 5-hydroxypentylphosphonic acid, 6-hydroxyhexylphosphonic acid, 7-hydroxyhepcylphosphonic acid, 8-hydroxy octylphosphonic acid, 9-hydroxynonylphosphonic acid, 10-hydroxydecylphosphonic acid, 11-hydroxyundecylphosphonic acid, 12-hydroxydodecylphosphonic acid, 13-hydroxydotridecylphosphonic acid, 14-hydroxytetradecylphosphonic acid, 15-hydroxypentadecylphosphonic acid, 16-hydroxyhexadecylphosphonic acid, 17-hydroxyheptadecylphosphonic acid, 18-hydroxyoctadecylphosphonic acid, 19-hydroxynonadecylphosphonic acid, 20-hydroxyicosylphosphonic acid, 3-hydroxy propyl dihydrogen phosphate, 4-hydroxybutyl dihydrogen phosphate, 5-hydroxypentyl dihydrogen phosphate, 6-hydroxyhexyl dihydrogen phosphate, 7-hydroxyhepcyl dihydrogen phosphate, 8-hydroxyoctyl dihydrogen phosphate phosphates, 9-hydroxynonyl dihydrogen phosphate, 10-hydroxydecyl dihydrogen phosphate, 11-hydroxyundecyl dihydrogen phosphate, 12-hydroxydodecyl dihydrogen phosphate, 13-hydroxydotridecyl dihydrogen phosphate, 14-hydroxytetradecyldihydrogenphosphate, 15-hydroxypentadecyldihydrogenphosphate, 16-hydroxyhexadecyldihydrogenphosphate, 17-hydroxyheptadecyldihydrogenphosphate, 18-hydroxyoctadecyldihydrogenphosphate, 19 -hydroxynonadecyldihydrogenphosphate, 20-hydroxyicosyldihydrogenphosphate, 3-carboxypropylphosphonic acid, 4-carboxybutylphosphonic acid, 5-carboxypentylphosphonic acid, 6-carboxyhexylphosphonic acid, 7-carboxy heptylphosphonic acid, 8-carboxyoctylphosphonic acid, 9-carboxynonylphosphonic acid, 10-carboxydecylphosphonic acid, 11-carboxyundecylphosphonic acid, 12-carboxydodecylphosphonic acid, 13-carboxydotridecylphosphonic acid, 14-carboxytetradecylphosphonic acid, 15-carboxypentadecylphosphonic acid, 16-carboxyhexadecylphosphonic acid, 17-carboxyheptadecylphosphonic acid, 18-carboxyoctadecylphosphonic acid, 19-carboxynonadecylphosphonic acid, 20-carboxy and icosylphosphonic acid. These may be used individually by 1 type, or may use 2 or more types together.

When the layer (Y) of the multilayer structure contains the inorganic phosphorus compound (BI) and the organic phosphorus compound (BOb), the number of moles of the organic phosphorus compound (BOb) in the layer (Y) M _BOb and the inorganic phosphorus compound (BI ) and the number of moles M _BI of M _BOb /M _BI satisfies the relationship of 1.0 × 10 ^-4 ≤ M _BOb / M _BI ≤ 2.0 × 10 ^-2 , and the adhesion is better. from the point of view that it satisfies the relationship of 3.5×10 ⁻⁴ ≦M _BOb /M _BI ≦1.0×10 ⁻² is more preferable. It is particularly preferable to satisfy the relationship x10 ^-4 ≤ M _BOb /M _BI ≤ 6.0 x 10 ^-3 . The number of moles M _BI of the inorganic phosphorus compound (BI) in M _BOb /M _BI means the inorganic phosphorus compound (BI) used to form the reaction product (D).

When the layer (Y) contains an organic phosphorus compound (BOb), the surface of the layer (Y) of the multilayer structure on the side not in contact with the substrate (X) measured by X-ray photoelectron spectroscopy (XPS method) The C/Al ratio at ~5 nm is preferably in the range of 0.1 to 15.0, more preferably in the range of 0.3 to 10.0, and in the range of 0.5 to 5.0 is particularly preferred. Good adhesion is exhibited when the organophosphorus compound (BOb) is present on the surface of the layer (Y).

[Polymer (F)]
The layer (Y) may contain a polymer (F) having at least one functional group selected from the group consisting of carbonyl groups, hydroxyl groups, carboxyl groups, carboxylic acid anhydride groups, and salts of carboxyl groups. Polymer (F) is preferably a polymer having at least one functional group selected from the group consisting of hydroxyl groups and carboxyl groups.

Examples of the polymer (F) include polyethylene glycol; polyvinyl alcohol, modified polyvinyl alcohol containing 1 to 50 mol% of an α-olefin unit having 4 or less carbon atoms, polyvinyl alcohol-based polymers such as polyvinyl acetal (polyvinyl butyral, etc.); Polysaccharides such as cellulose and starch; (meth)acrylic acid polymers such as polyhydroxyethyl (meth)acrylate, poly(meth)acrylic acid, and ethylene-acrylic acid copolymers; ethylene-maleic anhydride copolymers Examples include hydrolysates, hydrolysates of styrene-maleic anhydride copolymers, and hydrolysates of isobutylene-maleic anhydride alternating copolymers, and other maleic acid polymers. Among them, polyethylene glycol and polyvinyl alcohol-based polymers are preferred. Preferred aspects of the polyvinyl alcohol-based polymer used as the polymer (F) are the same as those of the vinyl alcohol-based resin contained in the layer (Z).

The polymer (F) may be a homopolymer of a monomer having a polymerizable group, or may be a copolymer of two or more monomers, or may be a hydroxyl group and/or a carboxy group. may be a copolymer of a monomer having and a monomer not having the group. In addition, as a polymer (F), you may mix and use 2 or more types of polymers (F).

Although the molecular weight of the polymer (F) is not particularly limited, the weight average molecular weight of the polymer (F) is preferably 5,000 or more, more preferably 8,000 or more, in order to obtain a multilayer structure having superior gas barrier properties and mechanical strength. More preferably, 10,000 or more is even more preferable. The upper limit of the weight average molecular weight of the polymer (F) is not particularly limited, and is, for example, 1,500,000 or less.

From the viewpoint of maintaining good appearance of the multilayer structure, the content of the polymer (F) in the layer (Y) is preferably less than 50% by mass, more preferably 20% by mass or less, based on the mass of the layer (Y). It is preferably 10% by mass or less, more preferably 0% by mass. Polymer (F) may or may not have reacted with the components in layer (Y).

Layer (Y) may further contain other components. Other components that can be contained in the layer (Y) include, for example, inorganic acid metal salts such as carbonates, hydrochlorides, nitrates, hydrogencarbonates, sulfates, hydrogensulfates, borates, oxalates, and acetic acid. Salts, metal salts of organic acids such as tartrates and stearates, metal complexes such as cyclopentadienyl metal complexes (e.g. titanocene), cyano metal complexes (e.g. Prussian blue), layered clay compounds, cross-linking agents, polymers Polymer compounds other than (BOa) and the polymer (F), plasticizers, antioxidants, ultraviolet absorbers, flame retardants and the like can be mentioned. The content of the other component in the layer (Y) in the multilayer structure is preferably 50% by mass or less, more preferably 20% by mass or less, even more preferably 10% by mass or less, and particularly preferably 5% by mass or less, It may be 0% by mass (not including other components).

[Layer (W)]
The multilayer structure of the present invention may comprise a layer (W) containing at least one selected from the group consisting of the organic phosphorus compound (BO) and the polymer (F) on the layer (Y). When the multilayer structure of the present invention comprises layer (W), layer (W) is preferably laminated directly with layer (Y). Preferred aspects of the phosphorus compound (BO) and polymer (F) that can be contained in the layer (W) are as described above. By including the layer (W) in the multilayer structure of the present invention, there is a tendency that the bending resistance is improved and the adhesion with another layer (J) described later is improved.

The layer (W) may further contain other components, for example, inorganic acid metal salts such as carbonates, hydrochlorides, nitrates, hydrogen carbonates, sulfates, hydrogen sulfates, borates, oxalic acid Organic acid metal salts such as salts, acetates, tartrates and stearates, metal complexes such as cyclopentadienyl metal complexes (e.g. titanocene), cyano metal complexes (e.g. Prussian blue), layered clay compounds, cross-linking agents , organic phosphorus compounds (BO) and polymer compounds other than the polymer (F), plasticizers, antioxidants, ultraviolet absorbers, flame retardants, and the like. The content of the other components in the layer (W) is preferably 50% by mass or less, more preferably 20% by mass or less, still more preferably 10% by mass or less, particularly preferably 5% by mass or less, and 0% by mass (other ) may be used.

The multilayer structure may contain an inorganic vapor deposition layer in an arrangement other than the substrate (X). Preferred aspects are the same as the preferred aspects of the inorganic deposition layer (X') described above.

