JP7218200B2 - 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-layer structure in which a gas barrier layer composed of aluminum or aluminum oxide is formed on a plastic film has been well known in the past. It is used as a constituent member of protective sheets for electronic devices that require gas barrier properties and water vapor barrier properties. Many of such gas barrier layers are formed on plastic films by dry processes such as physical vapor deposition (PVD) and chemical vapor deposition (CVD). However, these vapor-deposited films lack the flexibility of the inorganic compound thin film used for the gas barrier layer, are vulnerable to rubbing and bending, and have poor adhesion to the base material. During the post-processing of the packaging material such as printing, lamination and bag making, there is a problem that cracks are generated in the thin film and the gas barrier property is remarkably lowered.

In response to this problem, in Patent Document 1, an aqueous solution containing at least one of a water-soluble polymer and (a) a metal alkoxide and/or its hydrolyzate or (b) tin chloride, or water / It describes a method for improving the gas barrier properties and protecting the deposited layer by applying a coating agent containing an alcohol mixed solution as a main component to form a highly flexible gas barrier overcoat layer.

On the other hand, in recent years, a method of constructing a barrier layer through a process of applying a coating liquid has been used. Patent Document 2 describes, as a composite structure having a gas barrier layer containing aluminum, for example, a composite structure having a transparent gas barrier layer composed of a reaction product of aluminum oxide particles and a phosphorus compound. As one method for forming a gas barrier layer, a method is described in which a coating liquid containing aluminum oxide particles and a phosphorus compound is applied onto a plastic film, followed by drying and heat treatment.

Further, in Patent Document 3, a layer containing a polymer having a plurality of phosphorus atoms and a polymer having an ether bond and having no glycosidic bond is laminated adjacent to a layer having an aluminum atom, so that retort treatment is performed. It is described that it has good interlaminar adhesive strength even after being processed, and maintains a high level of gas barrier properties when subjected to physical stress such as stretching.

Japanese Patent No. 2790054 WO2011/122036 WO2016/103716

However, when the multilayer structure described in Patent Documents 1 to 3 is used as a packaging material, bending after being subjected to severe conditions such as retort treatment (hereinafter sometimes simply referred to as "after retort treatment") The gas barrier property may be insufficient due to physical stress (hereinafter sometimes simply referred to as “bending”) such as, and there is a demand for a gas barrier multilayer structure that has good properties even after bending after retort processing. there is

The object of the present invention is to achieve excellent gas barrier properties and water vapor barrier properties, maintain the gas barrier properties and water vapor barrier properties even after bending after retort treatment, and have high interlayer adhesive strength ( It is to provide a novel multilayer structure having a peel strength), a packaging material and a product using the same. Another object of the present invention is to provide a protective sheet for electronic devices using a novel multi-layer structure that has excellent gas barrier properties and water vapor barrier properties and can maintain these barrier properties even after a dump heat test. That's what it is. In this specification, the point that gas barrier properties and water vapor barrier properties can be maintained even after bending after retort treatment, and the point that it has high interlayer adhesive strength (peel strength) that does not cause poor appearance such as interlayer peeling after retort treatment. , is sometimes simply expressed as “retort resistance”.

According to the present invention, the above objects are achieved by providing the following inventions.
[1] A multilayer structure comprising a substrate (X), a layer (Y), and a layer (Z), wherein the layer (Y) comprises a metal oxide (A) containing aluminum and an inorganic phosphorus compound ( B) contains the reaction product (D), the layer (Z) contains the polymer (G) and the hydrolytic condensate (La) of the compound (L) having a hydrolyzable characteristic group, and the compound ( L) includes compound (L ¹ ) and compound (L ² ), compound (L ¹ ) is a silicon compound having an organic group having a glycidyl group and a hydrolyzable characteristic group, and compound (L ² ) is , a silicon compound having no organic group having a glycidyl group and having a hydrolyzable characteristic group, [total mass of organic components derived from the polymer (G) and the hydrolytic condensate (La) W _{G + La} ] and [mass W _La of the inorganic component derived from the hydrolytic condensate (La)] have a mass ratio W _G+La /W _La of 0.10 or more and 0.70 or less, and the inorganic phosphorus compound (B) is , phosphoric acid, polyphosphoric acid, phosphorous acid, phosphonic acid and at least one compound selected from the group consisting of derivatives thereof;
[2] The compound (L ¹ ) has the following general formula (I)
^SiX1pZqR1 _{( 4-pq) (} ^I )
[In formula (I) above, X ¹ is any one selected from the group consisting of F, Cl, Br, I, R ² O--, R ³ COO--, (R ⁴ CO) ₂ CH--, and NO ₃ 1, Z represents an organic group having a glycidyl group, and R ¹ , R ² , R ³ and R ⁴ each independently represents a group consisting of an alkyl group, an aralkyl group, an aryl group and an alkenyl group. represents any one group selected from the above, p represents an integer of 1 to 3, and q represents an integer of 1 to 3. 2≦(p+q)≦4. When multiple X ¹ are present, those X ¹ may be the same or different. When there are multiple Z's, those Z's may be the same or different. When multiple R ¹ are present, those R ¹ may be the same or different. ]
is at least one compound represented by
Compound (L ² ) has the following general formula (II)
^SiX2rR5 _{(4-r) (} ^II )
[In formula (II) above, X ² is any one selected from the group consisting of F, Cl, Br, I, R ⁶ O--, R ⁷ COO--, (R ⁸ CO) ₂ CH--, and NO ₃ R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represent any one group selected from the group consisting of an alkyl group, an aralkyl group, an aryl group and an alkenyl group; represents an integer from 1 to 4. When multiple X ² are present, those X ² may be the same or different. ^When there are multiple R5's, those R5's may be the ^same or different. ]
The multilayer structure of [1], which is at least one compound represented by;
[3] The multilayer structure of [1] or [2], wherein the polymer (G) is a water-soluble polymer (Ga);
[4] The water-soluble polymer (Ga) is at least one selected from the group consisting of water-soluble polyvinyl alcohol, water-soluble polyacrylic acid, water-soluble polymethacrylic acid, water-soluble polyvinylpyrrolidone, water-soluble polyamide, and water-soluble polyurethane. The multilayer structure of [3], which is a seed polymer;
[5] The multilayer structure of [3] or [4], wherein the water-soluble polymer (Ga) contains at least water-soluble polyvinyl alcohol or water-soluble polyamide;
[6] The multilayer structure of any one of [3] to [5], wherein the water-soluble polymer (Ga) contains water-soluble polyvinyl alcohol and water-soluble polyacrylic acid;
[7] The multilayer structure of any one of [1] to [6], wherein at least one pair of layer (Z) and layer (Y) are arranged adjacent to each other;
[8] The multilayer structure of any one of [1] to [7], wherein the substrate (X) comprises at least one layer selected from the group consisting of thermoplastic resin films and paper;
[9] Containing a polymer (G), a hydrolytic condensate (La) of a compound (L) having a hydrolyzable characteristic group, and a solvent,
Compound (L) includes compound (L ¹ ) and compound (L ² ),
Compound (L ¹ ) has the following general formula (I)
^SiX1pZqR1 _{( 4-pq) (} ^I )
[In formula (I) above, X ¹ is any one selected from the group consisting of F, Cl, Br, I, R ² O--, R ³ COO--, (R ⁴ CO) ₂ CH--, and NO ₃ 1, Z represents an organic group having a glycidyl group, and R ¹ , R ² , R ³ and R ⁴ each independently represents a group consisting of an alkyl group, an aralkyl group, an aryl group and an alkenyl group. represents any one group selected from the above, p represents an integer of 1 to 3, and q represents an integer of 1 to 3. 2≦(p+q)≦4. When multiple X ¹ are present, those X ¹ may be the same or different. When there are multiple Z's, those Z's may be the same or different. When multiple R ¹ are present, those R ¹ may be the same or different. ]
is at least one compound represented by
Compound (L ² ) has the following general formula (II)
^SiX2rR5 _{(4-r) (} ^II )
[In formula (II) above, X ² is any one selected from the group consisting of F, Cl, Br, I, R ⁶ O--, R ⁷ COO--, (R ⁸ CO) ₂ CH--, and NO ₃ R ⁵ , R ⁶ , R ⁷ and R ⁸ represent any one group selected from the group consisting of an alkyl group, an aralkyl group, an aryl group and an alkenyl group, and r represents 1 to 4 represents an integer of When multiple X ² are present, those X ² may be the same or different. ^When there are multiple R5's, those R5's may be the ^same or different. ]
is at least one compound represented by [total mass W _G+La of the organic components derived from the polymer (G) and the hydrolytic condensate (La)] and [derived from the hydrolytic condensate (La) A coating liquid in which the mass ratio W _G+La /W _La of the mass W _La of the inorganic component is 0.10 or more and 0.70 or less;
[10] By applying a coating liquid (S) containing a metal oxide (A) containing aluminum, an inorganic phosphorus compound (B), and a solvent onto a substrate (X), and removing the solvent. A step (I) of forming a layer (Y) precursor layer, and a hydrolytic condensate of a polymer (G) and a compound (L) having a hydrolyzable characteristic group on the layer (Y) precursor layer. Step (II) of applying a coating liquid (T) containing (La) and a solvent and removing the solvent to form a layer (Z) precursor layer, and a layer (Y) precursor layer and layer (Z) The method for producing a multilayer structure according to any one of [1] to [8], comprising step (III) of heat-treating the precursor layer to form layer (Y) and layer (Z);
[11] A packaging material comprising the multilayer structure of any one of [1] to [8];
[12] The packaging material of [11], which is a vertical form-fill-seal bag, a vacuum packaging bag, a pouch, a laminate tube container, an infusion bag, a paper container, a strip tape, a lid material for a container, or an in-mold label container;
[13] A vacuum insulator in which the packaging material of [12] is a vacuum packaging bag, the vacuum packaging bag contains a content, the content is a core material, and the inside of the vacuum packaging bag is decompressed;
[14] A protective sheet for an electronic device, comprising the multilayer structure of any one of [1] to [8];
[15] The electronic device protective sheet of [14], which is a protective sheet for protecting the surface of a photoelectric conversion device, an information display device, or a lighting device;
[16] An electronic device having the protective sheet of [14] or [15] is provided.

According to the present invention, the gas barrier property and the water vapor barrier property are excellent, the gas barrier property and the water vapor barrier property can be maintained even after bending after retort treatment, and the high interlayer adhesive strength ( peel strength), a packaging material and a product using the same can be obtained. Also, a protective sheet for an electronic device using a novel multilayer structure that has excellent gas barrier properties and water vapor barrier properties and can maintain the barrier properties even after a dump heat test can be obtained.

The invention is illustrated below by means of examples. In the following description, substances, conditions, methods, numerical ranges, etc. may be exemplified, but the present invention is not limited to such exemplifications. In addition, the exemplified substances may be used singly or in combination of two or more unless otherwise noted.

[Multilayer structure]
The multilayer structure of the present invention comprises a substrate (X), a layer (Y) and a layer (Z). Layer (Y) is a reaction product (D) (hereinafter simply " Also referred to as "reaction product (D)"). The layer (Z) contains a hydrolytic condensate (La) of a polymer (G) and a compound (L) having a hydrolyzable characteristic group (hereinafter also simply referred to as "compound (L)"), and a compound ( L) includes compound (L ¹ ) and compound (L ² ), compound (L ¹ ) is a silicon compound having an organic group having a glycidyl group and a hydrolyzable characteristic group, and compound (L ² ) is , a silicon compound having no organic group having a glycidyl group and having a hydrolyzable characteristic group, [total mass of organic components derived from the polymer (G) and the hydrolytic condensate (La) W _{G + La} ] and [mass W _La of the inorganic component derived from the hydrolytic condensate (La)] have a mass ratio W _G+La /W _La of 0.10 or more and 0.70 or less, and the inorganic phosphorus compound (B) is , phosphoric acid, polyphosphoric acid, phosphorous acid, phosphonic acid and derivatives thereof. Here, W _G+La /W _La can be measured using TOF-SIMS or the like. For W _G+La and the weight W _La of the inorganic component derived from the hydrolyzed condensate (La), values calculated from the weights of raw materials used in preparing the composition are used. That is, in the examples of the present invention, it is assumed that the compound (L) is completely hydrolyzed and condensed to form a hydrolytic condensate (La), and the organic component (having a glycidyl group) derived from the hydrolytic condensate (La) is (organic groups, etc.) and inorganic components are calculated, and the mass of the organic component of the polymer (G) is added. Unless otherwise noted in the following description, the term "multilayer structure" means a multilayer structure including a substrate (X), a layer (Y) and a layer (Z).

