JP6899733B2 - Multi-layer structure and its manufacturing method, packaging materials and products using it, and protective sheet for electronic devices - Google Patents

Description

The present invention relates to a multilayer structure and a method for producing the same, packaging materials and products using the same, and a protective sheet for an electronic device.

A multi-layer structure in which a gas barrier layer containing aluminum or aluminum oxide is formed on a plastic film has been well known in the past, and for example, a packaging material for protecting an article (for example, food) that is easily denatured by oxygen. It is used as a component of a protective sheet for electronic devices that require gas barrier properties and water vapor barrier properties. Most of the gas barrier layers are formed on the plastic film by a dry process such as physical vapor deposition (PVD) or chemical vapor deposition (CVD).

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 1 describes, 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 a composite structure having a gas barrier layer containing aluminum. As one of the methods for forming the gas barrier layer, a method of applying a coating liquid containing aluminum oxide particles and a phosphorus compound on a plastic film, and then drying and heat-treating is described.

On the other hand, Patent Document 2 describes that by providing an anchor coat layer between the base material layer and the thin-film deposition layer, deterioration of the barrier property after storage under high temperature and high humidity is suppressed.

International Publication 2011/122030 Japanese Unexamined Patent Publication No. 2013-199066

However, when the multilayer structure described in Patent Documents 1 and 2 is used as a packaging material, the temperature is 120 ° C. in a state where the packaging material is physically stressed, such as a state in which the contents are aerated or a state in which the packaging material is bent. When the retort treatment is performed under conditions exceeding (for example, 125 ° C.) (hereinafter, may be referred to as “harsh conditions”), the layers between the base material and the gas barrier layer may be peeled off, resulting in poor appearance.

Therefore, there is a demand for a gas barrier multilayer structure having good properties even after retort treatment under harsh conditions.

An object of the present invention is to have excellent gas barrier property and water vapor barrier property, maintain the barrier property even after retort treatment under harsh conditions, and have high interlayer adhesive strength (peeling strength) that does not cause appearance defects such as delamination. It is an object of the present invention to provide a novel multilayer structure having the above, packaging materials and products using the same. One of the other objects of the present invention is to provide a protective sheet for an electronic device using a novel multilayer structure which is excellent in gas barrier property and water vapor barrier property and can maintain the barrier property even after a dump heat test. There is.

According to the present invention, the above object is
[1] The layer (Z) includes a base material (X), a layer (Z) laminated on the base material (X), and a layer (Y) laminated on the layer (Z). However, a compound (BH) in which a phosphorus atom having at least one hydroxyl group and a polar group are bonded by an alkylene chain having 20 or less carbon atoms or a polyoxyalkylene chain, and the layer (Y) contains aluminum ( A multilayer structure in which the compound (A) containing aluminum containing A) contains a compound (Ab) containing a reaction product (D) of a metal oxide containing aluminum (Aa) and an inorganic phosphorus compound (BI). body;
[2] The multilayer structure of [1] in which the polar group of the phosphorus compound (BH) is a carboxyl group or a hydroxyl group;
[3] A group in which a phosphorus atom having at least one hydroxyl group of the phosphorus compound (BH) is composed of a phosphoric acid group, a phosphorous acid group, a phosphonic acid group, a phosphonic acid group, a phosphinic acid group, and a phosphinic acid group. A multilayer structure of [1] or [2], which is at least one functional group selected from the above;
[4] The multilayer structure according to any one of [1] to [3], which ^{has an oxygen permeability of 2.0 mL / (m 2} · day · atm) or less under the conditions of 20 ° C. and 85% RH;
[5] The multilayer structure according to any one of [1] to [4], which ^{has a moisture permeability of 2.0 g / (m 2} · day) or less under the conditions of 40 ° C. and 90/0% RH;
[6] The multilayer structure according to any one of [1] to [5], wherein the base material (X) contains at least one layer selected from the group consisting of a thermoplastic resin film and paper;
[7] The method for producing a multilayer structure according to [1], wherein a phosphorus atom and a polar group having at least one hydroxyl group are formed on the base material (X) by an alkylene chain having 20 or less carbon atoms or a polyoxyalkylene chain. A step (I) of forming a layer (Z) by applying a coating liquid (R) containing a bonded phosphorus compound (BH) and a solvent, a compound (A) containing aluminum, and an inorganic phosphorus compound. A step (II) of forming a layer (Y) precursor by applying a coating liquid (S) containing (BI) and a solvent onto the layer (Z), and a heat treatment of the layer (Y) precursor. A production method comprising the step (III) of forming a layer (Y) by the above-mentioned.
[8] A packaging material containing the multilayer structure according to any one of [1] to [6];
[9] The packaging material of [8] further having a layer formed by the extruded coat laminate;
[10] A vertical bag filling 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, [8] or [9]. Packaging material;
[11] A product in which at least a part of the packaging material according to any one of [8] to [10] is used;
[12] The product of [11], wherein the product contains a content, the content is a core material, the inside of the product is depressurized, and the product functions as a vacuum insulator;
[13] A protective sheet for an electronic device containing the multilayer structure according to any one of [1] to [6];
[14] A protective sheet for an electronic device according to [13], which is a protective sheet for protecting the surface of a photoelectric conversion device, an information display device, or a lighting device;
[15] An electronic device having the protective sheet according to [13] or [14];
Is achieved by providing.