[Manufacturing method of multilayer structure]
Since the items described for the multilayer structure of the present invention can be applied to the manufacturing method of the present invention, redundant description may be omitted. In addition, the matters described for the manufacturing method of the present invention can be applied to the multilayer structure of the present invention.

As a method for producing a multilayer structure of the present invention, for example, a coating liquid (R) containing a resin (C) and a solvent is applied onto a substrate (X), and then the solvent is removed to form a layer (Z). In step (I), a coating liquid (S) containing a metal oxide containing aluminum (A), an inorganic phosphorus compound (BI), and a solvent is applied onto the layer (Z), and then the solvent is removed to form a layer (Y ) a step (II) of forming a precursor layer, and a step (III) of forming a layer (Y) containing a reaction product (D) by heat-treating the layer (Y) precursor layer, mentioned. Further, when manufacturing a multilayer structure containing the organic phosphorus compound (BO) or the polymer (F), the coating liquid (S) used in step (II) contains the organic phosphorus compound (BO) or the polymer (F). A step of preparing a coating liquid (T) containing an organic phosphorus compound (BO) or a polymer (F) and coating it on the surface of the layer (Y) precursor layer obtained in step (II) ( IV).

[Step (I)]
In step (I), a layer (Z) is formed by applying a coating liquid (R) containing a resin (C) and a solvent onto a substrate (X) and then removing the solvent. A coating liquid (R) is obtained by mixing a resin (C) and a solvent.

The solvent used for the coating liquid (R) is not particularly limited, but preferably contains water as a main component, and may contain only water. Alcohols such as methanol, ethanol and isopropanol are preferably used as other solvents when water is used as the main component.

The solid content concentration of the coating liquid (R) is preferably 0.01 to 10% by mass, more preferably 0.05 to 5% by mass, from the viewpoint of the storage stability of the coating liquid and the coatability to the substrate. 0.1 to 2% by mass is more preferable. The solid content concentration can be calculated, for example, by dividing the mass of the solid content remaining after the solvent of the coating liquid (R) is distilled off by the mass of the coating liquid (R) subjected to the treatment.

Application of the coating liquid (R) is not particularly limited, and a known method can be employed. Examples of coating methods include casting method, dipping method, roll coating method, gravure coating method, screen printing method, reverse coating method, spray coating method, kiss coating method, die coating method, metering bar coating method, and chamber doctor combined coating. method, curtain coating method, bar coating method, and the like.

The thickness of the layer (Z) formed after applying the coating liquid (R) to the substrate (X) can be controlled by the solid content concentration of the coating liquid (R) or the coating method. For example, in the case of the gravure coating method, the cell volume of the gravure roll may be changed.

There is no particular limitation on the method for removing the solvent of the coating liquid (R) after coating on the substrate (X), and a known drying method can be applied. The drying method includes, for example, a hot air drying method, a hot roll contact method, an infrared heating method, a microwave heating method, and the like.

[Step (II)]
In step (II), a coating liquid (S) containing a metal oxide (A) containing aluminum, an inorganic phosphorus compound (BI), and a solvent is applied onto the layer (Z), and then the solvent is removed to form a layer ( Y) forming a precursor layer; A coating liquid (S) is obtained by mixing a metal oxide containing aluminum (A), an inorganic phosphorus compound (BI) and a solvent.

Specific means for adjusting the coating liquid (S) include a method of mixing a dispersion of the metal oxide (A) and a solution containing the inorganic phosphorus compound (BI); A method of adding an inorganic phosphorus compound (BI) and mixing may be mentioned. The temperature at which these are mixed is preferably 50° C. or lower, more preferably 30° C. or lower, and even more preferably 20° C. or lower. The coating liquid (S) may contain other compounds (eg, organic phosphorus compounds (BO) and polymers (F)), and if necessary, acetic acid, hydrochloric acid, nitric acid, trifluoroacetic acid, and trichloro It may contain at least one acid compound (Q) selected from the group consisting of acetic acid.

A dispersion liquid of the metal oxide (A) can be obtained, for example, by mixing the compound (E), water, and, if necessary, an acid catalyst or an organic solvent, according to a technique employed in a known sol-gel method, to obtain a compound ( E) can be prepared by condensation or hydrolytic condensation. When a dispersion of the metal oxide (A) is obtained by condensation or hydrolytic condensation of the compound (E), the resulting dispersion may be subjected to a specific treatment (the acid compound (Q) peptization in the presence of, etc.) may be performed. The solvent used for preparing the dispersion of the metal oxide (A) is not particularly limited, but alcohols such as methanol, ethanol and isopropanol; water; or mixed solvents thereof are preferred.

The solvent used for the solution containing the inorganic phosphorus compound (BI) may be appropriately selected according to the type of the inorganic phosphorus compound (BI), but preferably contains water. The solvent may contain an organic solvent (for example, alcohols such as methanol) as long as it does not interfere with the dissolution of the inorganic phosphorus compound (BI).

The solid content concentration of the coating liquid (S) is preferably 1 to 20% by mass, more preferably 2 to 15% by mass, more preferably 3 to 10% by mass, from the viewpoint of the storage stability of the coating liquid and the coatability to the substrate. is more preferred. The solid content concentration can be calculated, for example, by dividing the mass of the solid content remaining after the solvent of the coating liquid (S) is distilled off by the mass of the coating liquid (S) subjected to the treatment.

The coating liquid (S) has a viscosity measured with a Brookfield type rotational viscometer (SB type viscometer: rotor No. 3, rotation speed 60 rpm) of 3,000 mPa s or less at the temperature during coating. , more preferably 2,500 mPa·s or less, even more preferably 2,000 mPa·s or less. When the viscosity is 3,000 mPa·s or less, the leveling property of the coating liquid (S) is improved, and a multilayer structure having a more excellent appearance can be obtained. The viscosity of the coating liquid (S) is preferably 50 mPa·s or more, more preferably 100 mPa·s or more, and even more preferably 200 mPa·s or more.

In the coating liquid (S), the molar ratio of aluminum atoms to phosphorus atoms is preferably in the range of aluminum atoms:phosphorus atoms=1.0:1.0 to 3.6:1.0, and 1.1 : 1.0 to 3.0:1.0, more preferably 1.11:1.00 to 1.50:1.00. The molar ratio between aluminum atoms and phosphorus atoms can be calculated by performing a fluorescent X-ray analysis of the dry matter of the coating liquid (S).

Application of the coating liquid (S) is not particularly limited, and a known method can be employed. Examples of coating methods include casting method, dipping method, roll coating method, gravure coating method, screen printing method, reverse coating method, spray coating method, kiss coating method, die coating method, metering bar coating method, and chamber doctor combined coating. method, curtain coating method, bar coating method, and the like.

There is no particular limitation on the method for removing the solvent (drying treatment) after coating the coating liquid (S), and a known drying method can be applied. The drying method includes, for example, a hot air drying method, a hot roll contact method, an infrared heating method, a microwave heating method, and the like.

The drying temperature is preferably lower than the flow initiation temperature of the substrate (X). The drying temperature after coating of the coating liquid (S) may be, for example, about 60 to 180° C., more preferably 60° C. or higher and lower than 140° C., further preferably 70° C. or higher and lower than 130° C., and 80° C. or higher. Less than 120°C is particularly preferred. The drying time is not particularly limited, but is preferably from 1 second to less than 1 hour, more preferably from 5 seconds to less than 15 minutes, and even more preferably from 5 seconds to less than 300 seconds. In particular, when the drying temperature is 100° C. or higher (for example, 100 to 140° C.), the drying time is preferably 1 second or more and less than 4 minutes, more preferably 5 seconds or more and less than 4 minutes, and further preferably 5 seconds or more and less than 3 minutes. preferable. When the drying temperature is lower than 100° C. (eg, 60 to 99° C.), the drying time is preferably 3 minutes or more and less than 1 hour, more preferably 6 minutes or more and less than 30 minutes, and even more preferably 8 minutes or more and less than 25 minutes. When the drying treatment conditions for the coating liquid (S) are within the above range, there is a tendency to obtain a multilayer structure having better gas barrier properties.

[Step (III)]
In step (III), the layer (Y) precursor layer formed in step (II) is heat-treated to form layer (Y). In step (III), a reaction proceeds to produce a reaction product (D). In order to allow the reaction to proceed sufficiently, the heat treatment temperature is preferably 140° C. or higher, more preferably 170° C. or higher, even more preferably 180° C. or higher, and particularly preferably 190° C. or higher. When the heat treatment temperature is low, it takes a long time to obtain a sufficient reaction rate, which causes a decrease in productivity. The heat treatment temperature varies depending on the type of substrate (X) and the like. For example, when a thermoplastic resin film made of a polyamide resin is used as the substrate (X), the heat treatment temperature is preferably 270° C. or lower. When a thermoplastic resin film made of a polyester resin is used as the substrate (X), the heat treatment temperature is preferably 240° C. or lower. The heat treatment may be performed in an air atmosphere, a nitrogen atmosphere, an argon atmosphere, or the like. The heat treatment time is preferably 1 second to 1 hour, more preferably 1 second to 15 minutes, even more preferably 5 to 300 seconds.