[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; and glass. Among them, thermoplastic resins and fiber aggregates are preferred, and thermoplastic resins are more preferred. The form of the base material (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 and paper, more preferably a thermoplastic resin film, and still more preferably a thermoplastic 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; When the multilayer structure is used as a packaging material, the material of the substrate (X) is preferably at least one thermoplastic resin selected from the group consisting of polyethylene, polypropylene, polyethylene terephthalate, nylon-6, and nylon-66.

When a film made of a thermoplastic resin 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 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. When paper is used as the substrate (X), a multilayer structure for paper containers 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.

[Layer (Y)]
The layer (Y) contains a reaction product (D) of a metal oxide containing aluminum (A) and an inorganic phosphorus compound (B). The metal oxide containing aluminum (A) and the inorganic phosphorus compound (B) are described below.

[Metal oxide containing aluminum (A)]
The metal oxide (A) containing aluminum is usually reacted in the form of particles with the inorganic phosphorus compound (B). Metal atoms constituting the metal oxide containing aluminum (A) (these may be collectively referred to as "metal atoms (M)") are at least one selected from metal atoms belonging to groups 2 to 14 of the periodic table It is preferably a metal atom of the species, including at least aluminum. The metal atom (M) may be aluminum alone, or may include aluminum and other metal atoms. In addition, you may use together 2 or more types of metal oxides (A) as a metal oxide (A).

The proportion of aluminum in the metal atoms (M) is preferably 50 mol % or more, more preferably 60 to 100 mol %, even more preferably 80 to 100 mol %, and may consist essentially of aluminum. 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.

Metal oxide (A) is preferably a hydrolytic condensate of compound (E) containing metal atom (M) to which a hydrolyzable characteristic group is bonded. Examples of the characteristic group include R ⁹ of general formula [III] described later. 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]
Since the metal oxide (A) whose reaction with the inorganic phosphorus compound (B) is easily controlled is easily formed, and the resulting multilayer structure has excellent gas barrier properties, the compound (E) is represented by the following general formula [III] At least one compound (Ea) represented by is preferably included.
Al(R9) _k (R10) ^{3 -} _k [III]
In the formula, R ⁹ is a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), NO ₃ , an alkoxy group having 1 to 9 carbon atoms, an aryloxy group having 5 to 9 carbon atoms, or 2 to 9 carbon atoms. an acyloxy group having 3 to 9 carbon atoms, an alkenyloxy group having 3 to 9 carbon atoms, a β-diketonato group having 5 to 15 carbon atoms, or a diacylmethyl group having an acyl group having 1 to 9 carbon atoms. R ¹⁰ represents an alkyl group having 1 to 9 carbon atoms, an aralkyl group having 7 to 10 carbon atoms, an alkenyl group having 2 to 9 carbon atoms, or an aryl group having 6 to 10 carbon atoms. The alkoxy group, aryloxy group, acyloxy group, alkenyloxy group, β-diketonato group, diacylmethyl group, alkyl group, aralkyl group, alkenyl group and aryl group may have a substituent. k represents an integer of 1 to 3; When two or more R ⁹ are present, each R ⁹ may be the same or different. When there are multiple R ¹⁰ s, the R ^10s may be the same or different.

The compound (E) may contain at least one compound (Eb) represented by the following general formula [IV] in addition to the compound (Ea).
_M1 ( ^R11 ) _m ( ^R12 ) ^nm [IV]
In the formula, M ¹ represents at least one metal atom selected from metal atoms other than aluminum atoms and belonging to groups 2 to 14 of the periodic table. R ¹¹ is a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), NO ₃ , an alkoxy group having 1 to 9 carbon atoms, an aryloxy group having 5 to 9 carbon atoms, an acyloxy group having 2 to 9 carbon atoms; , represents an alkenyloxy group having 3 to 9 carbon atoms, a β-diketonato group having 5 to 15 carbon atoms, or a diacylmethyl group having an acyl group having 1 to 9 carbon atoms. R ¹² represents an alkyl group having 1 to 9 carbon atoms, an aralkyl group having 7 to 10 carbon atoms, an alkenyl group having 2 to 9 carbon atoms, or an aryl group having 6 to 10 carbon atoms. The alkoxy group, aryloxy group, acyloxy group, alkenyloxy group, β-diketonato group, diacylmethyl group, alkyl group, aralkyl group, alkenyl group and aryl group may have a substituent. m represents an integer from 1 to n. n is ^equal to the valence of M1. When two or more R ¹¹ are present, each R ¹¹ may be the same or different. When two or more R ¹² are present, each R ¹² may be the same or different.

Substituents that each group represented by R ⁹ , R ¹⁰ , R ¹¹ and R ¹² may have include, for example, an alkyl group having 1 to 6 carbon atoms; a methoxy group, an ethoxy group, an n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, n-pentyloxy group, isopentyloxy group, n-hexyloxy group, cyclopropyloxy group, cyclobutyloxy group, cyclopentyl alkoxy groups having 1 to 6 carbon atoms such as oxy group and cyclohexyloxy group; methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, isopropoxycarbonyl group, n-butoxycarbonyl group, isobutoxycarbonyl group, sec-butoxy alkoxycarbonyl groups having 1 to 6 carbon atoms such as carbonyl group, tert-butoxycarbonyl group, n-pentyloxycarbonyl group, isopentyloxycarbonyl group, cyclopropyloxycarbonyl group, cyclobutyloxycarbonyl group, cyclopentyloxycarbonyl group; Aromatic hydrocarbon groups such as phenyl group, tolyl group and naphthyl group; halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; acyl groups having 1 to 6 carbon atoms; aralkyl groups having 7 to 10 carbon atoms; aralkyloxy groups having 7 to 10 carbon atoms; alkylamino groups having 1 to 6 carbon atoms; and dialkylamino groups having alkyl groups having 1 to 6 carbon atoms.

R ⁹ and R ¹¹ are a halogen atom, NO ₃ , an alkoxy group having 1 to 6 carbon atoms, an acyloxy group having 2 to 6 carbon atoms, a β-diketonato group having 5 to 10 carbon atoms, or a A diacylmethyl group having an acyl group is preferred, and an alkoxy group having 1 to 6 carbon atoms is more preferred.

R ¹⁰ is preferably an alkyl group having 1 to 6 carbon atoms. k in formula [III] is preferably 3.

R ¹² is preferably an alkyl group having 1 to 6 carbon atoms. M ¹ is preferably a metal atom belonging to Group 4 of the periodic table, more preferably titanium or zirconium. When M ¹ is a metal atom belonging to Group 4 of the periodic table, m in formula [IV] is preferably 4. Although boron and silicon are sometimes classified as semimetals, they are included in metals in this specification.

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.

Examples of the compound (Eb) include tetrakis(2,4-pentanedionato)titanium, tetramethoxytitanium, tetraethoxytitanium, tetraisopropoxytitanium, tetra-n-butoxytitanium, tetrakis(2-ethylhexoxy)titanium, and the like. Titanium compounds; zirconium compounds such as tetrakis(2,4-pentanedionato)zirconium, tetra-n-propoxyzirconium, tetra-n-butoxyzirconium, and the like. These may be used individually by 1 type, and may use 2 or more types of compounds (Eb) together.

In the compound (E), the ratio of the compound (Ea) to the compound (E) is preferably 50 mol% or more, more preferably 80 mol% or more, further preferably 90 mol% or more, as long as the effects of the present invention can be obtained. , 95 mol % or more is particularly preferable, and the compound (E) may consist essentially of the compound (Ea). The ratio of compounds other than compound (Ea) (for example, compound (Eb)) to compound (E) is preferably 20 mol% or less, more preferably 10 mol% or less, further preferably 5 mol% or less, and 0 mol%. may be

By hydrolyzing the compound (E), at least part of the hydrolyzable characteristic groups of the compound (E) are converted to hydroxyl groups. Furthermore, the condensation of the hydrolyzate forms a compound in which the metal atom (M) is linked via the oxygen atom (O). When this condensation is repeated, a compound is formed which can be regarded as substantially a metal oxide (A). 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 hydrolytic condensation to occur, it is important that 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 intended 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). At least one selected from the group consisting of compounds obtained by condensing a part of the complete hydrolyzate of can be used.

It is preferable that the metal oxide (A) to be mixed with the inorganic phosphorus compound (B) to be described later does not substantially contain phosphorus atoms.

[Inorganic phosphorus compound (B)]
The inorganic phosphorus compound (B) contains a site that can react with the metal oxide (A), and typically contains a plurality of such sites (atomic groups or functional groups), preferably 2 to 20. do. 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 the inorganic phosphorus compound (B) 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 and derivatives thereof (eg, salts (eg, sodium phosphate), halides (eg, phosphoryl chloride), dehydrates (eg, diphosphorus pentoxide)), and the like.

One of these inorganic phosphorus compounds (B) may be used alone, or two or more thereof may be used in combination. Among them, it is preferable to use phosphoric acid alone, or to use phosphoric acid in combination with another inorganic phosphorus compound (B). The use of phosphoric acid improves the stability of the coating liquid (S) described later and the gas barrier properties of the obtained multilayer structure. When phosphoric acid and another inorganic phosphorus compound (B) are used together, the proportion of phosphoric acid in the inorganic phosphorus compound (B) is preferably 50 mol% or more, more preferably 70 mol% or more, and 90 mol% or more. is more preferable, and the inorganic phosphorus compound (B) may consist essentially of phosphoric acid.

[Reaction product (D)]
A reaction product (D) is obtained by a reaction between a metal oxide (A) and an inorganic phosphorus compound (B). Here, the reaction product (D) also includes compounds produced by reacting the metal oxide (A), the inorganic phosphorus compound (B), and other compounds. Layer (Y) may partially contain metal oxide (A) and/or inorganic phosphorus compound (B) that do not participate in the reaction. From the viewpoint of developing good gas barrier properties and water vapor barrier properties, the proportion of the reaction product (D) in the layer (Y) is preferably 80% by mass or more, more preferably 90% by mass or more, and further preferably 95% by mass or more. Preferably, 97.5% by mass or more is particularly preferable. The layer (Y) may consist essentially of the reaction product (D). In addition, the component of the layer (Z) may permeate into the layer (Y). In that case, the ratio of the components of the reaction product (D) and the layer (Z) in the layer (Y) is preferably 50% by mass or more, more preferably 90% by mass or more, further preferably 95% by mass or more. 5% by mass or more is particularly preferred. Layer (Y) may consist essentially of the components of reaction product (D) and layer (Z).

In the reaction product (D), the molar ratio between the metal atoms constituting the metal oxide (A) and the phosphorus atoms derived from the inorganic phosphorus compound (B) is [metal atoms constituting the metal oxide (A)] : [phosphorus atom derived from inorganic phosphorus compound (B)] = preferably in the range of 1.0:1.0 to 3.6:1.0, 1.1:1.0 to 3.0: It is more preferably in the range of 1.0. Outside this range, the gas barrier performance is lowered. The molar ratio can be adjusted by adjusting the mixing ratio of the metal oxide (A) and the inorganic phosphorus compound (B) in the coating liquid for forming the reaction product (D). The molar ratio is usually the same as in the coating liquid.