According to the present invention, a novel multilayer structure having excellent gas barrier properties and water vapor barrier properties and excellent retort resistance under harsh conditions can be obtained. That is, according to the present invention, not only the gas barrier property and the water vapor barrier property are excellent, but also the excellent gas barrier property and the water vapor barrier property can be maintained even after the retort treatment under harsh conditions, and appearance defects such as delamination occur. A novel multilayer structure having no high interlayer adhesive strength (peeling strength), and packaging materials and products using the same can be obtained. In addition, a protective sheet for an electronic device using a novel multilayer structure having excellent gas barrier properties and water vapor barrier properties and capable of maintaining the barrier properties even after a dump heat test can be obtained.

The rear view which shows one form of the vertical bag filling seal bag which is an example of the product of this invention. The perspective view which shows one form of the flat pouch which is an example of the product of this invention. The front view which shows one form of the blood transfusion bag which is an example of the product of this invention. The schematic diagram which shows one form of the in-mold label container which is an example of the product of this invention. The perspective view which shows a part of the extrusion coat laminating apparatus used for manufacturing the multilayer structure which concerns on one Embodiment of this invention typically. The schematic diagram which shows an example of the vacuum insulation body which is an example of the product of this invention. The schematic diagram which shows another example of the vacuum insulation body which is an example of the product of this invention. A partial cross-sectional view of an electronic device which is an example of the product of the present invention.

The present invention will be described below with an example. In the following description, substances, conditions, methods, numerical ranges, etc. may be exemplified, but the present invention is not limited to such examples. Further, unless otherwise specified, the exemplified substances may be used alone or in combination of two or more.

Unless otherwise noted, in the present specification, the meaning of "laminating a specific layer on a specific member (base material, layer, etc.)" means that the specific layer is brought into contact with the member. In addition to the case of laminating, the case of laminating the specific layer on the member with another layer sandwiched between them is included. The same applies to the descriptions of "forming a specific layer on a specific member (base material, layer, etc.)" and "arranging a specific layer on a specific member (base material, layer, etc.)". Further, unless otherwise specified, the meaning of "coating a liquid (coating liquid, etc.) on a specific member (base material, layer, etc.)" means that the liquid is directly applied to the member. In addition, the case where the liquid is applied to another layer formed on the member is included.

In this specification, a reference numeral (Y) may be added to distinguish the layer (Y) from other layers, such as “layer (Y)”. Unless otherwise noted, sign (Y) has no technical meaning. The same applies to the base material (X), the compound (A) and other codes. However, this excludes cases where it is clear that a specific element is exhibited, such as a hydrogen atom (H).

[Multi-layer structure]
The multilayer structure of the present invention includes a base material (X), a layer (Z) laminated on the base material (X), and a layer (Y) laminated on the layer (Z). The layer (Y) contains a compound (A) containing aluminum (hereinafter, also simply referred to as “compound (A)”). Further, the compound (A) is a reaction product (D) (hereinafter, hereinafter, a reaction product (D)) of a metal oxide (Aa) containing aluminum (hereinafter, also simply referred to as “metal oxide (Aa)”) and an inorganic phosphorus compound (BI). It includes a compound (Ab) containing (hereinafter, also simply referred to as “reaction product (D)”) (hereinafter, also simply referred to as “compound (Ab)”). The layer (Z) is a phosphorus compound (BH) in which a polar group is bonded to a phosphorus atom having at least one hydroxyl group by an alkylene chain or a polyoxyalkylene chain having 20 or less carbon atoms (hereinafter, simply "phosphorus compound (BH)). ”). In the following description, unless otherwise noted, the term "multilayer structure" means a multi-layer structure including a substrate (X), a layer (Y) and a layer (Z).