From the viewpoint of exhibiting better barrier performance, step (III) preferably includes a first heat treatment step (III-1) and a second heat treatment step (III-2). When the heat treatment is performed in two or more stages, the temperature of the second stage heat treatment (hereinafter referred to as the second heat treatment) is preferably higher than the temperature of the first stage heat treatment (hereinafter referred to as the first heat treatment), and the temperature of the first heat treatment It is more preferably 15° C. or higher, more preferably 20° C. or higher, and particularly preferably 30° C. or higher.

In addition, the heat treatment temperature in step (III) (the temperature of the first heat treatment in the case of heat treatment in two or more stages) is higher than the drying temperature in step (II) because a multilayer structure having good properties can be obtained. preferably 30° C. or higher, more preferably 50° C. or higher, even more preferably 55° C. or higher, particularly preferably 60° C. or higher.

When the heat treatment of step (III) is performed in two or more stages, the temperature of the first heat treatment is preferably 140° C. or higher and lower than 200° C., and the temperature of the second heat treatment is preferably 180° C. or higher and 270° C. or lower. Preferably, the temperature of the second heat treatment is higher than the temperature of the first heat treatment, more preferably 15° C. or more, and even more preferably 25° C. or more. In particular, when the heat treatment temperature is 200° C. or higher, the heat treatment time is preferably 0.1 seconds to 10 minutes, more preferably 0.5 seconds to 15 minutes, and even more preferably 1 second to 3 minutes. When the heat treatment temperature is lower than 200° C., the heat treatment time is preferably 1 second to 15 minutes, more preferably 5 seconds to 10 minutes, even more preferably 10 seconds to 5 minutes.

[Step (IV)]
When the organophosphorus compound (BO), the polymer (F) and/or other components are used in the production method, the organophosphorus compound (BO), the polymer (F) and/or the other components and a solvent are mixed to obtain Coating liquid (T) obtained in step (II) on layer (Y) precursor, layer (Y) obtained in step (III) or layer (Y) precursor layer after step (III-1) It may have a step (IV) of coating and drying. When step (IV) is performed after step (III), heat treatment is preferably performed under the same conditions as in step (III) after the drying treatment in step (IV). Further, when step (IV) is performed after step (III-1), step (III-2) is preferably performed after the drying treatment of step (IV).

The solvent used in the coating liquid (T) may be appropriately selected according to the type of the organic phosphorus compound (BO), but alcohols such as methanol, ethanol, and isopropanol; water; or a mixed solvent thereof. preferable.

The concentration of solids in the coating liquid (T) is preferably 0.01 to 60% by mass, more preferably 0.1 to 50% by mass, from the viewpoint of storage stability and coatability of the solution, and 0.2 to 40% by mass is more preferred. The solid content concentration can be determined by a method similar to the method described for the coating liquid (S).

As with the application of the coating liquid (S), the method of applying the coating liquid (T) is not particularly limited, and known methods can be employed.

The conditions for the solvent removal method (drying treatment) after applying the coating liquid (T) in step (IV) can be the same as the drying treatment conditions after applying the coating liquid (S) in step (II). .

[Other layer (J)]
The multilayer structure of the present invention may contain other layers (J) in order to improve various properties (eg, heat sealability, barrier properties, mechanical properties). Such a multilayer structure of the present invention can be obtained, for example, by laminating the layer (Y) (and the layer (W) as necessary) on the substrate (X) with the layer (Z) interposed therebetween, followed by further can be produced by adhering or forming the layer (J) of directly or via an adhesive layer. Examples of the other layer (J) include, but are not limited to, an ink layer; a thermoplastic resin layer such as a polyolefin layer and an ethylene-vinyl alcohol copolymer resin layer.

The multilayer structure of the present invention may contain an ink layer for printing a product name, pattern, or the like. Examples of the ink layer include a film obtained by drying a liquid in which a polyurethane resin containing a pigment (e.g., titanium dioxide) is dispersed in a solvent. A film obtained by drying a resist for forming electronic circuit wiring may also be used. Examples of coating methods for the ink layer include gravure printing, wire bar, spin coater, die coater, and various other coating methods. The thickness of the ink layer is preferably 0.5-10.0 μm, more preferably 1.0-4.0 μm.

By using a polyolefin layer as the outermost layer of the multilayer structure of the present invention, it is possible to impart heat sealability to the multilayer structure and improve the mechanical properties of the multilayer structure. Polyolefin is preferably polypropylene or polyethylene from the viewpoint of improving heat sealability and mechanical properties. Moreover, in order to improve the mechanical properties of the multilayer structure, it is preferable to laminate at least one film selected from the group consisting of a film made of polyester, a film made of polyamide, and a film made of hydroxyl group-containing polymer. From the viewpoint of improving mechanical properties, the polyester is preferably polyethylene terephthalate, the polyamide is preferably nylon-6, and the hydroxyl group-containing polymer is preferably ethylene-vinyl alcohol copolymer.

Another layer (J) may be a layer formed by extrusion coat lamination. The extrusion coat lamination method that can be used in the present invention is not particularly limited, and known methods may be used. In a typical extrusion coat lamination method, a laminated film is produced by feeding a molten thermoplastic resin to a T-die and cooling the thermoplastic resin taken out from a flat slit of the T-die.

Examples of the extrusion coat lamination method other than the single lamination method include a sandwich lamination method and a tandem lamination method. The sandwich lamination method is a method in which a molten thermoplastic resin is extruded onto one base material, and a second base material is supplied from another unwinder (unwinder) and laminated to produce a laminate. The tandem lamination method is a method in which two single lamination machines are connected to produce a laminate having a five-layer structure at one time.

[Adhesive layer (I)]
In the multilayer structure of the present invention, the adhesion layer (I) may be used to increase the adhesion between the layer (Y) and other members (for example, another layer (J), etc.). The adhesive layer (I) may be composed of an adhesive resin. As the adhesive resin, a two-liquid reaction type polyurethane adhesive obtained by mixing and reacting a polyisocyanate component and a polyol component is preferable. Also, by adding a small amount of additive such as a known silane coupling agent to the anchor coating agent or adhesive, the adhesiveness can be further enhanced in some cases. Silane coupling agents include, but are not limited to, silane coupling agents having reactive groups such as isocyanate groups, epoxy groups, amino groups, ureido groups, and mercapto groups. By bonding the layer (Y) to another member, it is possible to more effectively suppress deterioration of the gas barrier property or appearance when the multilayer structure of the present invention is subjected to processing such as printing or lamination. , the drop strength of the packaging material using the multilayer structure of the present invention can be increased. The thickness of the adhesive layer (I) is preferably 0.01-10.0 μm, more preferably 0.03-5.0 μm.