In the infrared absorption spectrum of layer (Y), the maximum absorption wavenumber in the region of 800 to 1,400 cm ^-1 is preferably in the range of 1,080 to 1,130 cm ^-1 . In the process of reacting the metal oxide (A) and the inorganic phosphorus compound (B) to form the reaction product (D), the metal atom (M) derived from the metal oxide (A) and the inorganic phosphorus compound (B) and a phosphorus atom (P) derived from form a bond represented by M--O--P through 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). As a result of examination by the present inventors, when the characteristic absorption band based on M—O—P bonding is observed in the region of 1,080 to 1,130 cm ⁻¹ , the obtained multilayer structure is an excellent gas barrier. It was found to express sexuality. In particular, when the characteristic absorption band is the strongest absorption in the region of 800 to 1,400 cm ⁻¹ where absorption derived from bonding between various atoms and oxygen atoms is generally observed, the obtained multilayer structure was found to exhibit even better 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 (B) are mixed in advance and then hydrolyzed and condensed, the metal atoms derived from the metal compound and the inorganic phosphorus compound (B) 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 1,400 cm ^-1 is outside the range of 1,080 to 1,130 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 1,400 cm ^-1 is preferably 200 cm ^-1 or less, and 150 cm ^-1 from the viewpoint of the gas barrier properties of the resulting multilayer structure. ¹ or less is more preferable, 100 cm ^-1 or less is more preferable, and 50 cm ^-1 or less is particularly preferable.

The infrared absorption spectrum of the layer (Y) can be measured, for example, by an attenuated total reflection method using a Fourier transform infrared spectrophotometer. Measurement can be performed by separating the layer (Y) plane of the multilayer structure from the other layers in a measurement area of 800 to 1400 cm ^-1 by a reflection method. However, if it is not possible to measure by the above method, reflectance measurement such as reflection absorption method, external reflection method, attenuated total reflection method, etc., or transmittance measurement such as Nujol method, tablet method, etc. by scraping layer (Y) from the multilayer structure. It is not limited to these.

[Polymer (F)]
Layer (Y) may contain a polymer (F). The polymer (F) is a polymer having at least one functional group selected from the group consisting of hydroxyl groups, carboxyl groups, carboxylic acid anhydride groups, and salts of carboxyl groups. The polymer (F) may be a homopolymer of a monomer having at least one functional group selected from the group consisting of hydroxyl groups, carboxyl groups, carboxylic acid anhydride groups, and salts of carboxyl groups. It may be a copolymer having monomers.

Examples of the polymer (F) include polyvinyl alcohol polymers such as polyethylene glycol; polyvinyl alcohol; modified polyvinyl alcohol containing 1 to 50 mol% of an α-olefin unit having 4 or less carbon atoms; Polysaccharides such as cellulose and starch; (meth)acrylic acid polymers such as polyhydroxyethyl (meth)acrylate, poly(meth)acrylic acid, and ethylene-acrylic acid copolymer; ethylene-maleic anhydride copolymer Maleic acid polymers such as a hydrolyzate of coalescence, a hydrolyzate of a styrene-maleic anhydride copolymer, a hydrolyzate of an isobutylene-maleic anhydride alternating copolymer, and the like. Among them, polyethylene glycol and polyvinyl alcohol-based polymers are preferred. As the polymer (F), two or more types of polymer (F) may be mixed and used.

Although the molecular weight of the polymer (F) is not particularly limited, the number average molecular weight of the polymer (F) is , is preferably 5,000 or more, more preferably 8,000 or more, and even more preferably 10,000 or more. The upper limit of the number average molecular weight of the polymer (F) is not particularly limited, and is, for example, 1,500,000 or less.

When the layer (Y) contains the polymer (F), the proportion of the polymer (F) in the layer (Y) is preferably 20% by mass or less from the viewpoint of achieving both flexibility, gas barrier properties, and water vapor barrier properties. , is more preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 2.5% by mass or less. The polymer (F) may or may not react with other components in the layer (Y).

[Polymer (C) having a phosphorus atom]
The layer (Y) may contain a polymer (C) having a phosphorus atom (hereinafter sometimes abbreviated as "polymer (C)"). Polymer (C) is typically a polymer having functional groups containing phosphorus atoms. Such functional groups include, for example, phosphoric acid group, phosphorous acid group, phosphonic acid group, phosphonous acid group, phosphinic acid group, phosphinic acid group, and functional groups derived from these (e.g., salts, (partial) ester compounds, halides (e.g., chlorides), dehydrates) and the like, and the polymer (C) may have one of these functional groups alone or two or more of them. . As the functional group containing a phosphorus atom, a phosphoric acid group and a phosphonic acid group are preferable, and a phosphonic acid group is more preferable. Examples of the polymer (C) include 6-[(2-phosphonoacetyl)oxy]hexyl acrylate, 2-phosphonooxyethyl methacrylate, phosphonomethyl methacrylate, 11-phosphonoundecyl methacrylate, 1,1-diphosphono Phosphono (meth) acrylic acid esters such as ethyl methacrylate; Vinyl phosphonic acids such as vinylphosphonic acid, 2-propene-1-phosphonic acid, 4-vinylbenzylphosphonic acid, and 4-vinylphenylphosphonic acid; Vinylphosphinic acid, 4 -vinylphosphinic acids such as vinylbenzylphosphinic acid; homopolymers or copolymers of monomers having a functional group containing a phosphorus atom such as; Among them, polymers of phosphono(meth)acrylic acid esters and vinylphosphonic acids are preferred, polymers of vinylphosphonic acids are more preferred, and poly(vinylphosphonic acid) is even more preferred. Further, as the polymer (C), two or more kinds of polymers composed of a single monomer may be mixed and used. The polymer (C) can also be obtained by homopolymerizing or copolymerizing vinylphosphonic acid derivatives such as vinylphosphonic acid halides and vinylphosphonic acid esters, followed by hydrolysis.

When the layer (Y) contains the polymer (C), the proportion of the polymer (C) in the layer (Y) is preferably 20% by mass or less from the viewpoint of achieving both flexibility, gas barrier properties, and water vapor barrier properties. , is more preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 2.5% by mass or less.

The layer (Y) may partially contain the components of the layer (Z). When the layer (Y) contains the component of the layer (Z), the affinity with the layer (Z) is improved, and the retort resistance of the multilayer structure of the present invention can be further enhanced in some cases.

Layer (Y) may further comprise other components. Such other ingredients include inorganic acid metal salts such as carbonates, hydrochlorides, nitrates, hydrogencarbonates, sulfates, hydrogensulfates, and borates; oxalates, acetates, tartrates, stearic acid Organic acid metal salts such as salts; Metal complexes such as cyclopentadienyl metal complexes (e.g., titanocene) and cyano metal complexes (e.g., Prussian blue); Layered clay compounds; Crosslinking agents; Polymers other than polymer (F) compounds; plasticizers; antioxidants; UV absorbers; flame retardants and the like. 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).

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 in the range of 0.05 μm to 4.0 μm. , 0.1 μm to 2.0 μm. By making the layer (Y) thin, it is possible to suppress the dimensional change of the multilayer structure during processing such as printing and lamination. 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.

[Layer (Z)]
Layer (Z) contains polymer (G) and hydrolyzed condensate (La) of compound (L). Compound (L) is a compound (L ¹ ) which is a silicon compound having an organic group having a glycidyl group and a characteristic hydrolyzable group, and does not have an organic group having a glycidyl group and has a characteristic hydrolyzable group. Contains compound (L ² ) which is a silicon compound. Since the layer (Z) contains the polymer (G) and the hydrolyzed condensate (La) of the compound (L), the multilayer structure of the present invention exhibits gas barrier properties and water vapor barrier properties even after bending after retort treatment. can be maintained, and it has a high interlayer adhesive strength that does not cause appearance defects such as delamination after retort processing.

[Polymer (G)]
The polymer (G) is preferably a hydrophilic polymer, preferably a water-soluble polymer (Ga) or a water-dispersible polymer (Gb), which is a water-soluble polymer (Ga). is more preferable. As used herein, the water-soluble polymer (Ga) is completely dissolved when 10 g of the polymer is mixed with 100 ml of water, stirred at 95° C. for about 1 hour, and then cooled to room temperature (25° C.). means something In addition, the water-dispersible polymer (Gb) means a polymer having a polar group that does not fall under the water-soluble polymer (Ga) and is dispersible in water with an average particle size of 1 to 1000 nm. is not particularly limited, but hydroxyl group, carboxyl group, sulfonyl group, phosphoric acid group, amino group and salts thereof are preferred. The average particle size is the average primary particle size, and is determined by a laser diffraction scattering method or electron microscope observation of particles. Specifically, the laser diffraction scattering method is convenient for measuring the particle size of particles of 100 nm or more, and the electron microscope observation is convenient for measuring the particle size of ultrafine particles of less than 100 nm. 100 nm is a value measured by a laser diffraction scattering method. The laser diffraction scattering method can be measured using a 0.2% sodium hexametaphosphate aqueous solution as a dispersion medium with a laser diffraction particle size distribution analyzer (SALD-2300: manufactured by Shimadzu Corporation).

Although the molecular weight of the polymer (G) is not particularly limited, the weight average molecular weight is preferably 5,000 or more, more preferably 8,000 or more, and even more preferably 10,000 or more. The weight average molecular weight is preferably 7,000,000 or less, more preferably 3,500,000 or less, even more preferably 1,000,000 or less, and 100,000 or less. Especially preferred. If the weight-average molecular weight is outside this range, sufficient adhesion may not be obtained.

Examples of water-soluble polymers (Ga) include water-soluble vinyl alcohol resins, water-soluble acrylic resins, water-soluble methacrylic resins, water-soluble acrylamide resins, water-soluble polyester resins, water-soluble polyethylene glycol resins, and water-soluble polyethylene. Oxide resin, water-soluble polypropylene oxide resin (polyethylene oxide-polypropylene oxide block copolymer, etc.), water-soluble vinyl-modified resin (water-soluble polyvinylpyrrolidone, etc.), water-soluble polyamide resin, water-soluble polyurethane resin, water-soluble epoxy resin, water Polyoxazoline group-containing resins, water-soluble modified styrene resins, water-soluble modified silicone resins and water-soluble polysaccharides are preferred. Water-soluble polysaccharides include starch, dextran, dextrin, pullulan, agar, locust bean gum, guar gum, tamarind seed gum, karaya gum, chitosan, gum arabic, alginic acid, sodium alginate, carrageenan, xanthan gum, curdlan, gellan gum, gelatin, Cellulose derivatives (eg, carboxymethylcellulose sodium, carboxymethylcellulose calcium, methylcellulose, hydroxypropylcellulose, hydroxyethylcellulose, etc.) and the like. Water-dispersible polymers (Gb) include water-dispersible polyester resins, water-dispersible polyamide resins, water-dispersible acrylic resins, water-dispersible vinyl alcohol resins, water-dispersible polyethylene oxide resins, and water-dispersible polypropylene oxide. Resins, water-dispersible ethylene-vinyl alcohol copolymer (EVOH) resins, water-dispersible vinyl-modified resins, water-dispersible epoxy resins, water-dispersible oxazoline group-containing resins, water-dispersible modified styrene resins, and water-dispersible modified silicones Resin etc. are mentioned suitably.

Since the water-soluble polymer (Ga) is expected to react with the glycidyl group of the compound (L ¹ ), water-soluble polyvinyl alcohol, water-soluble polyacrylic acid, water-soluble polymethacrylic acid, water-soluble polyethylene glycol resin, It preferably contains water-soluble polyethylene oxide resin, water-soluble polyvinylpyrrolidone, water-soluble polyamide, water-soluble polyurethane, etc. Water-soluble polyvinyl alcohol, water-soluble polyacrylic acid, water-soluble polymethacrylic acid, water-soluble polyvinylpyrrolidone, water-soluble polyamide , and water-soluble polyurethane, more preferably water-soluble polyvinyl alcohol or water-soluble polyamide, and particularly preferably water-soluble polyvinyl alcohol.