[Base material (X)]
The material of the base material (X) is not particularly limited, and a base material made of various materials can be used. Examples of the material of the base material (X) include resins such as thermoplastic resins and thermosetting resins; fiber aggregates such as cloth and paper; wood; glass and the like. Among them, a thermoplastic resin and a fiber aggregate are preferable, and a thermoplastic resin is more preferable. The form of the base material (X) is not particularly limited, and may be a layer such as a film or a sheet. The base material (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 even more preferably a thermoplastic resin film.

Examples of the thermoplastic resin used for the base material (X) include polyolefin resins such as polyethylene and polypropylene; polyethylene terephthalate (PET), polyethylene-2,6-naphthalate, polybutylene terephthalate, and copolymers thereof. Polyester resin; Polyamide resin such as nylon-6, nylon-66, nylon-12; hydroxyl group-containing polymer such as polyvinyl alcohol, ethylene-vinyl alcohol copolymer; polystyrene; poly (meth) acrylic acid ester; polyacrylonitrile; Examples thereof include polyvinyl acetate; polycarbonate; polyarylate; regenerated cellulose; polyimide; polyetherimide; polysulphon; polyethersulphon; polyether ether ketone; ionomer resin and the like. When the multilayer structure is used as a packaging material, the material of the base material (X) is preferably at least one thermoplastic resin selected from the group consisting of polyethylene, polypropylene, polyethylene terephthalate, nylon-6, and nylon-66.

The surface of the base material (X) preferably has a functional group capable of reacting with the polar group of the phosphorus compound (BH) described later. Such a base material (X) can be prepared by selecting the material of the base material (X) or performing a surface treatment such as a hydrophilic treatment on the base material (X).

Examples of the method for surface treatment of the base material (X) include UV ozone treatment, high-concentration ozone water treatment, excimer ozone treatment, corona treatment, oxygen plasma treatment, AP plasma treatment, and the like, which are easy to carry out industrially. From the viewpoint of sex, corona treatment is preferable.

When the film made of the thermoplastic resin is used as the base material (X), the base material (X) may be a stretched film or a non-stretched film. A stretched film, particularly a biaxially stretched film, is preferable because the obtained multilayer structure is excellent in processability (printing, laminating, etc.). 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 the paper used for the base material (X) include kraft paper, high-quality paper, imitation paper, glassin paper, parchment paper, synthetic paper, white paperboard, Manila balls, milk carton base paper, cup base paper, and ivory paper. Be done. When paper is used as the base material (X), a multilayer structure for a paper container can be obtained.

When the base material (X) is layered, the thickness thereof is preferably 1 to 1,000 μm, more preferably 5 to 500 μm, and 9 to 5 from the viewpoint of improving the mechanical strength and workability of the obtained multilayer structure. ~ 200 μm is more preferable.

[Layer (Z)]
The layer (Z) contains a phosphorus compound (BH) in which a phosphorus atom having at least one hydroxyl group and a polar group are bonded by an alkylene chain having 20 or less carbon atoms or a polyoxyalkylene chain. The layer (Z) may contain other components such as additives as long as the action of the present invention is not impaired. The phosphorus compound (BH) will be described below.

[Phosphorus compound (BH)]
The multilayer structure of the present invention contains a phosphorus compound (BH) in the layer (Z). The phosphorus compound (BH) has a polar group bonded to a phosphorus atom having at least one hydroxyl group via an alkylene chain or a polyoxyalkylene chain having 20 or less carbon atoms. Since the phosphorus compound (BH) has both a polar group having a high affinity for the base material (X) and a phosphorus atom having at least one hydroxyl group capable of reacting with the component contained in the layer (Y), the base material (BH) has a base material. From the viewpoint of improving the adhesion between the (X) and the layer (Z) and the layer (Z) and the layer (Y) and maintaining the interlayer adhesive force even after the retort treatment, it is possible to suppress appearance defects such as delamination. It will be possible. When the surface of the base material (X) has a functional group capable of reacting with the polar group, the reaction proceeds between the base material (X) and the phosphorus compound (BH), and the interlayer adhesion can be further enhanced. ..