[Configuration of multilayer structure]
Specific examples of the structure of the multilayered structure of the present invention are shown below, but each specific example may be a structure in which a plurality of specific examples are combined. In specific examples, the substrate (X) and the other layer (J) are described with specific resin names. Further, when the layer (Y)/layer (Z) is positioned between the layers (substrate (X) and another layer (J)) in which specific resin names are described, the layer (Z)/ The order of lamination with the layer (Y) may be replaced. Here, "/" means lamination via an adhesive layer or directly. (1) layer (Y)/layer (Z)/polyester layer,
(2) layer (Y)/layer (Z)/polyester layer/layer (Z)/layer (Y),
(3) layer (Y)/layer (Z)/polyamide layer,
(4) layer (Y)/layer (Z)/polyamide layer/layer (Z)/layer (Y),
(5) layer (Y)/layer (Z)/polyolefin layer,
(6) layer (Y)/layer (Z)/polyolefin layer/layer (Z)/layer (Y),
(7) layer (Y)/layer (Z)/hydroxyl group-containing polymer layer,
(8) layer (Y)/layer (Z)/hydroxyl group-containing polymer layer/layer (Z)/layer (Y),
(9) layer (Y) / layer (Z) / paper layer,
(10) layer (Y)/layer (Z)/paper layer/layer (Z)/layer (Y),
(11) layer (Y)/layer (Z)/inorganic deposition layer/polyester layer,
(12) layer (Y)/layer (Z)/inorganic deposition layer/polyamide layer,
(13) layer (Y)/layer (Z)/inorganic deposition layer/polyolefin layer,
(14) layer (Y)/layer (Z)/inorganic deposition layer/hydroxyl group-containing polymer layer,
(15) layer (Y)/layer (Z)/polyester layer/polyamide layer/polyolefin layer,
(16) layer (Y)/layer (Z)/polyester layer/layer (Z)/layer (Y)/polyamide layer/polyolefin layer,
(17) polyester layer/layer (Y)/layer (Z)/polyester layer/layer (Z)/layer (Y)/inorganic deposition layer/hydroxyl-containing polymer layer/polyolefin layer,
(18) polyester layer/layer (Z)/layer (Y)/polyamide layer/polyolefin layer,
(19) layer (Y)/layer (Z)/polyamide layer/polyester layer/polyolefin layer,
(20) layer (Y)/layer (Z)/polyamide layer/layer (Z)/layer (Y)/polyester layer/polyolefin layer,
(21) polyamide layer/layer (Z)/layer (Y)/polyester layer/polyolefin layer,
(22) layer (Y)/layer (Z)/polyolefin layer/polyamide layer/polyolefin layer,
(23) layer (Y)/layer (Z)/polyolefin layer/layer (Z)/layer (Y)/polyamide layer/polyolefin layer,
(24) polyolefin layer/layer (Z)/layer (Y)/polyamide layer/polyolefin layer,
(25) layer (Y)/layer (Z)/polyolefin layer/polyolefin layer,
(26) layer (Y)/layer (Z)/polyolefin layer/layer (Z)/layer (Y)/polyolefin layer,
(27) polyolefin layer/layer (Y)/layer (Z)/polyolefin layer,
(28) layer (Y)/layer (Z)/polyester layer/polyolefin layer,
(29) layer (Y)/layer (Z)/polyester layer/layer (Z)/layer (Y)/polyolefin layer,
(30) polyester layer/layer (Z)/layer (Y)/polyolefin layer,
(31) layer (Y)/layer (Z)/polyamide layer/polyolefin layer,
(32) layer (Y)/layer (Z)/polyamide layer/layer (Z)/layer (Y)/polyolefin layer,
(33) polyamide layer/layer (Z)/layer (Y)/polyolefin layer,
(34) layer (Y)/layer (Z)/polyester layer/paper layer,
(35) layer (Y)/layer (Z)/polyamide layer/paper layer,
(36) layer (Y)/layer (Z)/polyolefin layer/paper layer,
(37) polyolefin layer/paper layer/polyolefin layer/layer (Z)/layer (Y)/polyester layer/polyolefin layer,
(38) polyolefin layer/paper layer/polyolefin layer/layer (Z)/layer (Y)/polyamide layer/polyolefin layer,
(39) polyolefin layer/paper layer/polyolefin layer/layer (Z)/layer (Y)/polyolefin layer,
(40) paper layer/polyolefin layer/layer (Z)/layer (Y)/polyester layer/polyolefin layer,
(41) polyolefin layer/paper layer/layer (Y)/layer (Z)/polyolefin layer,
(42) paper layer/layer (Y)/layer (Z)/polyester layer/polyolefin layer,
(43) paper layer/layer (Y)/layer (Z)/polyolefin layer,
(44) layer (Y)/layer (Z)/paper layer/polyolefin layer,
(45) layer (Y)/layer (Z)/polyester layer/paper layer/polyolefin layer,
(46) polyolefin layer/paper layer/polyolefin layer/layer (Y)/layer (Z)/polyolefin layer/hydroxyl group-containing polymer layer,
(47) polyolefin layer/paper layer/polyolefin layer/layer (Y)/layer (Z)/polyolefin layer/polyamide layer,
(48) polyolefin layer/paper layer/polyolefin layer/layer (Y)/layer (Z)/polyolefin layer/polyester layer,
(49) inorganic deposition layer/layer (Y)/layer (Z)/polyester layer,
(50) inorganic vapor deposition layer/layer (Y)/layer (Z)/polyester layer/layer (Z)/layer (Y)/inorganic vapor deposition layer,
(51) inorganic deposition layer/layer (Y)/layer (Z)/polyamide layer,
(52) inorganic vapor deposition layer/layer (Y)/layer (Z)/polyamide layer/layer (Z)/layer (Y)/inorganic vapor deposition layer,
(53) inorganic deposition layer/layer (Y)/layer (Z)/polyolefin layer,

(54) Inorganic vapor deposition layer/Layer (Y)/Layer (Z)/Polyolefin layer/Layer (Z)/Layer (Y)/Inorganic vapor deposition layer In the above examples, the inorganic vapor deposition layer is an aluminum vapor deposition layer and/or an oxidation layer. A vapor deposition layer of aluminum is preferred. In the above examples, the hydroxyl group-containing polymer layer is preferably an ethylene-vinyl alcohol copolymer. In the above examples, the polyolefin layer is preferably a polyethylene film or a polypropylene film. In the above examples, the polyester layer is preferably a PET film. Also, in the above examples, the polyamide layer may be a nylon film.

The multilayer structure of the present invention preferably has a structure in which the substrate (X)/layer (Z)/layer (Y) are directly laminated from the viewpoint of improving resistance to severe autoclave treatment. Moreover, a multilayer structure having a plurality of configurations of substrate (X)/layer (Z)/layer (Y) is preferable because it is more excellent in gas barrier properties. When a plurality of gas barrier layers are used in the multilayer structure of the present invention, at least one layer structure of substrate (X)/layer (Z)/layer (Y) is present on the outer layer side of other gas barrier layers. It is preferable because deterioration of the gas barrier layer (eg, inorganic deposition layer) of the inner layer due to outside air (eg, water vapor) or the like can be suppressed.

[Use]
Since the multilayer structure of the present invention has good oxygen barrier properties and water vapor barrier properties, it can be applied to various uses such as packaging materials, protective sheets for electronic devices, and moisture-proof sheets. It is suitable for use as a packaging material because it has good appearance and gas barrier properties even after autoclave treatment under severe conditions. Moreover, since the multilayer structure of the present invention can maintain excellent gas barrier properties and water vapor barrier properties even after a dump heat test, it is also suitably used as a protective sheet for electronic devices.

[Packaging material]
The packaging material of the present invention may be composed only of the multilayer structure of the present invention, or may be composed of the multilayer structure of the present invention and other members.

Packaging materials according to preferred embodiments of the present invention include inorganic gases (e.g., hydrogen, helium, nitrogen, oxygen, carbon dioxide), natural gas, water vapor, and organic compounds that are liquid at normal temperature and pressure (e.g., ethanol, gasoline vapor). It has barrier properties against

When the packaging material of the present invention is a packaging bag, the multilayer structure may be used for the entire packaging bag, or the multilayer structure may be used for part of the packaging bag. For example, 50% to 100% of the area of the packaging bag may be composed of the multilayer structure. The same applies when the packaging material is something other than a packaging bag (for example, a container or a lid material).

The packaging material of the present invention can be made in various ways. For example, a container (packaging material) is produced by bonding a sheet-like multilayer structure or a film material containing the multilayer structure (hereinafter simply referred to as "film material") and forming it into a predetermined container shape. may Molding methods include thermoforming, injection molding, extrusion blow molding and the like. Alternatively, a container (packaging material) may be produced by forming a layer (Z) and a layer (Y) on a substrate (X) molded into a predetermined container shape.

The packaging material according to the present invention is preferably used as a food packaging material. In addition to packaging materials for food, the packaging material according to the present invention can be preferably used as a packaging material for packaging chemicals such as agricultural chemicals and pharmaceuticals; medical equipment; industrial materials such as machine parts and precision materials; .

Products using the packaging material of the present invention include, for example, vertical bag-making filling seal bags, vacuum packaging bags, pouches, laminated tube containers, infusion bags, container lids, paper containers, strip tapes, in-mold label containers or A vacuum insulator and the like can be mentioned.

A vertical form-fill-seal bag is a bag obtained by forming a multilayer structure (film material) of the present invention using a vertical form-fill-seal machine (also called a vertical form-fill-seal machine). A vertical bag-making and filling machine, for example, seals (joins) the sides and bottom of a supplied film material so that the opposite surfaces are formed to form a bag with an upper opening, and Items are supplied from above the bag to fill the inside of the bag. Subsequently, the vertical form-fill-seal machine seals the upper part of the bag, cuts the upper part, and discharges it as a vertical form-fill-seal bag.

A vacuum packaging bag is a bag that is used in a state in which the inside of the bag obtained by making a bag using the multilayer structure of the present invention is decompressed. Since the inside of the bag is depressurized, in the vacuum packaging bag, the film material that separates the inside and outside of the bag is usually deformed so as to be in contact with the contents accommodated in the bag. The contents are typically foods such as corn on the cob, beans, bamboo shoots, potatoes, chestnuts, tea leaves, meat, fish, and sweets.

A pouch is a container provided with the multi-layered structure (film material) of the present invention as a partition separating the inside and the outside for containing contents. Pouches are suitable for containing liquid or slurry contents, but can also be used for containing solid contents. The contents are typically beverages, seasonings, liquid diets and other foods, and detergents, liquid soaps and other daily necessities.

A laminate tube container includes a body portion provided with the multilayer structure (laminate film) of the present invention as a partition wall separating the inside and outside of the container, a pouring portion for taking out the contents stored inside the container, It has The body of the laminate tube container has, for example, a tubular shape with one end closed, and the pouring part is arranged on the other end side.