Examples of water-soluble polyamides include copolymerized polyamides containing 6-nylon and a hydrophilic component, and modified polyamides obtained by chemically modifying 6-nylon. Moreover, the water-soluble polyamide may contain an ester bond or a urethane bond in addition to the amide bond. Specific copolyamides include polyamides having sulfonic acid groups or sulfonate groups in side chains, polyamides containing polyether segments, and polyamides having basic nitrogen. Among the above polyamides, polyamides containing basic nitrogen and/or polyamides containing polyether segments are more preferable. A polyamide having a basic nitrogen is a polymer containing a basic nitrogen in a portion of the main chain or side chain. The basic nitrogen is an amino group (including an unsubstituted amino group, a monosubstituted amino group, a disubstituted amino group, or a 5- to 6-membered cyclic amino group, excluding a nitrogen atom that constitutes an amide group). is a nitrogen atom that Substituents possessed by the monosubstituted amino group and the disubstituted amino group include linear or branched alkyl groups having 1 to 6 carbon atoms, halogen atoms, and the like. A polyamide having a tertiary amino group in the main chain is preferable as the polyamide having a basic nitrogen. A polyamide having a basic nitrogen can be obtained by subjecting a monomer having a basic nitrogen alone or using other monomers to condensation polymerization, polyaddition reaction, or the like. The monomer components of polyamides containing basic nitrogen and/or polyamides containing polyether segments are for all polyamide constituents i.e. aminocarboxylic acid units (including in the case of lactams as raw materials), dicarboxylic acid units and It is preferably 10 mol % or more and 100 mol % or less, more preferably 20 mol % or more and 80 mol % or less, based on the sum of the diamine units, since the water solubility is high.

The degree of saponification of the water-soluble polyvinyl alcohol is preferably 60 mol% or more and 99.95 mol% or less, more preferably 70 mol% or more and 99.9 mol% or less, and even more preferably 80 mol% or more and 99.9 mol% or less. The viscosity of the water-soluble polyvinyl alcohol is preferably 1 to 150 mPa·s, more preferably 2 to 100 mPa·s, even more preferably 3 to 80 mPa·s. The degree of saponification and viscosity of water-soluble polyvinyl alcohol can be measured according to JIS K 6726:1994, and the viscosity can be measured with a B-type rotational viscometer. The water-soluble polyvinyl alcohol is acid-modified polyvinyl alcohol modified with carboxylic acid, dicarboxylic acid, sulfonic acid, etc., and modified polyvinyl alcohol containing 15 mol% or less of monomer units other than vinyl alcohol units such as ethylene. There may be.

Water-soluble polyacrylic acid has one or more carboxyl groups or one or more carboxylic anhydride groups in one polymer molecule. Specifically, it is possible to use a polymer containing one or more structural units having one or more carboxyl groups, such as acrylic acid units, methacrylic acid units, maleic acid units, itaconic acid units, etc., in one polymer molecule. can. Polymers containing structural units having a carboxylic anhydride structure such as maleic anhydride units and phthalic anhydride units can also be used. The structural unit having one or more carboxyl groups and/or the structural unit having a carboxylic anhydride structure may contain one type or two or more types. The structural unit having one or more carboxyl groups and/or the structural unit having a carboxylic anhydride structure are highly water-soluble, so the content is preferably 10 mol% or more, and preferably 40 mol% or more. It is more preferably 70 mol % or more, and may be 100 mol %.

From the viewpoint of obtaining a multilayer structure having better barrier properties and retort resistance, two water-soluble polymers (Ga) having functional groups capable of intermolecular reaction are mixed as the polymer (G). may be used. Examples of the water-soluble polymer (Ga) include a combination of water-soluble polyvinyl alcohol and water-soluble polyacrylic acid.

When two kinds of water-soluble polymers (Ga) are used, the mass of the one with the higher content in the layer (Z) is W _Ga1 and the mass of the other one is W _Ga2 , the mass ratio W _Ga1 /W _Ga2 is From the viewpoint of improving retort resistance, it is preferably 1.0 or more and 20.0 or less, more preferably 1.5 or more and 10.0 or less, and particularly preferably 3.0 or more and 7.5 or less. Polymer (G) may be used alone or in combination of two or more.

[Hydrolysis condensate (La)]
By hydrolyzing compound (L), at least part of the hydrolyzable characteristic groups of compound (L) are substituted with hydroxyl groups. Further, by condensation of the hydrolyzate, a hydrolytic condensate (La), which is a compound in which metal atoms are bonded via oxygen, is formed. Here, in order for this hydrolytic condensation to occur, it is important that the compound (L) has a hydrolyzable characteristic group (functional group). If these groups are not bonded, the hydrolytic condensation reaction does not occur or becomes extremely slow, making it difficult to obtain the effects of the present invention. Although Si may be classified as a metalloid element, in this specification, Si is described as a metal. Examples of the hydrolyzable characteristic group possessed by compound (L) include X ¹ in formula (I) and X ² in formula (II), which will be described later. The hydrolyzed condensate (La) can be produced from a specific raw material using, for example, a known sol-gel method. Raw materials include compound (L), partially hydrolyzed compound (L), completely hydrolyzed compound (L), partially hydrolyzed and condensed compound (L), compound ( L) may be completely hydrolyzed and partially condensed, or a combination thereof. These raw materials may be produced by known methods, or commercially available ones may be used. Although not particularly limited, for example, a condensate obtained by hydrolytic condensation of about 2 to 10 molecules can be used as a raw material.

Compound (L ¹ ) is a silicon compound having an organic group having a glycidyl group and a hydrolyzable characteristic group. Compound (L ¹ ) has the following general formula (I)
^SiX1pZqR1 _{( 4-pq) (} ^I )
[In formula (I) above, X ¹ is any one selected from the group consisting of F, Cl, Br, I, R ² O--, R ³ COO--, (R ⁴ CO) ₂ CH--, and NO ₃ 1, Z represents an organic group having a glycidyl group, and R ¹ , R ² , R ³ and R ⁴ each independently represents a group consisting of an alkyl group, an aralkyl group, an aryl group and an alkenyl group. represents any one group selected from the above, p represents an integer of 1 to 3, and q represents an integer of 1 to 3. 2≦(p+q)≦4. When multiple X ¹ are present, those X ¹ may be the same or different. When there are multiple Z's, those Z's may be the same or different. When multiple R ¹ are present, those R ¹ may be the same or different. ] is preferably at least one compound represented by In the present invention, the compound (L ¹ ) can strongly bind the hydrolytic condensate (La) of the compound (L) and the polymer (G) by a covalent bond. By using the compound (L ¹ ) as a part of the compound (L), the obtained multilayer structure has excellent gas barrier properties and water vapor barrier properties, and can maintain the gas barrier properties and water vapor barrier properties even after bending after retort treatment. , it has a high interlaminar adhesive strength that does not cause appearance defects such as delamination even after retorting.

R ¹ , R ² , R ³ and R ⁴ are, for example, an alkyl group having 1 to 10 carbon atoms, an aralkyl group having 7 to 110 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aryl group having 2 to 9 carbon atoms. It is an alkenyl group, preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms.

In formula (I), the glycidyl group in the "organic group having a glycidyl group" represented by Z contributes to the formation of a covalent bond with the functional group in the polymer (G). Z in formula (I) may have only one glycidyl group, but may have a plurality of glycidyl groups.

In a preferred example, X ¹ is a halogen atom or a C 1-4 alkoxy group (R ² O—), Z is a C 1-4 alkyl group having a glycidyl group, and R ¹ is a carbon an alkyl group of numbers 1 to 4, p is 2 or 3, q is 1 or 2, and 3≤(p+q)≤4. In a particularly preferred example, X ¹ is a halogen atom or a C 1-4 alkoxy group (R ² O—), Z is a C 1-4 alkyl group having a glycidyl group, and p is 3. and q is 1.

Specific examples of the compound (L ¹ ) include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltriisopropoxysilane, γ-glycidoxypropyltributoxysilane. Silanes, γ-glycidoxypropyltrichlorosilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane. Among them, γ-glycidoxypropyltrimethoxysilane and γ-glycidoxypropyltriethoxysilane are preferred as the compound (L ¹ ).

Compound (L ² ) is a silicon compound having no organic group having a glycidyl group and having a hydrolyzable characteristic group. Compound (L ² ) preferably does not have an organic group having a reactive functional group (epoxy group, isocyanate group, mercapto group, hydroxyl group, ureido group, oxazoline group, carbodiimide group, halogen atom, etc.). Compound (L ² ) has the following general formula (II)
^SiX2rR5 _{(4-r) (} ^II )
[In formula (II) above, X ² is any one selected from the group consisting of F, Cl, Br, I, R ⁶ O--, R ⁷ COO--, (R ⁸ CO) ₂ CH--, and NO ₃ R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represent any one group selected from the group consisting of an alkyl group, an aralkyl group, an aryl group and an alkenyl group; represents an integer from 1 to 4. When multiple X ² are present, those X ² may be the same or different. ^When there are multiple R5's, those R5's may be the ^same or different. ]
It is preferably at least one compound represented by. In the present invention, the retort resistance of the gas barrier layer can be improved by using the compound (L ² ) as part of the compound (L).

R ⁵ , R ⁶ , R ⁷ and R ⁸ are, for example, an alkyl group having 1 to 10 carbon atoms, an aralkyl group having 7 to 110 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aryl group having 2 to 9 carbon atoms. It is an alkenyl group, preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms.

In a preferred example, X ² is a halogen atom or a C 1-4 alkoxy group (R ⁶ O—), R ⁵ is a C 1-4 alkyl group, and r is 3 or 4. In a particularly preferred example, X ² is a halogen atom or an alkoxy group having 1 to 4 carbon atoms (R ⁶ O--) and r is 4.

Specific examples of compound (L ² ) include tetrachlorosilane, tetrabromosilane, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, octyltrimethoxysilane, phenyltrimethoxysilane, and vinyltrimethoxysilane. , vinyltriethoxysilane, chlorotrimethoxysilane, chlorotriethoxysilane, dichlorodimethoxysilane, dichlorodiethoxysilane, trichloromethoxysilane, trichloroethoxysilane, and vinyltrichlorosilane. Among them, tetramethoxysilane and tetraethoxysilane are preferred as the compound (L ² ).

The ratio ( _ML1 / _ML2 ) of the total number of moles M _L1 of silicon atoms derived from the compound (L ¹ ) and the total number of moles M _L2 of silicon atoms derived from the compound (L ² ) in the layer (Z) is 0.1/99.9 or more is preferable, 0.5/99.5 or more is more preferable, 1.0/99.0 or more is still more preferable, and 1.5/98.5 is particularly preferable. _ML1 / _ML2 is preferably 30.0/70.0 or less, more preferably 20.0/80.0 or less, still more preferably 8.0/92.0 or less, and 4.0/96.0 or less. Especially preferred. When M _L1 /M _L2 is 0.1/99.9 or more, the multilayer structure of the present invention is more excellent in retort resistance. Further, when M _L1 /M _L2 is 30.0/70.0 or less, the multilayer structure of the present invention is more excellent in barrier properties after bending after retort treatment.

As long as the effect of the present invention can be obtained, compound (L) may have a silicon compound other than compound (L ¹ ) and compound (L ² ), but the ratio thereof is preferably 20 mol % or less, and 10 mol % or less, more preferably 5 mol % or less, and even 0 mol %. That is, compound (L) may consist essentially of compound (L ¹ ) and compound (L ² ).

In the layer (Z), [total mass W _G+La of organic components derived from polymer (G) and hydrolytic condensate (La)] and [mass W of inorganic components derived from hydrolytic condensate (La) _La ], the mass ratio W _G+La /W _La is preferably in the range of 0.10 or more and 0.70 or less. When W _G+La /W _La is 0.10 or more, the coatability is improved. Excellent barrier properties even after stress. From the viewpoint of further improving coatability and retort resistance, W _{G + La} /W _La is more preferably in the range of 0.15 or more and 0.55 or less, and more preferably in the range of 0.25 or more and 0.45 or less. It is particularly preferred to have

As long as the effects of the present invention can be obtained, the layer (Z) may contain a compound other than the polymer (G) and the hydrolytic condensate (La), but the ratio thereof is preferably 20% by mass or less, and 10% by mass. It is more preferably 5% by mass or less, more preferably 5% by mass or less, and may be 0% by mass. That is, the layer (Z) may consist essentially of the polymer (G) and the hydrolyzed condensate (La).

Examples of methods for forming the layer (Z) include 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. .

The thickness of layer (Z) is preferably in the range of 0.1 to 2.0 μm, more preferably in the range of 0.2 to 1.5 μm, particularly preferably in the range of 0.3 to 1.0 μm. When the thickness of the layer (Z) is 0.1 μm or more, the barrier property after bending after retort treatment tends to be good, and when the thickness of the layer (Z) is 2.0 μm or less, the layer ( The production stability of Z) (especially prevention of cracking during drying) tends to be improved. The thickness of the layer (Z) can be measured by the method described in Examples below.