The phosphorus compound (BH) is, for example, the following general formula [I].
U ¹ −R ⁵ −U ² [I]
(In the formula, U ¹ represents a phosphorus atom-containing group having at least one hydroxyl group, R ⁵ represents a linear or branched alkylene group or polyoxyalkylene group having 1 to 20 carbon atoms, and U ² is polar. Represents a group.)
Indicated by. ^{The linear or branched alkylene group or polyoxyalkylene group of R 5} of the general formula [I] has a carbon number of carbon atoms from the viewpoint of improving the solubility in the solvent used in the coating liquid (R) described later. It is preferably 20 or less, more preferably 18 or less, and even more preferably 14 or less.

Examples of a phosphorus atom-containing group having at least one hydroxyl group represented by U ^{1 (U 1} of the general formula [I]) include a phosphoric acid group, a phosphorous acid group, a phosphonic acid group, a phosphonic acid group, and a phosphinic acid. Examples thereof include a group and a phosphinic acid group. Among them, a phosphoric acid group and a phosphonic acid group are preferable, and a phosphonic acid group is more preferable. The ^{polar group represented by U 2} can react with other adjacent members such as an ink layer and an adhesive layer (I). Examples of such a polar group include a hydroxyl group, a carboxyl group, an amino group and the like. Among them, a hydroxyl group and a carboxyl group are preferable, and a hydroxyl group is particularly preferable.

Specific examples of the phosphorus compound (BH) include 3-hydroxypropylphosphonic acid, 4-hydroxybutylphosphonic acid, 5-hydroxypentylphosphonic acid, 6-hydroxyhexylphosphonic acid, 7-hydroxyheptylphosphonic acid, and 8-hydroxyoctyl. Phosphonate, 9-hydroxynonylphosphonic acid, 10-hydroxydecylphosphonic acid, 11-hydroxyundecylphosphonic acid, 12-hydroxydodecylphosphonic acid, 13-hydroxytridecylphosphonic acid, 14-hydroxytetradecylphosphonic acid, 15- Hydroxypentadecylphosphonic acid, 16-hydroxyhexadecylphosphonic acid, 17-hydroxyheptadecylphosphonic acid, 18-hydroxyoctadecylphosphonic acid, 19-hydroxynonadesylphosphonic acid, 20-hydroxyicosylphosphonic acid, 3-hydroxypropyldi Hydrogen phosphate, 4-hydroxybutyl dihydrogen phosphate, 5-hydroxypentyl dihydrogen phosphate, 6-hydroxyhexyl dihydrogen phosphate, 7-hydroxyheptyl dihydrogen phosphate, 8-hydroxyoctyl dihydrogen phosphate, 9 -Hydroxynonyldihydrogen phosphate, 10-hydroxydecyldihydrogen phosphate, 11-hydroxyundecyldihydrogen phosphate, 12-hydroxydodecyldihydrogen phosphate, 13-hydroxytridecyldihydrogen phosphate, 14-hydroxytetra Decyldihydrogen phosphate, 15-hydroxypentadecyldihydrogen phosphate, 16-hydroxyhexadecyldihydrogen phosphate, 17-hydroxyheptadecyldihydrogen phosphate, 18-hydroxyoctadecyldihydrogen phosphate, 19-hydroxynonadecil Dihydrogen phosphate, 20-hydroxyicosyl dihydrogen phosphate, 3-carboxypropyl phosphonic acid, 4-carboxybutyl phosphonic acid, 5-carboxypentyl phosphonic acid, 6-carboxyhexyl phosphonic acid, 7-carboxyhepcil phosphonic acid , 8-carboxyoctylphosphonic acid, 9-carboxynonylphosphonic acid, 10-carboxydecylphosphonic acid, 11-carboxyundecylphosphonic acid, 12-carboxydodecylphoate Shonic acid, 13-carboxydotridecylphosphonic acid, 14-carboxytetradecylphosphonic acid, 15-carboxypentadecylphosphonic acid, 16-carboxyhexadecylphosphonic acid, 17-carboxyheptadecylphosphonic acid, 18-carboxyoctadecylphosphonic acid , 19-carboxynonadesylphosphonic acid, 20-carboxyicosylphosphonic acid and the like. These may be used alone or in combination of two or more phosphorus compounds (BH).