An infusion bag is a bag (bag) for containing infusions such as amino acid infusions, electrolyte infusions, carbohydrate infusions, and fat emulsions for infusions. The infusion bag may have a spout member in addition to the bag body that accommodates the contents. In addition, the infusion bag may have a hanging hole for hanging the bag. In the infusion bag, the film material separating the inside and the outside for containing the infusion comprises the multilayer structure of the present invention.

The container lid material has a film material (multilayer structure of the present invention) that functions as a part of the partition wall that separates the inside of the container from the outside of the container in a state where the container is formed by being combined with the container body. A container lid is a container (with a lid) that is combined with a container body so as to seal the opening of the container body by heat sealing, adhesive bonding (sealing), or the like, and has a sealed space inside. container). The container lid is usually joined to the container body at its peripheral edge. In this case, the central portion surrounded by the peripheral portion faces the inner space of the container. The container body is, for example, a cup-shaped, tray-shaped, or other molded body, and includes a flange portion, a wall surface portion, and the like for sealing the lid member for the container.

A paper container is a container in which a partition separating an inside and an outside containing contents includes a paper layer. The paper container has, for example, a shape such as a gable top type or a brick type. These shapes have a bottom wall for self-supporting paper containers.

A vacuum insulator is a thermal insulator provided with a covering material and a core material arranged inside surrounded by the covering material, and the inside where the core material is arranged is decompressed. As the core material, for example, a powder such as perlite powder, a fibrous material such as glass wool, a resin foam such as urethane foam, a hollow container, a honeycomb structure, or the like can be used. In a vacuum insulator, the cladding, which acts as a barrier, comprises a multi-layer structure.

Examples of the layer structure of the multilayer structure suitable for the vacuum insulator include the following.
(1) Polyolefin layer/ethylene-vinyl alcohol copolymer layer/inorganic vapor deposition layer/polyamide layer/layer (Y)/layer (Z)/polyester layer (2) Polyolefin layer/inorganic vapor deposition layer/polyester layer/inorganic vapor deposition layer / Polyester layer / Layer (Y) / Layer (Z) / Polyester layer (3) Polyolefin layer / Ethylene-vinyl alcohol copolymer layer / Inorganic deposition layer / Layer (Y) / Layer (Z) / Polyester layer / Layer ( Y) / layer (Z) / polyester layer (4) polyolefin layer / inorganic deposition layer / polyester layer / layer (Y) / layer (Z) / polyester layer / layer (Y) / layer (Z) / polyester layer (5 ) Polyolefin layer/polyamide layer/inorganic vapor deposition layer/polyester layer/layer (Y)/layer (Z)/polyester layer (6) Polyolefin layer/ethylene-vinyl alcohol copolymer layer/inorganic vapor deposition layer/inorganic vapor deposition layer/polyester Layer/Layer (Y)/Layer (Z)/Polyester layer By combining with an inorganic deposition layer, gas barrier properties can be improved and reduction in thermal conductivity can be suppressed. Further, the polyolefin layer may be changed to a polyethylene-vinyl alcohol copolymer layer, and the change to an ethylene-vinyl alcohol copolymer layer has the effect of suppressing a decrease in thermal conductivity at high temperatures. When the above layer structure is used as an outer packaging material for a vacuum insulator, it is preferable that the polyolefin layer side is the inner layer (heat seal layer) and the polyester layer side is the outer layer. The layer structure described above tends to suppress the deterioration of the inner layer due to outside air such as water vapor due to long-term use, which is preferable. Materials that can be used in the layer structure described above are not particularly limited, but the resins and films described in this embodiment can be preferably used.

Heat-sealing is sometimes performed in the above-mentioned products that are molded products (for example, vertical form-fill-seal bags). If heat-sealing is to be performed, it is usually necessary to place a heat-sealable layer on the inner side of the molded article or on both the inner and outer sides of the molded article. When the heat-sealable layer is present only on the inner side of the molded product (bag), the sealing of the trunk portion is generally a joining-the-hands sealing. If the heat-sealable layer is on both the inside and outside sides of the molded article, the body seal is usually an envelope seal. A polyolefin layer is preferred as the heat-sealable layer.

The protective sheet for the electronic device of the present invention may contain the multilayer structure of the present invention, or may be composed only of the multilayer structure of the present invention. The electronic device protective sheet is used for the purpose of protecting the electronic device from the external environment. can be placed. That is, the protective sheet of the present invention is usually arranged on the surface of the electronic device main body via the sealing material. The electronic device main body is not particularly limited, and examples thereof include a photoelectric conversion device, an information display device, an illumination device, and the like.

The protective sheet of the electronic device of the present invention may include, for example, a surface protective layer arranged on one surface or both surfaces of the multilayer structure. As the surface protective layer, a layer made of a scratch-resistant resin is preferable. Moreover, it is preferable that the surface protective layer of a device such as a solar cell that is used outdoors is made of a resin having high weather resistance (for example, light resistance). Moreover, when protecting a surface that needs to transmit light, a surface protective layer having high translucency is preferable. Materials for the surface protective layer (surface protective film) include, for example, poly(meth)acrylate, polycarbonate, polyethylene terephthalate, polyethylene-2,6-naphthalate, polyvinyl fluoride (PVF), polyvinylidene fluoride (PVDF), Polytetrafluoroethylene (PTFE), polychlorotrifluoroethylene (PCTFE), ethylene-tetrafluoroethylene copolymer (ETFE), ethylene-chlorotrifluoroethylene copolymer (ECTFE), tetrafluoroethylene-perfluoroalkyl vinyl ether Copolymers (PFA), tetrafluoroethylene-hexafluoropropylene copolymers (FEP) and the like can be mentioned. An example of a protective sheet includes a poly(meth)acrylate layer disposed on one surface.

Various additives (for example, ultraviolet absorbers) may be added to the surface protective layer in order to increase the durability of the surface protective layer. A preferred example of a surface protective layer with high weather resistance is an acrylic resin layer to which an ultraviolet absorber is added. Examples of UV absorbers include, but are not limited to, benzotriazole, benzophenone, salicylate, cyanoacrylate, nickel, and triazine UV absorbers. Further, other stabilizers, light stabilizers, antioxidants, etc. may be used in combination.

Moreover, the multilayer structure of the present invention can also be utilized as a moisture-proof sheet. For example, in decorative board applications, it is possible to prevent warpage that occurs due to moisture absorption/desorption due to changes in indoor temperature and humidity by attaching it to the back of decorative boards used for indoor door panels and the like.

Next, the present invention will be described in more detail with reference to Examples, but the present invention is not limited by these Examples, and many modifications are possible within the scope of the technical idea of the present invention. It is possible by those who have ordinary knowledge in the field.

<Materials used in Examples and Comparative Examples>
Resin (C)
・C-1: "Kuraray Poval (registered trademark) 60-98" (manufactured by Kuraray Co., Ltd., PVA, saponification degree 98.0 to 99.0 mol%, viscosity (4% by mass, 20 ° C.) 54.0 to 66.0mPa s)
・C-2: “Kuraray Poval (registered trademark) 5-98” (manufactured by Kuraray Co., Ltd., PVA, saponification degree 98.0 to 99.0 mol%, viscosity (4% by mass, 20 ° C.) 5.2 to 6.0 mPa·s)
・C-3: “Kuraray Poval (registered trademark) 5-82” (manufactured by Kuraray Co., Ltd., PVA, saponification degree 80.0 to 83.0 mol%, viscosity (4% by mass, 20 ° C.) 4.5 to 5.2mPa s)
・C-4: “Kuraray Poval (registered trademark) 48-80” (manufactured by Kuraray Co., Ltd., PVA, saponification degree 78.5 to 80.5 mol%, viscosity (4% by mass, 20 ° C.) 45.0 to 51.0mPa s)
・C-5: “Kuraray Poval (registered trademark) 25-98R” (manufactured by Kuraray Co., Ltd., PVA, saponification degree 98.0 to 99.0 mol%, viscosity (4% by mass, 20 ° C.) 20.0 to 30.0mPa s)
・C-6: "Kuraray Poval (registered trademark) 32-97KL" (manufactured by Kuraray Co., Ltd., PVA, saponification degree 95.0 to 99.0 mol%, viscosity (4% by mass, 20 ° C.) 29.0 to 34.0mPa s)
・C-7: “Kuraray Poval (registered trademark) L-10” (manufactured by Kuraray Co., Ltd., PVA, saponification degree 71.5 to 73.5 mol%, viscosity (4% by mass, 20 ° C.) 5.0 to 7.0mPa s)
· C-8: "Kuraray Poval (registered trademark) LM10-HD" (manufactured by Kuraray Co., Ltd., PVA, saponification degree 38.0 to 42.0 mol%, viscosity (4% by mass, 20 ° C.) 4.5 to 5.7mPa s)
· C-9: "Kuraray Poval (registered trademark) RS-2117" (manufactured by Kuraray Co., Ltd., PVA, saponification degree 97.5 to 99.0 mol%, viscosity (4% by mass, 20 ° C.) 25.0 to 30.0mPa s)
Polyester/polyester: "Elitel (trademark) KA5071S" (manufactured by Unitika Ltd., polyester-based aqueous dispersion, solid content concentration 30% by mass)
Polyurethane/polyurethane: "Takelac (trademark) W5030" (manufactured by Mitsui Chemicals, Inc., polyurethane-based aqueous dispersion, solid content concentration 30% by mass)
Base material (X), adhesive layer (I), other layer (J)
・ PET12: stretched polyethylene terephthalate film; manufactured by Toray Industries, Inc., “Lumirror (trademark) P60” (trade name), thickness 12 μm
・PET50: polyethylene terephthalate film with improved adhesion to ethylene-vinyl acetate copolymer; manufactured by Toyobo Co., Ltd., “Shine Beam (trademark) Q1A15” (trade name), thickness 50 μm
・ ONY15: stretched nylon film; manufactured by Unitika Ltd., “Emblem (trademark) ONBC” (trade name), thickness 15 μm
・ CPP50: unstretched polypropylene film; manufactured by Mitsui Chemicals Tohcello Co., Ltd., “RXC-22” (trade name), thickness 50 μm
・ CPP70: unstretched polypropylene film; manufactured by Mitsui Chemicals Tohcello Co., Ltd., “RXC-22” (trade name), thickness 70 μm
・ CPP100: unstretched polypropylene film; manufactured by Mitsui Chemicals Tohcello Co., Ltd., “RXC-22” (trade name), thickness 100 μm
・VM-XL: Aluminum vapor deposition biaxially stretched EVOH; manufactured by Kuraray Co., Ltd., “VM-XL”, thickness 15 μm, unless otherwise specified, the order of lamination is Al vapor deposition layer / EVOH layer ・2 Liquid adhesive: "Takelac" (registered trademark) "A-520"(brand); manufactured by Mitsui Chemicals, Inc. and "Takenate" (registered trademark) "A-50"(brand); manufactured by Mitsui Chemicals, Inc.