The effect of maintaining the gas barrier properties and water vapor barrier properties of the layer (Z) is greater when applied to the layer (Y) than when applied to a deposited layer of aluminum or aluminum oxide. Although the details of the reason are not clear, the layer (Y) has a larger surface roughness and gaps than the inorganic deposition layer, and the components of the layer (Z) easily penetrate into the layer (Y), or the adhesion area is large. Therefore, it is estimated that the protective effect will be more pronounced. It is presumed that the protective effect becomes more pronounced in the water vapor barrier property evaluation after bending after retort treatment.

[Inorganic deposition layer]
The multilayer structure of the present invention may further contain an inorganic deposition layer. The inorganic deposited layer may be a metal (e.g., aluminum), metal oxide (e.g., silicon oxide, aluminum oxide), metal nitride (e.g., silicon nitride), metal oxynitride (e.g., silicon oxynitride), or metal carbide. It may be formed of a nitride (for example, silicon carbonitride) or the like.

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

The thickness of the inorganic vapor deposition layer varies depending on the type of components constituting the inorganic vapor deposition layer, but is preferably 0.002 to 0.5 μm, more preferably 0.005 to 0.2 μm, and more preferably 0.01 to 0.1 μm. More preferred. The thickness may be selected within this range so that the multilayer structure has good barrier properties and mechanical properties. When the thickness of the inorganic vapor deposition layer is less than 0.002 μm, the reproducibility of the barrier properties of the inorganic vapor deposition layer against oxygen and water vapor tends to decrease, and the inorganic vapor deposition layer does not exhibit sufficient barrier properties. There is also Further, when the thickness of the inorganic deposition layer exceeds 0.5 μm, the barrier properties of the inorganic deposition layer tend to deteriorate when the multilayer structure is pulled or bent.

[Other layer (J)]
The multilayer structure of the present invention may contain other layers (J) for imparting various properties (eg, heat sealability, barrier properties, mechanical properties). Such a multilayer structure of the present invention can be produced, for example, by bonding or forming another layer (J) on the multilayer structure of the present invention directly or via an adhesive layer (I) described below. 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.

By providing the ink layer in the multilayer structure of the present invention, it is possible to print a product name, a 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. Alternatively, a film obtained by drying a resist for forming electronic circuit wiring may 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 providing the multilayer structure of the present invention with a polyolefin layer, the mechanical properties of the multilayer structure can be improved. Further, by providing the polyolefin layer as the outermost layer of the multilayer structure of the present invention, heat sealability can be imparted. 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.

[Adhesive layer (I)]
In the multilayer structure of the present invention, when laminating the substrate (X), the layer (Y), the layer (Z) and another layer (J), by providing the adhesive layer (I) between the layers, the interlayer can increase the adhesion of The adhesive layer (I) may be composed of an adhesive resin. The adhesive layer (I) composed of an adhesive resin can be formed by applying a known adhesive to the surface of each layer. The adhesive is preferably a two-liquid reaction type polyurethane adhesive in which a polyisocyanate component and a polyol component are mixed and reacted. In some cases, the adhesiveness can be further enhanced by adding a small amount of additive such as a known silane coupling agent to the adhesive. 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. The adhesive layer (I) is preferably formed between the substrate (X) and the layer (Y), and strongly bonds the substrate (X) and the layer (Y) via the adhesive layer (I). By doing so, when the multilayer structure of the present invention is subjected to processing such as printing or lamination, it is possible to more effectively suppress deterioration of the gas barrier property or appearance, and further, packaging using the multilayer structure of the present invention. The drop strength of the material 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]
A specific example of the configuration of the multilayer structure of the present invention is shown. The multilayer structures described as specific examples below may further include other members (for example, other layers (J)). Hereinafter, the structure in which the layer (Y) and the layer (Z) are laminated adjacent to each other may be referred to as a layer (YZ). As for the layer (YZ), the layer (Y) and the layer (Z) may be laminated in any order. Note that "/" described in the following specific examples means that the two layers sandwiching the "/" may be directly laminated or may be laminated via the adhesive layer (I).
(1) layer (YZ)/polyester layer,
(2) layer (YZ)/polyester layer/layer (YZ),
(3) layer (YZ)/polyamide layer,
(4) layer (YZ)/polyamide layer/layer (YZ),
(5) layer (YZ)/polyolefin layer,
(6) layer (YZ)/polyolefin layer/layer (YZ),
(7) layer (YZ) / hydroxyl group-containing polymer layer,
(8) layer (YZ)/hydroxyl group-containing polymer layer/layer (YZ),
(9) layer (YZ) / paper layer,
(10) layer (YZ)/paper layer/layer (YZ),
(11) layer (YZ)/inorganic deposition layer/polyester layer,
(12) layer (YZ)/inorganic deposition layer/polyamide layer,
(13) layer (YZ)/inorganic deposition layer/polyolefin layer,
(14) layer (YZ)/inorganic deposition layer/hydroxyl group-containing polymer layer,
(15) layer (YZ)/polyester layer/polyamide layer/polyolefin layer,
(16) layer (YZ)/polyester layer/layer (YZ)/polyamide layer/polyolefin layer,
(17) polyester layer/layer (YZ)/polyester layer/layer (YZ)/inorganic deposition layer/hydroxyl-containing polymer layer/polyolefin layer,
(18) polyester layer/layer (YZ)/polyamide layer/polyolefin layer,
(19) layer (YZ)/polyamide layer/polyester layer/polyolefin layer,
(20) layer (YZ)/polyamide layer/layer (YZ)/polyester layer/polyolefin layer,
(21) polyamide layer/layer (YZ)/polyester layer/polyolefin layer,
(22) layer (YZ)/polyolefin layer/polyamide layer/polyolefin layer,
(23) layer (YZ)/polyolefin layer/layer (YZ)/polyamide layer/polyolefin layer,
(24) polyolefin layer/layer (YZ)/polyamide layer/polyolefin layer,
(25) layer (YZ)/polyolefin layer/polyolefin layer,
(26) layer (YZ)/polyolefin layer/layer (Y)/polyolefin layer,
(27) polyolefin layer/layer (YZ)/polyolefin layer,
(28) layer (YZ) / polyester layer / polyolefin layer,
(29) layer (YZ)/polyester layer/layer (YZ)/polyolefin layer,
(30) polyester layer/layer (YZ)/polyolefin layer,
(31) layer (YZ)/polyamide layer/polyolefin layer,
(32) layer (YZ)/polyamide layer/layer (YZ)/polyolefin layer,
(33) polyamide layer/layer (YZ)/polyolefin layer,
(34) layer (YZ)/polyester layer/paper layer,
(35) layer (YZ)/polyamide layer/paper layer,
(36) layer (YZ) / polyolefin layer / paper layer,
(37) polyolefin layer/paper layer/polyolefin layer/layer (YZ)/polyester layer/polyolefin layer,
(38) polyolefin layer/paper layer/polyolefin layer/layer (YZ)/polyamide layer/polyolefin layer,
(39) polyolefin layer/paper layer/polyolefin layer/layer (YZ)/polyolefin layer,
(40) paper layer/polyolefin layer/layer (YZ)/polyester layer/polyolefin layer,
(41) polyolefin layer/paper layer/layer (YZ)/polyolefin layer,
(42) paper layer/layer (YZ)/polyester layer/polyolefin layer,
(43) paper layer/layer (YZ)/polyolefin layer,
(44) layer (YZ) / paper layer / polyolefin layer,
(45) layer (YZ) / polyester layer / paper layer / polyolefin layer,
(46) polyolefin layer/paper layer/polyolefin layer/layer (YZ)/polyolefin layer/hydroxyl-containing polymer layer,
(47) polyolefin layer/paper layer/polyolefin layer/layer (YZ)/polyolefin layer/polyamide layer,
(48) polyolefin layer/paper layer/polyolefin layer/layer (YZ)/polyolefin layer/polyester layer,
(49) inorganic deposition layer/layer (YZ)/polyester layer,
(50) inorganic vapor deposition layer/layer (YZ)/polyester layer/layer (YZ)/inorganic vapor deposition layer,
(51) inorganic deposition layer/layer (YZ)/polyamide layer,
(52) inorganic vapor deposition layer/layer (YZ)/polyamide layer/layer (YZ)/inorganic vapor deposition layer,
(53) Inorganic deposition layer/layer (YZ)/polyolefin layer,
(54) Inorganic vapor deposition layer/layer (YZ)/polyolefin layer/layer (YZ)/inorganic vapor deposition layer In the above examples, the inorganic vapor deposition layer is preferably an aluminum vapor deposition layer and/or an aluminum oxide vapor deposition layer. 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.

In the multilayer structure of the present invention, it is preferable that at least one pair of layer (Z) and layer (Y) are arranged adjacent to each other. Z) and layer (Y) are more preferably directly laminated. The multilayer structure of the present invention has the layer (Y) on the substrate (X) and the layer (Z) on the layer (Y) because it can be relatively easily manufactured by the manufacturing method described below. preferable.

When the multilayer structure of the present invention is used as a protective sheet, the layer structure of the multilayer structure of the present invention includes (1) to (8), (11) to (33), and (49) to ( 54) is preferred.

The multilayer structure of the present invention has an oxygen permeability of 2.0 mL/(m ² ·day · atm) or less under the conditions of 20°C and 85% RH after the retort treatment described in Examples below. is preferably 0.50 mL/(m ² ·day·atm) or less, more preferably 0.30 mL/(m ² ·day·atm) or less.

The multilayer structure of the present invention has a moisture permeability of 2.0 g/(m ² ·day) or less under conditions of 40° C. and 90/0% RH after the retort treatment described in Examples below. It is preferably 1.0 g/(m ² ·day) or less, more preferably 0.5 g/(m ² ·day) or less.

The multilayer structure of the present invention has an oxygen permeability of 2.0 mL/(m ² ·day · atm) or less under the conditions of 20°C and 85% RH after being bent after retort treatment described in Examples below. is preferably 1.70 mL/(m ² ·day·atm) or less, more preferably 1.60 mL/(m ² ·day·atm) or less.

The multilayer structure of the present invention has a moisture permeability of 2.5 g/(m ² ·day) or less under the conditions of 40° C. and 90/0% RH after being bent after retort treatment described later in Examples. Some are preferable, those of 1.2 g/(m ² ·day) or less are more preferable, and those of 0.95 g/(m ² ·day) or less are even more preferable.

The multilayer structure of the present invention preferably has a peel strength of 300 g/15 mm or more, more preferably 450 g/15 mm or more, still more preferably 490 g/15 mm or more, and particularly preferably 510 or more after retort treatment, which will be described later in the examples. . Here, the peel strength of the multilayer structure of the present invention can be measured according to JIS K 6854-1: 1999, and the peel strength between the layer (Y) and the layer (Z) or the layer (Z) and the adhesive layer (I) Alternatively, among the peel strengths between other layers (J) (for example, ink layers), the weaker peel strength is measured.

[Extrusion coat lamination]
The multilayer structure of the present invention can be produced, for example, by laminating the layer (Y) and the layer (Z) on the base material (X), and then adding another layer (J) directly or via an adhesive layer by an extrusion coat lamination method. You may further have a layer formed by. The extrusion coat lamination method that can be used in the present invention is not particularly limited, and known methods can be applied. 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.

By using the laminate described above, it is possible to obtain a multilayer structure that maintains high barrier performance even after extrusion coating lamination and that has a small decrease in light transmittance.

[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.

The method for producing a multilayer structure of the present invention includes, for example, a layer (Y) precursor layer forming step (I) on a substrate (X), a layer (Z) precursor layer forming step (II), a layer (Y ) Precursor layer and layer (Z) A manufacturing method including a step of heat-treating a precursor layer to form layer (Y) and layer (Z). Since the metal oxide containing aluminum (A), the inorganic phosphorus compound (B), and the mass ratio thereof have been described above, duplicate descriptions of the manufacturing method will be omitted.