As a method for forming the layer (Z), for example, a well-known printing method such as an offset printing method, a gravure printing method, or a silk screen printing method; a well-known coating method such as a roll coat, a knife edge coat, or a gravure coat may be used. it can. It is also possible to store it in an aging room or the like at room temperature or higher for several days in order to promote the reaction.

The thickness of the layer (Z) is preferably in the range of 0.001 to 0.2 μm, more preferably in the range of 0.003 to 0.1 μm from the viewpoint of improving adhesion, and particularly preferably in the range of 0.005 to 0.05 μm. preferable. The thickness of the layer (Z) can be measured by the method described in Examples described later.

[Layer (Y)]
The layer (Y) contains an aluminum-containing compound (A), and the compound (A) is a compound (D) containing a reaction product (D) of an aluminum-containing metal oxide (Aa) and an inorganic phosphorus compound (BI). Ab) is included. The compound (A) and the inorganic phosphorus compound (BI) will be described below.

[Aluminum-containing compound (A)]
Compound (A) includes at least compound (Ab). In addition, it may contain a metal oxide (Aa) containing aluminum, a compound (Ac) which is an aluminum vapor deposition layer, or a compound (Ad) which is an aluminum oxide vapor deposition layer. Metal oxides (Aa), including aluminum, usually react with inorganic phosphorus compounds (BI) in the form of particles.

[Metal oxide containing aluminum (Aa)]
The metal atom constituting the metal oxide (Aa) containing aluminum (these may be collectively referred to as "metal atom (M)") is at least one selected from the metal atoms belonging to groups 2 to 14 of the periodic table. A species of metal atom, including at least aluminum. The metal atom (M) may be aluminum alone, or may contain aluminum and other metal atoms. As the metal oxide (Aa), two or more kinds of metal oxides (Aa) may be used in combination.

The ratio of aluminum to the metal atom (M) is preferably 50 mol% or more, more preferably 60 to 100 mol%, still more preferably 80 to 100 mol%. Examples of the metal oxide (Aa) include a metal oxide produced by a method such as a liquid phase synthesis method, a gas phase synthesis method, or a solid pulverization method.

The metal oxide (Aa) may be a hydrolyzed condensate of the compound (E) containing a metal atom (M) to which a hydrolyzable characteristic group is bonded. ^{Examples of the characteristic group include R 1 of} the general formula [II] described later. The hydrolyzed condensate of compound (E) can be considered substantially as a metal oxide (Aa). Therefore, in the present specification, the hydrolyzed condensate of compound (E) may be referred to as "metal oxide (Aa)". That is, in the present specification, "metal oxide (Aa)" can be read as "hydrolyzed condensate of compound (E)", and "hydrolyzed condensate of compound (E)" can be read as "metal oxidation". It can also be read as "thing (Aa)".

[Compound (E) containing a metal atom (M) to which a hydrolyzable characteristic group is bonded]
Since the reaction with the inorganic phosphorus compound (BI) can be easily controlled and the obtained multilayer structure has excellent gas barrier properties, the compound (E) is a compound (Ea) represented by the following general formula [II]. It is preferable to contain at least one kind.
Al (R ¹ ) _k (R ² ) _3-k [II]
In the formula, R ¹ has a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), NO ₃ , an alkoxy group having 1 to 9 carbon atoms which may have a substituent, and a substituent. An aryloxy group having 5 to 9 carbon atoms, an asyloxy group having 2 to 9 carbon atoms which may have a substituent, an alkenyloxy group having 3 to 9 carbon atoms which may have a substituent, and the like. It represents a β-diketonato group having 5 to 15 carbon atoms which may have a substituent or a diacylmethyl group having an acyl group having 1 to 9 carbon atoms which may have a substituent. R ² may have an alkyl group having 1 to 9 carbon atoms which may have a substituent, an aralkyl group having 7 to 10 carbon atoms which may have a substituent, and a carbon which may have a substituent. It represents an alkenyl group of number 2-9 or an aryl group having 6 to 10 carbon atoms which may have a substituent. k represents an integer of 1-3. When there are a plurality of ^{R 1 , R 1} may be the same as or different from each other. When there are a plurality of ^{R 2 , R 2} may be the same as or different from each other.