<Evaluation method>
(1) Thickness of Layer (Z) Using a focused ion beam (FIB), the multilayer structures obtained in Examples and Comparative Examples were cut to prepare sections for cross-sectional observation. The prepared section was fixed to the sample base with a carbon tape, and platinum ion sputtering was performed at an acceleration voltage of 30 kV for 30 seconds. A cross section of the multilayer structure was observed using a field emission transmission electron microscope, and the thickness of the layer (Z) was calculated. The measurement conditions were as follows.
Device: JEM-2100F manufactured by JEOL Ltd.
Accelerating voltage: 200 kV
Magnification: 250,000 times

(2) Oxygen Permeability of Multilayered Structure The multilayered structure obtained in Examples and Comparative Examples was attached to an oxygen permeation measuring device so that the substrate (X) faced the carrier gas side, and the oxygen permeability was measured by the isobaric method. was measured. The measurement conditions were as follows.
Device: MOCON OX-TRAN2/21 manufactured by MOCON
Temperature: 20°C
Humidity on the oxygen supply side: 85% RH
Carrier gas side humidity: 85% RH
Carrier gas flow rate: 10 mL/min Oxygen pressure: 1.0 atm
Carrier gas pressure: 1.0 atm

(3) Peeling between layers after autoclave treatment A 120 mm x 120 mm piece was cut out from each of the multilayer structures obtained in Examples and Comparative Examples, and heat-sealed on three sides to prepare a three-sided pouch. Next, a piece of 80 mm × 80 mm cut out from one side that is not heat-sealed is inserted into the filter paper moistened with deionized water, and then heat-sealed 90 mm from the end, so that a part is not heat-sealed. Got a pouch. Subsequently, the obtained pouch was autoclaved under the following conditions.
Autoclave treatment device: High pressure steam sterilizer HVE-50LB manufactured by Hirayama Seisakusho Co., Ltd.
Temperature: 135°C
Time: 120 minutes Maximum operating pressure: 0.228 MPa
After the autoclave treatment, the case where the appearance defect such as delamination did not exist on the entire surface was evaluated as "A", the case where it partially existed was evaluated as "B", and the case where it existed over the entire surface was evaluated as "C".

(4) Measurement of Moisture Permeability of Multilayered Structure The samples (multilayered structures) obtained in Examples and Comparative Examples were attached to a water vapor permeation measuring device so that the base material layer faced the carrier gas side, and measured by the isobaric method. The moisture permeability (water vapor permeability) was measured by The measurement conditions were as follows.
Apparatus: MOCON PERMATRAN W3/33 manufactured by MOCON
Temperature: 40°C
Humidity on steam supply side: 90% RH
Humidity on carrier gas side: 0% RH
Carrier gas flow rate: 50 mL/min

<Production Example 1>
4.8 parts by mass of polyvinyl alcohol “Kuraray Poval (registered trademark) 60-98” and 95.2 parts by mass of water are mixed and stirred in a water bath at 80°C for 5 hours to dissolve “60-98”. An aqueous PVA solution was obtained. Next, 0.3 parts by mass of the PVA aqueous solution, 69.8 parts by mass of water, and 29.9 parts by mass of methanol were mixed and stirred for 1 hour to obtain a coating liquid (R-1).

<Production Examples 2 to 9>
Coating solutions (R-1) to (R-9) were obtained in the same manner as in Production Example 1, except that the type of resin used and the melting temperature were changed as shown in Table 1.

<Production example of coating liquid (CR-1)>
1.0 parts by mass of a polyester water dispersion "Elitel KA5071S" (manufactured by Unitika Ltd.), 69.0 parts by mass of water, and 30.0 parts by mass of methanol are mixed and stirred for 1 hour to form a coating liquid (CR-1 ).

<Production example of coating liquid (CR-2)>
A coating liquid (CR- 2) was obtained.
<Production example of coating liquid (R-10)>
3.0 parts by mass of coating liquid (R-1) and 7.0 parts by mass of coating liquid (CR-1) were mixed and stirred for 1 hour to obtain coating liquid (R-10).

<Production example of coating liquid (S-1)>
230 parts by mass of distilled water was heated to 70° C. while stirring. 88 parts by mass of triisopropoxyaluminum was added dropwise to the distilled water over 1 hour, the liquid temperature was gradually increased to 95°C, and hydrolytic condensation was performed by distilling off the generated isopropanol. 4.0 parts by mass of a 60% by mass nitric acid aqueous solution was added to the obtained liquid, and the mixture was stirred at 95° C. for 3 hours to deflocculate aggregates of particles of the hydrolytic condensate. After that, the liquid was concentrated so that the solid content concentration was 10% by mass in terms of aluminum oxide to obtain a solution. 54.29 parts by mass of distilled water and 18.80 parts by mass of methanol were added to 22.50 parts by mass of the solution thus obtained, and the mixture was uniformly stirred to obtain a dispersion liquid. Subsequently, 4.41 parts by mass of an 85% by mass phosphoric acid aqueous solution was added dropwise while stirring the dispersion while maintaining the liquid temperature at 15°C, and the mixture was stirred at 15°C until the viscosity reached 1500 mPa s. Subsequently, a desired coating liquid (S-1) was obtained. The molar ratio of aluminum atoms to phosphorus atoms in the coating liquid (S-1) was aluminum atom:phosphorus atom=1.15:1.00.

[Example 1]
<Example 1-1>
First, PET12 (hereinafter sometimes abbreviated as “X-1”) was prepared as the base material (X). The coating liquid (R-1) was applied onto this substrate using a bar coater so that the thickness after drying was 10 nm. The coated film was dried at 140° C. for 1 minute to form a layer (Z-1) on the substrate. Subsequently, the coating liquid (S-1) was applied using a bar coater so that the thickness after drying was 0.3 μm. The coated film was dried at 120° C. for 3 minutes to form a layer (Y-1) precursor on the layer (Z-1). Thus, a structure having a structure of substrate (X-1)/layer (Z-1)/layer (Y-1) precursor was obtained. Subsequently, the layer (Y-1) was formed by heat-treating the structure at 180° C. for 1 minute. Further, heat treatment was performed at 220° C. for 1 minute. Thus, a multilayer structure (1-1-1) having a structure of substrate (X-1)/layer (Z-1)/layer (Y-1) was obtained.