[Step (I)]
In step (I), a coating liquid (S) containing a metal oxide (A) containing aluminum, an inorganic phosphorus compound (B), and a solvent is applied onto the substrate (X), and the solvent is removed to obtain Layer (Y) Precursor layer is formed. A coating liquid (S) is obtained by mixing a metal oxide containing aluminum (A), an inorganic phosphorus compound (B) and a solvent. When the multi-layer structure of the present invention further includes a vapor deposited layer of aluminum or a vapor deposited layer of aluminum oxide, these layers can be formed by the general vapor deposition method described above. Hereinafter, as a preferred embodiment, a mode using a metal oxide (A), an inorganic phosphorus compound (B), and a solvent will be described.

The coating liquid (S) can be prepared by mixing the metal oxide (A) and the inorganic phosphorus compound (B) in a solvent. Specifically, the coating liquid (S) is prepared by mixing a dispersion of the metal oxide (A) and a solution containing the inorganic phosphorus compound (B); It can be prepared by a method of adding (B) and mixing. 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 (for example, the polymer (F) and the polymer (C) having a phosphorus atom), and if necessary, acetic acid, hydrochloric acid, nitric acid, trifluoroacetic acid. , and at least one acid compound (Q) selected from the group consisting of trichloroacetic acid.

A dispersion 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 the dispersion of the metal oxide (A) is obtained by condensing or hydrolytically condensing the compound (E), the resulting dispersion may optionally be subjected to a specific treatment (treatment of the acid compound (Q) Peptization in the presence, etc.) may also 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.

A solution containing the inorganic phosphorus compound (B) can be prepared by dissolving the inorganic phosphorus compound (B) in a solvent. The solvent may be appropriately selected according to the type of the inorganic phosphorus compound (B), but it 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 (B).

The solid content concentration of the coating liquid (S) is preferably 1 to 20% by mass, more preferably 2 to 15% by mass, from the viewpoint of the storage stability of the coating liquid and the coatability to the substrate (X). ~10% by mass 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 usually 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 is more preferred, and 1.11:1.00 to 1.50:1.00 is particularly preferred. 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, for example, 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 Known methods such as a bar coating method, a chamber doctor combined coating method, a curtain coating method, and a bar coating method can be employed.

Usually, the layer (Y) precursor layer is formed by removing the solvent in the coating liquid (S) in step (I). The method for removing the solvent is not particularly limited, and known drying methods such as hot air drying, hot roll contact, infrared heating, and microwave heating can be applied. When the solvent content after drying and the average particle size of the reaction product (D) in the layer (Y) precursor layer are within the specific ranges, the obtained multilayer structure tends to have better retort resistance.

The solvent content of the layer (Y) precursor layer after drying is preferably 0.4% by mass or less, and more preferably 0.3% by mass or less from the viewpoint of exhibiting excellent barrier performance even after bending after retort treatment. When the solvent content of the layer (Y) precursor layer after the drying treatment is within the above range, the particle size of the reaction product (D) in the layer (Y) precursor layer can be reduced, and the subsequent heat treatment step (III) The average particle size of the reaction product (D) in the layer (Y) obtained in (1) is reduced, resulting in better barrier performance. The lower limit of the solvent content is not particularly limited, but from the viewpoint of production costs, it is usually preferably 0.01% by mass or more.

The average particle size of the reaction product (D) in the layer (Y) precursor layer after drying is preferably less than 5 nm, more preferably less than 4 nm, and more preferably less than 3 nm from the viewpoint of exhibiting excellent barrier performance even after bending after retorting. Less than is more preferred. Since the average particle size of the reaction product (D) in the layer (Y) precursor layer after the drying treatment is within the above range, the reaction product (D) in the layer (Y) formed through the subsequent steps is reduced. A smaller average particle size results in better barrier performance. The lower limit of the average particle size of the reaction product (D) in the layer (Y) precursor layer is not particularly limited, but may be, for example, 0.1 nm or more, or 1 nm or more.

In particular, by satisfying the solvent content and the average particle size of the reaction product (D) in the layer (Y) precursor layer, the reaction product (D) contained in the layer (Y) formed through the subsequent steps ) can be made to have an average particle size of 50 nm or less, resulting in better barrier performance.

In addition, in the infrared absorption spectrum of the layer (Y) precursor layer, the maximum absorbance AR in the range of 1,080 to 1,130 cm ^-1 and the maximum _{absorbance AP} in the range of 850 to 950 cm ^-1 is preferably _2.0 or _less , more preferably 1.4 or less. The absorbance maximum value A _R in the range of 1,080 to 1,130 cm ⁻¹ is based on the MOP bond as described above, and the absorbance maximum value A _P in the range of 850 to 950 cm ⁻¹ is M− Based on the OM bond. That is, the ratio A _R /A _P can be considered as an index representing the reaction rate of the aluminum-containing metal oxide (A) to the reaction product (D). In the present invention, the fact that the reaction of the metal oxide (A) to the reaction product (D) in the layer (Y) precursor layer after the drying process is suppressed to a certain amount or less contributes to good barrier performance. It is considered to be effective for obtaining a multilayer structure having Therefore, if the ratio A _R /A _P is greater than the above range, the resulting multilayer structure may have insufficient barrier performance.

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 80 to 180° C., but the solvent content and the average particle size of the reaction product (D) in the layer (Y) precursor layer In order to reduce the drying temperature after coating the coating liquid (S) is preferably less than 140 ° C., more preferably 60 ° C. or more and less than 140 ° C., more preferably 70 ° C. or more and less than 130 ° C., 80 ° C. or more and 120 ° C. Less than is particularly preferred. Although the drying time is not particularly limited, it 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.

[Step (II)]
In step (II), a coating liquid (T) containing a polymer (G), a hydrolytic condensate (La), and a solvent is applied onto the layer (Y) precursor layer obtained in step (I). . The coating liquid (T) is prepared, for example, by adding a solvent to compound (L ² ), then adding an acid catalyst and water, and performing hydrolytic condensation by a known sol-gel method to obtain a hydrolytic condensate of compound (L ² ). After formation, it can be prepared by adding the polymer (G) and the compound (L ¹ ). When the compound (L ¹ ) is added to a liquid containing the hydrolytic condensate of the compound (L ² ), acid and water, the hydrolytic condensation of the compound (L ¹ ) proceeds and the hydrolytic condensate (La ) is formed. As the solvent used for the coating liquid (T), alcohols such as methanol, ethanol and isopropanol; water; or mixed solvents thereof are preferable.

As the acid catalyst, known acids can be used, such as hydrochloric acid, sulfuric acid, nitric acid, p-toluenesulfonic acid, benzoic acid, acetic acid, lactic acid, butyric acid, carbonic acid, oxalic acid, maleic acid and the like. Among these, hydrochloric acid, sulfuric acid, nitric acid, acetic acid, lactic acid, and butyric acid are particularly preferred. The preferred amount of the acid catalyst to be used varies depending on the type of acid used, but is in the range of 1×10 ^-5 to 10 mol per 1 mol of the metal atom of the compound (L) used in step (I). It is preferably in the range of 1×10 ⁻⁴ to 5 mol, more preferably in the range of 5×10 ⁻⁴ to 1 mol. When the amount of the acid catalyst used is within this range, the gas barrier layer has a good fine structure and a higher gas barrier property can be obtained.

The preferred amount of water to be used varies depending on the type of compound (L ² ) used in step ( ^II ), but is It is preferably in the range of 0.05 to 10 mol, more preferably in the range of 0.1 to 5 mol, even more preferably in the range of 0.2 to 3 mol. When the amount of water used is within this range, the obtained multilayer structure has particularly excellent barrier properties. In step (II), when using a component containing water (for example, hydrochloric acid), it is preferable to determine the amount of water to be used in consideration of the amount of water introduced by the component.

Furthermore, in step (II), an organic solvent may be used as necessary. The organic solvent to be used is not particularly limited as long as it dissolves the compound (L ² ) used in step (II). For example, alcohols such as methanol, ethanol, isopropanol and normal propanol are preferably used. be done. More preferably, an alcohol having the same molecular structure (alkoxy component) as the alkoxy group of compound (L) used in step (II) is used. Specifically, methanol is preferred for tetramethoxysilane, and ethanol is preferred for tetraethoxysilane. The amount of the organic solvent used is not particularly limited, and usually the concentration of the compound (L ² ) used in step (II) is preferably 1 to 90% by mass, more preferably 10 to 80% by mass, still more preferably 10% by mass. It is an amount that is up to 60% by mass.

When hydrolytically condensing compound (L) in the reaction system of step (II), the temperature of the reaction system is not particularly limited, and is usually in the range of 2 to 100°C, preferably 4 to 60°C. and more preferably within the range of 5 to 40°C. The reaction time varies depending on the reaction conditions (amount and type of acid catalyst, etc.), but is usually in the range of 0.01 to 60 hours, preferably in the range of 0.1 to 12 hours, and more It is preferably within the range of 0.1 to 6 hours. Also, the reaction can be carried out in an atmosphere of various gases such as air, carbon dioxide, nitrogen and argon.

A layer (Z) precursor layer is formed by removing the solvent after applying the coating liquid (T). 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.

A method for removing the solvent of the coating liquid (T) is not particularly limited, 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), and more preferably lower by 15°C or more. The drying temperature after applying the coating liquid (T) may be, for example, about 90 to 240°C, preferably 100 to 200°C.

[Step (III)]
In step (III), the layer (Y) precursor layer and the layer (Z) precursor layer formed in steps (I) and (II) are heat-treated at a temperature of 140° C. or higher to form layer (Y) and layer (Z). This heat treatment temperature is preferably higher than the drying temperature after coating of the coating liquid (T).

In step (III), a reaction in which particles of the metal oxide (A) are bonded together via phosphorus atoms (phosphorus atoms derived from the inorganic phosphorus compound (B)), that is, a reaction product (D) is produced. Reaction proceeds. In addition, the hydrolytic condensation reaction of compound (L) and the reaction of hydrolytic condensate (La) (metal oxide site and glycidyl group site) and polymer (G) proceed. In order to allow the reaction to proceed sufficiently, the temperature of the heat treatment is preferably 140° C. or higher, more preferably 170° C. or higher, even more preferably 180° C. or higher, and 190° C. or higher. Especially preferred. When the heat treatment temperature is low, it takes a long time to obtain a sufficient degree of reactivity, which causes a decrease in productivity. The preferred upper limit of 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. Further, when a thermoplastic resin film made of a polyester-based 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 0.1 second to 1 hour, more preferably 1 second to 15 minutes, and even more preferably 5 to 300 seconds.

In order to reduce the solvent content and the average particle size of the reaction product (D), the heat treatment is preferably carried out in two or more stages while changing the treatment temperature. That is, 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 25° C. or higher, and particularly preferably 35° 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 30% higher than the drying temperature in step (II) because a multilayer structure having good properties can be obtained. C. or higher is preferred, 50.degree. C. or higher is more preferred, 55.degree. C. or higher is even more preferred, and 60.degree.

When the heat treatment of step (III) is performed in two or more stages, the temperature of the second heat treatment is higher than the temperature of the first heat treatment, the temperature of the first heat treatment is 140 ° C. or higher and lower than 200 ° C., and the temperature of the second heat treatment is It is preferably 180°C or higher and 270°C or lower. More preferably, the temperature of the second heat treatment is 15°C or higher than the temperature of the first heat treatment, the temperature of the first heat treatment is 140°C or higher and lower than 200°C, and the temperature of the second heat treatment is 180°C or higher and 270°C or lower. be. More preferably, the temperature of the second heat treatment is higher than the temperature of the first heat treatment by 25°C or higher, the temperature of the first heat treatment is 140°C or higher and lower than 200°C, and the temperature of the second heat treatment is 180°C or higher and 270°C or lower. be. In particular, when each heat treatment temperature is 200° C. or higher, each 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 each heat treatment temperature is lower than 200° C., each 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.

The multilayer structure of the present invention and the packaging material using the same are excellent in retort resistance. Therefore, the multilayer structure of the present invention and the packaging material using the same can be applied to various uses. In addition, the electronic device protective sheet and electronic device containing the multilayer structure of the present invention are excellent in gas barrier properties and water vapor barrier properties, and can maintain the barrier properties even after a dump heat test. can be used in

The packaging material of the present invention includes a multilayer structure comprising a substrate (X), a layer (Y) and a layer (Z). The packaging material may be composed only of the multilayer structure. That is, in the following description, "packaging material" may be read as "multilayer structure". The packaging material may be composed of the multilayer structure and other members. The packaging material of the present invention preferably has a layer formed by the extrusion coat laminate described above.