The compound (E) may contain at least one compound (Eb) represented by the following general formula [III] in addition to the compound (Ea).
M ¹ (R ³ ) _m (R ⁴ ) _nm [III]
In the formula, M ¹ represents at least one metal atom other than the aluminum atom and selected from the metal atoms belonging to groups 2 to 14 of the periodic table. R ³ may have a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), NO ₃ , an alkoxy group having 1 to 9 carbon atoms which may have a substituent, and a substituent. An aryloxy group having 5 to 9 carbon atoms, an asyloxy group having 2 to 9 carbon atoms which may have a substituent, an alkenyloxy group having 3 to 9 carbon atoms which may have a substituent, and a substituent. It represents a β-diketonato group having 5 to 15 carbon atoms which may have a substituent, or a diacylmethyl group having an acyl group having 1 to 9 carbon atoms which may have a substituent. R ⁴ has an alkyl group having 1 to 9 carbon atoms which may have a substituent, an aralkyl group having 7 to 10 carbon atoms which may have a substituent, and a carbon which may have a substituent. It represents an alkenyl group of number 2-9 or an aryl group having 6 to 10 carbon atoms which may have a substituent. m represents an integer of 1 to n. n is equal to the valence of ^{M 1.} If R ³ there are a plurality, R ³ may be different may be identical or different. If R ⁴ there are a plurality, R ⁴ may be different may be identical or different.

Examples of the alkoxy group represented by R ¹ and R ³ include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, and a benzyloxy group. Examples thereof include a diphenylmethoxy group, a trityloxy group, a 4-methoxybenzyloxy group, a methoxymethoxy group, a 1-ethoxyethoxy group, a benzyloxymethoxy group, a 2-trimethylsilylethoxy group and a 2-trimethylsilylethoxymethoxy group.

Examples of the aryloxy group represented by R ¹ and R ³ include a phenoxy group and a 4-methoxyphenoxy group.

Examples of the asyloxy group represented by R ¹ and R ³ include acetoxy group, ethylcarbonyloxy group, n-propylcarbonyloxy group, isopropylcarbonyloxy group, n-butylcarbonyloxy group, isobutylcarbonyloxy group and sec-butylcarbonyl. Examples thereof include an oxy group, a tert-butylcarbonyloxy group and an n-octylcarbonyloxy group.

Examples of the alkenyloxy group represented by R ¹ and R ³ include an allyloxy group, a 2-propenyloxy group, a 2-butenyloxy group, a 1-methyl-2-propenyloxy group, a 3-butenyloxy group, and a 2-methyl-2-. Propenyloxy group, 2-pentenyloxy group, 3-pentenyloxy group, 4-pentenyloxy group, 1-methyl-3-butenyloxy group, 1,2-dimethyl-2-propenyloxy group, 1,1-dimethyl-2 -Propenyloxy group, 2-methyl-2-butenyloxy group, 3-methyl-2-butenyloxy group, 2-methyl-3-butenyloxy group, 3-methyl-3-butenyloxy group, 1-vinyl-2-propenyloxy group , 5-Hexenyloxy group and the like.

Examples of the β-diketonato group represented by R ¹ and R ³ include 2,4-pentanedionato group, 1,1,1-trifluoro-2,4-pentanedionato group, 1,1,1,5. , 5,5-Hexafluoro-2,4-pentandionato group, 2,2,6,6-tetramethyl-3,5-heptandionat group, 1,3-butandionato group, 2-methyl-1,3- Examples thereof include a butandionato group, a 2-methyl-1,3-butandionato group, a benzoylacetonato group and the like.

Examples of the acyl group of the diacylmethyl group represented by R ¹ and R ³ include carbons such as formyl group, acetyl group, propionyl group (propanoyl group), butyryl group (butanoyl group), valeryl group (pentanoyl group) and hexanoyl group. The number 1 to 6 aliphatic acyl groups; aromatic acyl groups (aroyl groups) such as benzoyl groups and toluoil groups can be mentioned.

Examples of the alkyl group represented by R ² and R ⁴ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, and an isopentyl. Examples thereof include a group, an n-hexyl group, an isohexyl group, a 3-methylpentyl group, a 2-methylpentyl group, a 1,2-dimethylbutyl group, a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group.