An adhesive layer was formed on the layer (Y-1) of the multilayer structure (1-1-1) of Example 1, and ONY15 was laminated on the adhesive layer. Next, after forming an adhesive layer on the ONY15, CPP50 was laminated on the adhesive layer and aged by standing at 40° C. for 5 days. Thus, a multilayer structure (1-1-2) having a structure of substrate (X-1)/layer (Z-1)/layer (Y-1)/adhesive layer/ONY15/adhesive layer/CPP50 got Each of the two adhesive layers is coated with the two-component adhesive (Takelac (registered trademark) and Takenate (registered trademark)) using a bar coater so that the thickness after drying is 4 μm, and dried. formed by Regarding the obtained multilayer structure (1-1-2), according to the methods described in the above evaluation methods (1) to (4), the thickness of the layer (Z), the oxygen permeability of the multilayer structure, and the post-autoclave treatment Delamination and moisture permeability of the multilayer structure were measured. Further, after treating the multilayer structure (1-1-2) under the same conditions as the autoclave treatment conditions described in the evaluation method (3), the oxygen permeability is measured by the method described in the evaluation method (2). did. Table 2 shows the results.

<Examples 1-2 to 1-13, Comparative Examples 1-1 to 1-3>
Multilayer structures (1-2-2) to (1-13-2) in the same manner as in Example 1-1, except that the type of coating liquid and the film thickness of the layer (Z) were changed as shown in Table 1. , (C1-1-2) to (C1-3-2) were produced and evaluated. Table 2 shows the results.

[Example 2] Vertical bag-making filling seal bag <Example 2-1>
An adhesive layer was formed on the multilayer structure (1-1-1) prepared in Example 1-1, and ONY15 was laminated on the adhesive layer to obtain a laminate. Next, after forming an adhesive layer on the ONY of the laminate, CPP70 was laminated on the adhesive layer and aged by standing at 40° C. for 5 days to form a multilayer structure (2-1-1). got Each of the two adhesive layers was formed by applying a two-liquid type adhesive using a bar coater so that the thickness after drying was 3 μm, and drying. The multilayer structure (2-1-1) was cut into a width of 400 mm and supplied to a vertical form-fill-seal packaging machine (manufactured by Orihiro Co., Ltd.) so that the CPP layers were heat-sealed in contact with each other. A vertical form-fill-seal bag (2-1-2) (width 160 mm, length 470 mm) of the butt-joint type shown in FIG. A pouch was produced by heat-sealing the vertical bag-making fill-seal bag (2-1-2), and 300 mL of water was filled in the pouch. Subsequently, the obtained pouch was subjected to autoclave treatment under the same conditions as in Example 1-1.

<Comparative Examples 2-1 and 2-2>
Implemented except that (C1-2-1) and (C1-3-1) produced in Comparative Examples 1-2 and 1-3 were used instead of the multilayer structure (1-1-1). Vertical form-fill-seal bags (C2-1-2) to (C2-2-2) were produced in the same manner as the production of the vertical form-fill-seal bag (2-1-2) of Example 2-1. Then, each vertical form-fill-seal bag thus obtained was autoclaved in the same manner as in Example 2-1, resulting in significant delamination.

[Example 3] Flat pouch <Example 3-1>
The multilayer structure (2-1-1) prepared in Example 2-1 was cut into a width of 120 mm × 120 mm, and the two multilayer structures were superimposed so that the CPP layer was on the inside, and the three sides of the rectangle were A flat pouch (3-1-1) was formed by heat sealing. The flat pouch was filled with 100 mL of water. Subsequently, the obtained flat pouch was subjected to autoclave treatment under the same conditions as in Example 1-1.

<Comparative Examples 3-1 and 3-2>
(C1-2-1) and (C1-3-1) produced in Comparative Examples 1-2 and 1-3 instead of the multilayer structure (1-1-1) in Example 2-1 Flat pouches (C3-1-1) to (C3-2-1) were produced in the same manner as the flat pouch (3-1-1) of Example 3-1 except that the was used. Then, each of the obtained flat pouches was autoclaved in the same manner as in Example 3-1, resulting in significant delamination.

[Example 4] Infusion bag <Example 4-1>
Two 120 mm×100 mm multilayer structures were cut out from the multilayer structure (2-1-1) produced in Example 2-1. Subsequently, the two cut multilayer structures were superimposed so that the CPP layer was on the inside, and the peripheral edge was heat-sealed, and a polypropylene spout (plug member) was attached by heat-sealing. Thus, an infusion bag (4-1-1) having a structure similar to that of FIG. 3 was produced. An infusion bag (4-1-1) was filled with 100 mL of water and autoclaved under the same conditions as in Example 1-1.

<Comparative Examples 4-1 and 4-2>
(C1-2-1) and (C1-3-1) produced in Comparative Examples 1-2 and 1-3 instead of the multilayer structure (1-1-1) in Example 2-1 Infusion bags (C4-1-1) to (C4-2-1) were produced in the same manner as the infusion bag (4-1-1) of Example 4-1, except that . Then, each obtained infusion bag was autoclaved in the same manner as in Example 4-1, resulting in significant delamination.

[Example 5] Lid material for container <Example 5-1>
A circular multilayer structure with a diameter of 100 mm was cut out from the multilayer structure (2-1-1) produced in Example 2-1, and used as a cover material for a container. A container with a flange (“Hi-Retflex” (registered trademark), “HR78-84” (trade name) manufactured by Toyo Seikan Co., Ltd.) was prepared as the container body. This container has a cup shape with a top diameter of 78 mm and a height of 30 mm. The upper surface of the container is open, and the width of the flange formed on its periphery is 6.5 mm. The container is composed of a three-layer laminate of olefin layer/steel layer/olefin layer. Next, the container body was filled almost completely with water, and the cover material was heat-sealed to the flange to obtain a container with a lid (5-1-1). At this time, the CPP layer of the lid member was arranged so as to be in contact with the flange portion, and the lid member was heat-sealed. The lidded container (5-1-1) was autoclaved under the same conditions as in Example 1-1.

<Comparative Examples 5-1 and 5-2>
(C1-2-1) and (C1-3-1) produced in Comparative Examples 1-2 and 1-3 instead of the multilayer structure (1-1-1) in Example 2-1 Lid materials (C5-1-1) to (C5-2-1) were produced in the same manner as the lid material (5-1-1) of Example 5-1 except that the was used. As a result of autoclave treatment in the same manner as in Example 5-1 for each of the obtained lid members, significant delamination occurred in the lid portion.

[Example 6] In-mold label container <Example 6-1>
A two-part adhesive was applied to each of the two sheets of CPP 100 using a bar coater so that the thickness after drying was 3 μm, and dried. The two-component adhesive consists of "A-525S" of "Takelac" (registered trademark) manufactured by Mitsui Chemicals, Inc. and "A-50" of "Takenate" (registered trademark) manufactured by Mitsui Chemicals, Inc. A two-liquid reactive polyurethane adhesive was used. Next, two sheets of CPP and the multilayer structure (1-1-1) of Example 1-1 were laminated and aged by standing at 40° C. for 5 days. In this way, a multilayer label (6 -1-1) was obtained.

The multilayer label (6-1-1) was cut according to the shape of the inner wall surface of the female mold part of the container molding die, and attached to the inner wall surface of the female mold part. The male part was then pushed into the female part. Next, molten polypropylene (“EA7A” of “Novatech” (registered trademark) manufactured by Japan Polypropylene Corporation) was injected at 220° C. into the cavity between the male and female mold parts. Injection molding was performed in this manner to form the desired container (6-1-2). The container body had a thickness of 700 μm and a surface area of 83 cm ² . The entire outside of the container is covered with the multi-layer label (6-1-1), the joints are overlapped with the multi-layer label (6-1-1), and where the multi-layer label (6-1-1) does not cover the outside of the container I didn't. At this time, the appearance of the container (6-1-2) was good.

[Example 7] Extrusion coated laminate <Example 7-1>
After forming an adhesive layer on layer (Y) on multilayer structure (1-1-1) in Example 1-1, polyethylene resin (density: 0.917 g/cm ³ , melt flow rate: 8 g/10 minutes) was extrusion coat laminated at 295° C. onto the adhesive layer to a thickness of 20 μm. Thus, a laminate (7-1-1) having a structure of substrate (X-1)/layer (Z-1)/layer (Y-1)/adhesive layer (I)/polyethylene layer was obtained. Ta. The above adhesive layer (I) was formed by applying a two-liquid type adhesive using a bar coater so that the thickness after drying was 0.3 μm, and drying. This two-liquid type adhesive includes "Takelac" (registered trademark) "A-3210" manufactured by Mitsui Chemicals, Inc. and "Takenate" (registered trademark) "A-3070" manufactured by Mitsui Chemicals, Inc. A two-liquid reaction type polyurethane adhesive was used. When the laminate (8-1-2) was autoclaved under the same conditions as in Example 1-1, no delamination occurred and a good appearance was maintained.

<Comparative Examples 7-1 and 7-2>
Implemented except that (C1-2-1) and (C1-3-1) produced in Comparative Examples 1-2 and 1-3 were used instead of the multilayer structure (1-1-1). Laminates (C7-1-1) to (C7-2-1) were produced in the same manner as in Example 7-1. Each of the obtained laminates was autoclaved in the same manner as in Example 7-1, resulting in significant delamination of the lid portion.