The packaging material of the present invention has barrier properties against inorganic gases (e.g., hydrogen, helium, nitrogen, oxygen, carbon dioxide), natural gas, water vapor, and organic compounds that are liquid at normal temperature and normal pressure (e.g., ethanol, gasoline vapor). have.

When the packaging material of the present invention is a packaging bag, the multilayer structure of the present invention may be used in all of the packaging bag, or the multilayer structure of the present invention may be used in part of the packaging bag. may For example, 50% to 100% of the area of the packaging bag may be composed of the multilayer structure of the present invention. 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) may be produced by joining the sheet-like or film-like multilayer structure of the present invention and molding it into a predetermined container shape. Molding methods include thermoforming, injection molding, extrusion blow molding and the like. Alternatively, the container (packaging material) may be produced by forming the layer (Y) and the layer (Z) on the substrate (X) molded into the shape of a predetermined container. A container manufactured in this manner is sometimes referred to as a "packaging container" in this specification.

The packaging material of the present invention is preferably used as a food packaging material. In addition to packaging materials for food, the packaging material of 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; .

In addition, the packaging material of the present invention can be used after secondary processing for various molded articles. Such molded products include vertical form fill seal bags, vacuum packaging bags, pouches, laminated tube containers, infusion bags, paper containers, strip tapes, lid materials for containers, in-mold label containers, and even vacuum insulators. good. These moldings may be heat-sealed.

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.

Next, the present invention will be described more specifically with reference to Examples, but the present invention is not limited to these Examples, and many modifications are commonly made in the art within the scope of the technical idea of the present invention. It is possible by those who have knowledge of Analysis and evaluation in the following examples and comparative examples were performed as follows.

Materials used in Examples and Comparative Examples are shown.
PET12: Biaxially oriented polyethylene terephthalate film; manufactured by Toray Industries, Inc., "Lumirror (trademark) P60" (trade name), thickness 12 µm
ONY15: Biaxially 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, Inc., "RXC-22" (trade name), thickness 100 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
PVA-124: polyvinyl alcohol; "Kuraray Poval (trademark) PVA-124 (also known as Kuraray Poval (trademark) 60-98)" (trade name) manufactured by Kuraray Co., Ltd.
PVA-424H: polyvinyl alcohol; "Kuraray Poval (trademark) PVA-424H" (trade name) manufactured by Kuraray Co., Ltd.
P-95: Water-soluble nylon; manufactured by Toray Industries, Inc. "P-95" (trade name)
SD30: dextrin; "Sandec #30" (trade name) manufactured by Sanwa Starch Industry Co., Ltd.
PAA25000: Water-soluble polyacrylic acid; manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. "Polyacrylic acid 25000" (trade name)

(1) Thickness Measurement of Each Layer Using a focused ion beam (FIB), the multilayer structures obtained in Examples and Comparative Examples were cut to prepare sections (0.3 μm thick) 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 each layer was calculated. The measurement conditions were as follows.
Device: JEM-2100F manufactured by JEOL Ltd.
Accelerating voltage: 200 kV
Magnification: 250,000 times

(2) Measurement of oxygen permeability of multilayer structure The samples (multilayer structures) obtained in Examples and Comparative Examples were attached to an oxygen permeation measuring device so that the base material layer faced the carrier gas side, and so on. Oxygen permeability was measured by pressure method. 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) Measurement of Moisture Permeability of Multilayer Structures The samples (multilayer 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 were 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

(4) Bending treatment The samples (multilayer structures) obtained in Examples and Comparative Examples were cut into 210 mm × 297 mm (A4 size), and according to ASTM F-392, Gelbo Flex Tester (manufactured by Rigaku Kogyo Co., Ltd. ) was subjected to 50 cycles of flexion. A central portion of the bent multilayer structure was cut out as a sample for oxygen permeability and moisture permeability measurement.

(5) Evaluation of Adhesion The peel strength of the samples (multilayer structures) obtained in Examples and Comparative Examples was measured according to JIS K 6854-1:1999. The measurement was performed 5 times and the average value was adopted. The measurement conditions were as follows.
Apparatus: Autograph AGS-H manufactured by Shimadzu Corporation
Peeling speed: 250 mm/min Temperature: 23°C Humidity: 50% RH

<Production example of coating liquid (S-1)>
230 parts by mass of distilled water was heated to 70° C. while stirring. To the distilled water, 88 parts by mass of triisopropoxyaluminum was added dropwise over 1 hour, the liquid temperature was gradually raised to 95°C, and hydrolytic condensation was carried out 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 the dispersion was stirred while the liquid temperature was maintained at 15°C. Furthermore, 18.80 parts by mass of a methanol solution was added dropwise, and stirring was continued at 15° C. until the viscosity reached 1,500 mPa·s to obtain the desired coating liquid (S-1). The molar ratio of aluminum atoms to phosphorus atoms in the coating liquid (S-1) was aluminum atom:phosphorus atom=1.15:1.00.

<Production example of coating liquid (T-3) >
A TMOS methanol solution was prepared by dissolving 7.41 parts by mass of tetramethoxysilane (TMOS) in 7.41 parts by mass of methanol. While maintaining the temperature of this TMOS methanol solution at 10°C or less, 0.49 parts by mass of distilled water and 1.22 parts by mass of 0.2N hydrochloric acid were added, and the mixture was stirred at 10°C for 30 minutes for hydrolysis and A condensation reaction was carried out. Subsequently, after diluting with 18.84 parts by mass of methanol and 46.03 parts by mass of distilled water, 17.13 parts by mass of an aqueous solution of 5% polyvinyl alcohol (“PVA-124” manufactured by Kuraray Co., Ltd.) with stirring, 1 part of methanol 0.29 parts by mass of γ-glycidoxypropyltrimethoxysilane (GPTMOS) diluted with 0.18 parts by mass was sequentially added, and after stirring at room temperature for 30 minutes, a solution (T-3) was obtained.

<Production example of coating liquids (T-1), (T-2) , (T-4) to (T-14), (CT-1) to (CT-5)>
Preparation of coating liquid (T-3) except that the type of water-soluble polymer (Ga), the type of compound (L), W _G+La /W _La and M _L1 /M _L2 were changed as shown in Table 1 Coating liquids (T-1), (T-2) , (T-4) to (T-14), and (CT-1) to (CT-5) were obtained in the same manner as above.

<Production example of coating liquid (CT-6)>
A round-bottom flask (inner volume: 50 ml) equipped with a stirrer and a thermometer was purged with nitrogen, charged with 2.5 g of water as a solvent, and stirred with 10 g of vinylphosphonic acid, 2.5 g of water and 2,2′-azobis. A mixed solution of 25 mg of (2-amidinopropane) dihydrochloride was added dropwise to the round bottom flask. From this point on, a small amount of nitrogen gas was continuously flowed throughout the entire course of the polymerization. After the round-bottom flask was immersed in an oil bath and reacted at 80° C. for 3 hours, the reaction mixture was diluted with 15 g of water and filtered through a cellulose membrane (manufactured by Spectrum Laboratories, “Spectra/Por” (trade name)). bottom. Next, the solvent of the filtrate was distilled off with an evaporator, and the residue was vacuum-dried at 50° C. for 24 hours to obtain poly(vinylphosphonic acid) as a white polymer. When the molecular weight of this polymer was measured with a gel permeation chromatograph analyzer at a polymer concentration of 0.1 wt % using a 1.2 wt % NaCl aqueous solution as a solvent, the molecular weight was about 10,000 in terms of polyethylene glycol. . The purified polymer was dissolved in a mixed solvent of water and methanol (water:methanol = 7:3 in mass ratio). -6) was obtained.

<Production example of coating liquid (CT-7)>
A mixture containing 77% by mass of the poly(vinylphosphonic acid) obtained in the above Production Example and 23% by mass of polyethylene glycol having a number average molecular weight of 20,000 (“PEG-20000” manufactured by Sanyo Chemical Industries, Ltd.) was prepared. was dissolved in a mixed solvent of water and methanol (water:methanol=7:3 in mass ratio) to obtain a coating liquid (CT-7) having a solid concentration of 1% by mass.

[Example 1]
<Example 1-1>
PET12 (base material (X-1)) was prepared as the base material (X). The coating liquid (S-1) was applied onto this substrate 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 and then heat-treated at 180° C. for 1 minute to form a precursor layer of layer (Y-1) on the substrate. Then, the coating liquid (T-1) was applied using a bar coater so that the thickness after drying was 0.3 μm, dried at 120° C. for 3 minutes, and heat-treated at 220° C. for 1 minute. Thus, a multilayer structure (1-1-1) having a structure of substrate (X-1)/layer (Y-1)/layer (Z-1) was obtained.

An adhesive layer was formed on the obtained multilayer structure (1-1-1), and ONY15 was laminated on the adhesive layer to obtain a laminate. Next, after forming an adhesive layer on ONY15 of the laminate, CPP50 was laminated on the adhesive layer, and aged by standing at 40° C. for 3 days. Thus, a multilayer structure (1-1-2) having a structure of substrate (X-1)/layer (Y-1)/layer (Z-1)/adhesive layer/ONY15/adhesive layer/CPP50 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 two-liquid type adhesive includes “A-525S” (brand name) of “Takelac” (registered trademark) manufactured by Mitsui Chemicals, Inc. and “A-50” of “Takenate” (registered trademark) manufactured by Mitsui Chemicals, Inc. (brand name) was used.

A pouch of 21 cm×29 cm was cut from the multilayer structure (1-1-2) and heat-sealed to prepare a pouch, which was filled with 800 mL of water. Subsequently, the obtained pouch was subjected to retort treatment (hot water storage type) under the following conditions.
Retort processing equipment: Flavor Ace RSC-60 manufactured by Hisaka Seisakusho Co., Ltd.
Temperature: 120°C
Time: 30 minutes Pressure: 0.15 MPaG

After cooling for 1 hour in an atmosphere of 23° C. and 50% RH after retorting, a measurement sample was cut out from the pouch, and the oxygen permeability and moisture permeability of the sample were measured by the methods (2) and (3) above. Table 2 shows the results.

After cooling for 1 hour in an atmosphere of 23° C. and 50% RH after the retort treatment, a measurement sample was cut out from the pouch and subjected to bending treatment by the method (4). The oxygen permeability and moisture permeability of the sample were measured by the methods (2) and (3) above. Table 2 shows the results.

After the retort treatment, the pouch was dried for 24 hours in an atmosphere of 23° C. and 50% RH, and then the adhesion was measured by the method (5) above. Table 2 shows the results.

<Examples 1-2 to 1-14>
Multilayer structure (1-2-1) in the same manner as in Example 1-1, except that coating liquids (T-2) to (T-14) were used instead of coating liquid (T-1). ~ (1-14-1) and multilayer structures (1-2-2) ~ (1-14-2) were produced and evaluated. Results are shown in Tables 1 and 2. In Examples 1-10 to 1-12, the mass of the polyvinyl alcohol in the layer (Z) corresponding to the larger content corresponds to W _Ga1 , and the mass of the water-soluble polyacrylic acid corresponds to W _Ga2 .

<Example 1-15>
PET12 (base material (X-15)) was prepared as the base material (X). Coating liquid (S-1) was applied onto this substrate using a bar coater so that the thickness after drying was 0.3 μm, dried at 100° C. for 5 minutes, and a layer was formed on the substrate. A precursor layer of (Y-15) was formed. Then, the coating liquid (T-3) was applied using a bar coater so that the thickness after drying was 0.3 μm, dried at 120° C. for 3 minutes, and heat-treated at 220° C. for 1 minute. Thus, a multilayer structure (1-15-1) having a structure of substrate (X-15)/layer (Y-15)/layer (Z-15) was obtained. Multilayer structure (1-1-1) was replaced with multilayer structure (1-15-1) in the same manner as for multilayer structure (1-1-2) of Example 1-1. A structure (1-15-2) was produced and evaluated. Results are shown in Tables 1 and 2.