Examples of the aralkyl group represented by R ² and R ⁴ include a benzyl group and a phenylethyl group (phenethyl group).

Examples of the alkenyl group represented by R ² and R ⁴ include a vinyl group, a 1-propenyl group, a 2-propenyl group, an isopropenyl group, a 3-butenyl group, a 2-butenyl group, a 1-butenyl group and a 1-methyl-. 2-propenyl group, 1-methyl-1-propenyl group, 1-ethyl-1-ethenyl group, 2-methyl-2-propenyl group, 2-methyl-1-propenyl group, 3-methyl-2-butenyl group, 4-Pentenyl group and the like can be mentioned.

Examples of the aryl group represented by R ² and R ⁴ include a phenyl group, a 1-naphthyl group, a 2-naphthyl group and the like.

Substituents that each group represented by R ¹ , R ² , R ³ , and R ⁴ may have include, for example, an alkyl group having 1 to 6 carbon atoms; a methoxy group, an ethoxy group, an n-propoxy group, and the like. 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 An alkoxy group having 1 to 6 carbon atoms such as an oxy group and a cyclohexyloxy group; a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, an isopropoxycarbonyl group, an n-butoxycarbonyl group, an isobutoxycarbonyl group, a sec-butoxy. An alkoxycarbonyl group having 1 to 6 carbon atoms such as a carbonyl group, a tert-butoxycarbonyl group, an n-pentyloxycarbonyl group, an isopentyloxycarbonyl group, a cyclopropyloxycarbonyl group, a cyclobutyloxycarbonyl group, and a cyclopentyloxycarbonyl group; Aromatic hydrocarbon groups such as phenyl group, trill group and naphthyl group; halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; acyl group having 1 to 6 carbon atoms; aralkyl group having 7 to 10 carbon atoms; Examples thereof include an aralkyloxy group having 7 to 10 carbon atoms; an alkylamino group having 1 to 6 carbon atoms; and a dialkylamino group having an alkyl group having 1 to 6 carbon atoms.

Examples of R ¹ and R ³ include a halogen atom, NO ₃ , an alkoxy group having 1 to 6 carbon atoms which may have a substituent, and an acyloxy group having 2 to 6 carbon atoms which may have a substituent. A β-diketonato group having 5 to 10 carbon atoms which may have a substituent or a diacylmethyl group having an acyl group having 1 to 6 carbon atoms which may have a substituent is preferable and has a substituent. An alkoxy group having 1 to 6 carbon atoms which may be used is more preferable.

As R ² , an alkyl group having 1 to 6 carbon atoms which may have a substituent is preferable. The k of the formula [II] is preferably 3.

As R ⁴ , an alkyl group having 1 to 6 carbon atoms which may have a substituent is preferable. As M ¹ , metal atoms belonging to Group 4 of the periodic table are preferable, and titanium and zirconium are more preferable. When M ¹ is a metal atom belonging to Group 4 of the periodic table, m in the formula [III] is preferably 4. Boron and silicon may be classified as metalloids, but these are included in the metals in the present specification.

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

Examples of the compound (Eb) include tetrakis (2,4-pentandionato) titanium, tetramethoxytitanium, tetraethoxytitanium, tetraisopropoxytitanium, tetra-n-butoxytitanium, and tetrakis (2-ethylhexoxy) titanium. Titanium compounds; examples thereof include zirconium compounds such as tetrakis (2,4-pentandionato) zirconium, tetra-n-propoxyzirconium, and tetra-n-butoxyzirconium. These may be used alone or in combination of two or more compounds (Eb).

In the compound (E), the ratio of the compound (Ea) to the compound (E) is not particularly limited as long as the effect of the present invention can be obtained. The ratio of the compound other than the compound (Ea) (for example, the compound (Eb)) to the compound (E) is preferably 20 mol% or less, more preferably 10 mol% or less, further preferably 5 mol% or less, and 0 mol%. It may be.

When compound (E) is hydrolyzed, at least a part of the hydrolyzable characteristic groups of compound (E) is converted into hydroxyl groups. Further, the hydrolyzate is condensed to form a compound in which a metal atom (M) is bonded via an oxygen atom (O). When this condensation is repeated, a compound that can be regarded as a metal oxide is formed. A hydroxyl group is usually present on the surface of the metal oxide (Aa) thus formed.