[Example 8] Effect of filling <Example 8-1>
The flat pouch (3-1-1) prepared in Example 3-1 was filled with 500 mL of a 1.5% ethanol aqueous solution and autoclaved under the same conditions as in Example 1-1. As a result, delamination occurred. A good appearance was maintained.

<Examples 8-2 to 8-9>
Autoclave treatment was performed in the same manner as in Example 8-1, except that 500 mL of another filling was filled in the flat pouch (3-1-1) instead of 500 mL of the 1.5% ethanol aqueous solution. Then, a measurement sample was cut out from the flat pouch after the autoclave treatment, and the oxygen permeability of the sample was measured. Other fillers include 1.0% ethanol aqueous solution (Example 8-2), vinegar (Example 8-3), pH 2 citric acid aqueous solution (Example 8-4), edible oil (Example 8-5 ), ketchup (Example 8-6), soy sauce (Example 8-7), and ginger paste (Example 8-8). In both cases, the oxygen permeability of the samples after autoclaving was 0.2 cc/(m ² ·day·atm). Furthermore, the lidded container (6-1-2) prepared in Example 6-1 was almost completely filled with mandarin orange syrup and autoclaved in the same manner as in Example 8-1 (Example 8-9). . After the autoclave treatment, no delamination occurred and a good appearance was maintained.

As is clear from Examples 8-1 to 8-9, the packaging material of the present invention maintained a good appearance even after being autoclaved while being filled with various foods.

[Example 9] Vacuum insulator <Example 9-1>
The two-part adhesive used in Example 6-1 was coated on CPP50 so that the thickness after drying was 3 μm, and dried to form an adhesive layer. By bonding this CPP50 and the PET layer of the multilayer structure (2-1-1) prepared in Example 2-1, CPP/adhesive layer (I)/substrate (X-1)/layer (Z A laminate (9-1-1) having a structure of -1)/layer (Y-1)/adhesive layer (I)/ONY/adhesive layer (I)/CPP was obtained. Subsequently, the two-liquid reactive polyurethane adhesive was applied onto the ONY 15 so that the thickness after drying was 3 μm, and dried to form an adhesive layer. By bonding the ONY 15 and the laminate (9-1-1) together, a structure of CPP/adhesive layer (I)/laminate (9-1-1)/adhesive layer (I)/ONY is formed. A multilayer structure (9-1-2) having

The multilayer structure (9-1-2) was cut to obtain two laminates each having a size of 700 mm×300 mm. The two laminates were superimposed so that the CPP layers faced each other inside, and the three sides were heat-sealed with a width of 10 mm to prepare a three-sided bag. Next, a heat-insulating core material was filled from the opening of the three-sided bag, and the three-sided bag was sealed at 20° C. and an internal pressure of 10 Pa using a vacuum packaging machine. Thus, a vacuum insulator (9-1-3) was obtained. Silica fine powder was used for the heat-insulating core material. After leaving the vacuum insulator (9-1-3) under the conditions of 40° C. and 15% RH for 360 days, the pressure inside the vacuum insulator was measured using a Pirani vacuum gauge, and the result was 37.0 Pa. Ta.

<Example 9-2>
The two-part adhesive used in Example 6-1 was coated on CPP50 so that the thickness after drying was 3 μm, and dried to form an adhesive layer. By laminating this CPP50 and VM-XL, a laminate (9-2-1) having a structure of VM-XL/adhesive layer/CPP50 was obtained. Subsequently, on the layer (Y-1) of the multilayer structure (1-1-1) prepared in Example 1-1, the two-liquid reactive polyurethane adhesive was applied so that the thickness after drying was 3 μm. and dried to form an adhesive layer. Then, by bonding the multilayer structure (1-1-1) and the laminate (9-2-1) together, the substrate (X-1)/layer (Z-1)/layer (Y-1) )/adhesive layer/VM-XL/adhesive layer/CPP50 (9-2-2) was obtained. Furthermore, by the same method, another sheet of the multilayer structure (1-1-1) is attached to obtain a substrate (X-1)/layer (Z-1)/layer (Y-1)/adhesive layer A multilayer structure (9-2-3) having a layer configuration of / base material (X-1) / layer (Z-1) / layer (Y-1) / adhesive layer / VM-XL / adhesive layer / CPP50 Obtained. The multilayer structure (9-2-3) was cut to obtain two laminates each having a size of 700 mm×300 mm. The two laminates were superimposed so that the CPP layers faced each other inside, and the three sides were heat-sealed with a width of 10 mm to prepare a three-sided bag. Next, a heat-insulating core material was filled from the opening of the three-sided bag, and the three-sided bag was sealed at 20° C. and an internal pressure of 10 Pa using a vacuum packaging machine. Thus, a vacuum insulator (9-2-4) was obtained. Silica fine powder was used for the heat-insulating core material. After leaving the vacuum insulator (9-2-4) under the conditions of 40° C. and 15% RH for 360 days, the pressure inside the vacuum insulator was measured using a Pirani vacuum gauge, and the result was 28.0 Pa. Ta.

<Example 10-1>
An adhesive layer was formed on the multilayer structure (1-1-1) prepared in Example 1-1, and an acrylic resin film (thickness: 50 μm) was laminated on the adhesive layer to obtain a laminate. Subsequently, after forming an adhesive layer on the side of the substrate (X-1) of the multilayer structure (1-1-1) of the laminate, PET50 was laminated. In this way, a protection having a configuration of PET / adhesive layer (I) / substrate (X-1) / layer (Z-1) / layer (Y-1) / adhesive layer (I) / acrylic resin film A sheet (10-1-1) was obtained. Each of the two adhesive layers was formed by applying a two-liquid type adhesive to a thickness of 3 μm after drying and drying. The two-component adhesive consists of "A-1102" of "Takelac" (registered trademark) manufactured by Mitsui Chemicals, Inc. and "A-3070" of "Takenate" (registered trademark) manufactured by Mitsui Chemicals, Inc. A two-liquid reactive polyurethane adhesive was used.

Subsequently, as a durability test of the obtained protective sheet (10-1-1), a constant temperature and humidity tester was used to test the protective sheet for 1,000 hours in an atmosphere of 85° C. and 85% RH under atmospheric pressure. As a result of a storage test (dump heat test), good appearance was maintained without occurrence of delamination.

Claims (14)

A metal oxide comprising a substrate (X), a layer (Z) laminated on the substrate (X), and a layer (Y) laminated on the layer (Z), wherein the layer (Y) contains aluminum containing a reaction product (D) of the substance (A) and an inorganic phosphorus compound (BI), the layer (Z) containing a hydroxyl group-containing resin (C),
A multilayer structure in which the hydroxyl group-containing resin (C) accounts for 80% by mass or more of the layer (Z) . The hydroxyl-containing resin (C) has hydroxyl-containing monomer units, and the content of the hydroxyl-containing monomer units in the hydroxyl-containing resin (C) is the total amount of monomers constituting the hydroxyl-containing resin (C). 2. The multilayer structure according to claim 1 , which is 30 mol % or more based on the body unit. 3. The multilayer according to claim 1 or 2 , wherein the viscosity of the 4% by mass aqueous solution of the hydroxyl group-containing resin (C) is 1 mPa s or more and 100 mPa s or less, measured according to JIS K 6726 (1994). Structure. 4. The multilayer structure according to any one of claims 1 to 3 , wherein the hydroxyl group-containing resin (C) contains a vinyl alcohol resin. 5. The multilayer structure according to claim 4 , wherein the vinyl alcohol resin has a saponification degree of 40 to 99.9 mol %. Multilayer structure according to any one of the preceding claims, wherein the thickness of layer (Z) is in the range from 1 to 100 nm. A step (I) of applying a coating liquid (R) containing a hydroxyl-containing resin (C) and a solvent onto a substrate (X) and then removing the solvent to form a layer (Z); (A), an inorganic phosphorus compound (BI), and a coating liquid (S) containing a solvent are applied onto the layer (Z), and then the solvent is removed to form a layer (Y) precursor (II) and a step (III) of forming the layer (Y) by heat-treating the layer (Y) precursor. A packaging material comprising the multilayer structure according to any one of claims 1-6 . The packaging material according to claim 8 , which is a vertical form-fill-seal bag, a vacuum packaging bag, a pouch, a laminate tube container, an infusion bag, a lid material for a container, a paper container, a strip tape, or an in-mold label container. 10. A product at least partly of which the packaging material according to claim 8 or 9 is used. 11. The product of claim 10 , wherein the product comprises a content, the content being a core material, and the interior of the product being evacuated to act as a vacuum insulator. A protective sheet for an electronic device, comprising the multilayer structure according to any one of claims 1 to 6 . 13. The electronic device protective sheet according to claim 12 , which is a protective sheet for protecting the surface of a photoelectric conversion device, an information display device, or a lighting device. An electronic device comprising the protective sheet according to claim 12 or 13 .