<Comparative Example 1-1>
Multilayer structures (C1-1-1) and (C1-1-2) were produced and evaluated in the same manner as in Example 1-1 except that the coating liquid (T-1) was not used. Results are shown in Tables 1 and 2.

<Comparative Examples 1-2 to 1-5, 1-8 and 1-9>
The multilayer structure of Example 1 ( Multilayer structures (C1-2-1) to (C1-5-1), (C1-8-1) and (C1-9-1) were produced by the same method as in 1-1-1). Multilayer structures (C1-2-1) to (C1-5-1), (C1-8-1) and (C1-9-1) were used instead of the multilayer structure (1-1-1) Multilayer structures (C1-2-2) to (C1-5-2), (C1-8-2) and (C1 -9-2) was produced and evaluated. Results are shown in Tables 1 and 2.

<Comparative Example 1-6>
A multilayer structure (C1-6-1) and (C1-6-1) and ( C1-6-2) was produced and evaluated. Results are shown in Tables 1 and 2.

<Comparative Example 1-7>
A multilayer structure (C1-7-1) and (C1-7-1) and ( C1-7-2) was produced and evaluated. Results are shown in Tables 1 and 2.

[Example 2] Flat pouch <Example 2-1>
The multilayer structure (1-1-2) produced in Example 1-1 was cut into a width of 120 mm × 120 mm, 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 (2-1-1) was formed by heat sealing. The flat pouch was filled with 100 mL of water. The obtained flat pouch was subjected to retort treatment (hot water storage type) under the same conditions as in Example 1-1.

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

[Example 4] Lid material for container <Example 4-1>
A circular multilayer structure with a diameter of 100 mm was cut out from the multilayer structure (1-1-2) produced in Example 1-1, and used as a cover material for a container. In addition, a flanged container (“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 lid member was heat-sealed to the flange to obtain a lidded container (4-1-1). 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 (4-1-1) was subjected to retort treatment (hot water storage type) under the same conditions as in Example 1-1. bottom.

[Example 5] In-mold label container <Example 5-1>
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 CPP100 and the multilayer structure (1-1-1) of Example 1-1 are laminated, left to stand at 40 ° C. for 3 days for aging, CPP100 / adhesive layer / base material ( A multilayer label (5-1-1) having a structure of X-1)/layer (Y-1)/layer (Z-1)/adhesive layer/CPP100 was obtained.

The multilayer label (5-1-1) 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, melted polypropylene (“EA7A” of “Novatec” (registered trademark) manufactured by Japan Polypropylene Corporation) is injected into the cavity between the male mold part and the female mold part at 220° C., and injection molding is performed. The desired container (5-1-2) was molded. 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 (5-1-1), the joints are overlapped with the multi-layer label (5-1-1), and where the multi-layer label (5-1-1) does not cover the outside of the container I didn't. The appearance of the container (5-1-2) was good.

[Example 6] Extrusion coated laminate <Example 6-1>
After forming an adhesive layer on the layer (Z-1) on the multilayer structure (1-1-1) in Example 1-1, polyethylene resin (density: 0.917 g/cm ³ , melt flow rate: 8 g /10 min) was extrusion coated on the adhesive layer at 295 ° C. to a thickness of 20 μm, and substrate (X-1) / layer (Y-1) / layer (Z-1) / adhesion A laminate (6-1-1) having a structure of layer/polyethylene was obtained. The adhesive layer was formed by applying a two-liquid type adhesive using a bar coater to a thickness of 0.3 μm after drying 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 (6-1-1) was subjected to retort treatment (hot water storage type) under the same conditions as in Example 1-1, no delamination occurred and a good appearance was maintained.

[Example 7] Effect of filling <Example 7-1>
The flat pouch (2-1-1) prepared in Example 2-1 was filled with 500 mL of a 1.5% ethanol aqueous solution, and a retort processor (manufactured by Hisaka Seisakusho Co., Ltd., Flavor Ace RCS-60) was used. , 120° C. and 2.5 atm for 30 minutes in hot water.

<Examples 7-2 to 7-9>
Retort treatment was performed in the same manner as in Example 7-1, except that 500 mL of another filling was filled in the flat pouch (2-1-1) instead of 500 mL of the 1.5% ethanol aqueous solution. Then, a measurement sample was cut out from the flat pouch after the retort treatment, and the oxygen permeability of the sample was measured. Other fillers include 1.0% ethanol aqueous solution (Example 7-2), vinegar (Example 7-3), pH 2 citric acid aqueous solution (Example 7-4), edible oil (Example 7- 5), ketchup (Examples 7-6), soy sauce (Examples 7-7), and ginger paste (Examples 7-8) were used. In both cases, the oxygen permeability of the sample after retorting was 0.2 mL/(m2.day.atm). Furthermore, the lidded container (5-1-2) prepared in Example 5-1 was almost completely filled with orange syrup, and retort treatment was performed in the same manner as in Example 7-1 (Example 7-9). . After the retort treatment, no delamination occurred and a good appearance was maintained.

As is clear from Examples 7-1 to 7-9, the packaging material of the present invention maintained a good appearance even after being filled with various foods and subjected to retort treatment.

[Example 8] Vacuum insulator <Example 8-1>
The two-part adhesive used in Example 5-1 was coated on CPP50 so that the thickness after drying was 3 μm, and dried to form an adhesive layer. A laminate (8-1-1) was obtained by bonding this CPP and the PET layer of the multilayer structure (1-1-1) produced in Example 1-1. Subsequently, the two-liquid reaction type polyurethane adhesive was applied onto ONY so that the thickness after drying was 3 μm, and dried to form an adhesive layer. Then, by laminating this ONY and the laminate (8-1-1), CPP/adhesive layer/substrate (X-1)/layer (Y-1)/layer (Z-1)/adhesive layer /ONY, a multilayer structure (8-1-2) was obtained.

The multilayer structure (8-1-2) 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 is filled from the opening of the three-sided bag, and the three-sided bag is sealed at 20 ° C. and an internal pressure of 10 Pa using a vacuum packaging machine, and a vacuum insulator (8-1- 3) was obtained. Silica fine powder was used for the heat-insulating core material. After leaving the vacuum insulator (8-1-3) under the conditions of 40° C. and 15% RH for 360 days, the internal pressure of the vacuum insulator was measured using a Pirani vacuum gauge and found to be 37.0 Pa. rice field.

[Example 9] Protective sheet <Example 9-1>
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 multilayer structure (1-1-1) of the laminate, PET50 is laminated to obtain PET/adhesive layer/substrate (X-1)/layer (Y-1). )/layer (Z-1)/adhesive layer/acrylic resin film to obtain a protective sheet (9-1-1). 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 (9-1-1), 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), the protective sheet (9-1-1) maintained a good appearance without delamination.

INDUSTRIAL APPLICABILITY The present invention can be used for multilayer structures, packaging materials using the same, and methods for manufacturing multilayer structures. According to the present invention, the gas barrier property and the water vapor barrier property are excellent, and the gas barrier property and the water vapor barrier property can be maintained even after physical stress such as bending. ) can be obtained. Also, by using the multilayer structure of the present invention, excellent packaging materials and electronic devices can be obtained.

Claims (16)

A multilayer structure comprising a substrate (X), a layer (Y), and a layer (Z),
The layer (Y) contains a reaction product (D) of a metal oxide containing aluminum (A) and an inorganic phosphorus compound (B),
The layer (Z) contains a polymer (G) and a hydrolytic condensate (La) of a compound (L) having a hydrolyzable characteristic group,
Compound (L) includes compound (L ¹ ) and compound (L ² ),
Compound (L ¹ ) is a silicon compound having an organic group having a glycidyl group and a hydrolyzable characteristic group,
Compound (L ² ) is a silicon compound having no organic group having a glycidyl group and having a hydrolyzable characteristic group,
Mass ratio W of [total mass W _G+La of organic components derived from polymer (G) and hydrolytic condensate (La)] to [mass W _La of inorganic components derived from hydrolytic condensate (La)] _{G + La} /W _La is 0.10 or more and 0.70 or less,
A multilayer structure, wherein the inorganic phosphorus compound (B) is at least one compound selected from the group consisting of phosphoric acid, polyphosphoric acid, phosphorous acid, phosphonic acid and derivatives thereof. Compound (L ¹ ) has the following general formula (I)
^SiX1pZqR1 _{( 4-pq) (} ^I )
[In formula (I) above, X ¹ is any one selected from the group consisting of F, Cl, Br, I, R ² O--, R ³ COO--, (R ⁴ CO) ₂ CH--, and NO ₃ 1, Z represents an organic group having a glycidyl group, and R ¹ , R ² , R ³ and R ⁴ each independently represents a group consisting of an alkyl group, an aralkyl group, an aryl group and an alkenyl group. represents any one group selected from the above, p represents an integer of 1 to 3, and q represents an integer of 1 to 3. 2≦(p+q)≦4. When multiple X ¹ are present, those X ¹ may be the same or different. When there are multiple Z's, those Z's may be the same or different. When multiple R ¹ are present, those R ¹ may be the same or different. ]
is at least one compound represented by
Compound (L ² ) has the following general formula (II)
^SiX2rR5 _{(4-r) (} ^II )
[In formula (II) above, X ² is any one selected from the group consisting of F, Cl, Br, I, R ⁶ O--, R ⁷ COO--, (R ⁸ CO) ₂ CH--, and NO ₃ R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represent any one group selected from the group consisting of an alkyl group, an aralkyl group, an aryl group and an alkenyl group; represents an integer from 1 to 4. When multiple X ² are present, those X ² may be the same or different. ^When there are multiple R5's, those R5's may be the ^same or different. ]
2. The multilayer structure according to claim 1, which is at least one compound represented by: 3. A multilayer structure according to claim 1 or 2, wherein the polymer (G) is a water-soluble polymer (Ga). The water-soluble polymer (Ga) is at least one polymer selected from the group consisting of water-soluble polyvinyl alcohol, water-soluble polyacrylic acid, water-soluble polymethacrylic acid, water-soluble polyvinylpyrrolidone, water-soluble polyamide, and water-soluble polyurethane. 4. The multilayer structure of claim 3, which is a molecule. The multilayer structure according to claim 3 or 4, wherein the water-soluble polymer (Ga) contains at least water-soluble polyvinyl alcohol or water-soluble polyamide. A multilayer structure according to any one of claims 3 to 5, wherein the water-soluble polymer (Ga) comprises water-soluble polyvinyl alcohol and water-soluble polyacrylic acid. Multilayer structure according to any one of the preceding claims, wherein at least one pair of layer (Z) and layer (Y) are arranged adjacent to each other. The multilayer structure according to any one of claims 1 to 7, wherein the substrate (X) comprises at least one layer selected from the group consisting of thermoplastic resin films and paper. In the layer (Z), the [total mass W of the organic components derived from the polymer (G) and the hydrolytic condensate (La) _G+La ] and [mass W of the inorganic component derived from the hydrolytic condensate (La) _La ] mass ratio W _G+La /W _La is in the range of 0.25 or more and 0.45 or less. A layer (Y ) Step (I) of forming a precursor layer;
A coating liquid (T) containing a polymer (G), a hydrolytic condensate (La) of a compound (L) having a hydrolyzable characteristic group, and a solvent is applied onto the layer (Y) precursor layer. step (II) of forming a layer (Z) precursor layer by processing and removing the solvent;
heat treating the layer (Y) precursor layer and the layer (Z) precursor layer to form layer (Y) and layer ( Z ). A method for manufacturing the described multilayer structure. A packaging material comprising the multilayer structure according to any one of claims 1-9 . The packaging material according to claim 11, which is a vertical form-fill-seal bag, a vacuum packaging bag, a pouch, a laminated tube container, an infusion bag, a paper container, a strip tape, a lid material for a container, or an in-mold label container. 13. A vacuum insulator, wherein the packaging material according to claim 12 is a vacuum packaging bag, the vacuum packaging bag contains a content, the content is a core material, and the inside of the vacuum packaging bag is decompressed. A protective sheet for an electronic device, comprising the multilayer structure according to any one of claims 1 to 9 . 15. The electronic device protective sheet according to claim 14, 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 14 or 15.