In the present specification, a compound having a ratio of [the number of moles of an oxygen atom (O) bonded only to a metal atom (M)] / [the number of moles of a metal atom (M)] of 0.8 or more is a metal. It shall be included in the oxide (Aa). Here, the oxygen atom (O) bonded only to the metal atom (M) is the oxygen atom (O) in the structure represented by MOOM, and the structure represented by MOH. The oxygen atom bonded to the metal atom (M) and the hydrogen atom (H), such as the oxygen atom (O) in, is excluded. The ratio of the metal oxide (Aa) is preferably 0.9 or more, more preferably 1.0 or more, and even more preferably 1.1 or more. The upper limit of this ratio is not particularly limited, but is usually represented by n / 2, where n is the valence of the metal atom (M).

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

The hydrolyzed condensate of compound (E) may be produced from a specific raw material by, for example, a method adopted 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 a compound formed by condensing a part of the complete hydrolyzate of the above can be used.

The metal oxide (Aa) to be mixed with the inorganic phosphorus compound (BI) -containing material (composition containing the inorganic phosphorus compound (BI) or the inorganic phosphorus compound (BI)), which will be described later, substantially contains a phosphorus atom. It is preferable not to contain it.

[Inorganic phosphorus compound (BI)]
The inorganic phosphorus compound (BI) contains a site that can react with the metal oxide (Aa), and typically contains a plurality of such sites (atomic groups or functional groups), preferably 2 to 20. To do. Such a site includes a site capable of condensation reaction with a functional group (for example, a hydroxyl group) existing on the surface of the metal oxide (Aa), for example, a halogen atom directly bonded to a phosphorus atom or a site directly bonded to a phosphorus atom. Oxygen atoms and the like can be mentioned. A functional group (for example, a hydroxyl group) existing on the surface of the metal oxide (Aa) is usually bonded to a metal atom (M) constituting the metal oxide (Aa).

Examples of the inorganic phosphorus compound (BI) include phosphoric acid, diphosphoric acid, triphosphoric acid, and polyphosphoric acid, phosphite, phosphonic acid, phosphonic acid, phosphinic acid, and phosphine in which four or more molecules of phosphoric acid are condensed. Examples thereof include oxo acids of phosphorus such as acids and derivatives thereof (for example, salts (for example, sodium phosphate), halides (for example, phosphoryl chloride), dehydrated products (for example, diphosphorus pentoxide)) and the like.

One of these inorganic phosphorus compounds (BI) may be used alone, or two or more thereof may be used in combination. Of these, it is preferable to use phosphoric acid alone or to use phosphoric acid in combination with other inorganic phosphorus compounds (BI). When phosphoric acid is used, the stability of the coating liquid (S) described later and the gas barrier property of the obtained multilayer structure are improved. When phosphoric acid and other inorganic phosphorus compound (BI) are used in combination, it is preferable that 50 mol% or more of the inorganic phosphorus compound (BI) is phosphoric acid.

[Organophosphorus compound (BO)]
The layer (Y) may contain an organic phosphorus compound (BO). Examples of the functional group containing a phosphorus atom contained in the organic phosphorus compound (BO) include a phosphoric acid group, a phosphite group, a phosphonic acid group, a phosphonic acid group, a phosphinic acid group, a phosphinic acid group, and derived from these. Examples thereof include functional groups (eg, salts, (partial) ester compounds, halides (eg, chlorides), dehydrated products), and among them, a phosphate group and a phosphonic acid group are preferable, and a phosphonic acid group is more preferable.

The organic phosphorus compound (BO) is preferably a polymer (BOa) having a functional group containing the phosphorus atom. Examples of the polymer (BOa) include 6-[(2-phosphonoacetyl) oxy] hexyl acrylate, 2-phosphonooxyethyl methacrylate, phosphonomethyl methacrylate, 11-phosphonoundesyl methacrylate, and methacrylic acid. Polymers of phosphono (meth) acrylic acid esters such as 1,1-diphosphonoethyl; vinylphosphonic acids such as vinylphosphonic acid, 2-propen-1-phosphonic acid, 4-vinylbenzylphosphonic acid, 4-vinylphenylphosphonic acid Polymers of vinyl phosphinic acids such as vinylphosphinic acid and 4-vinylbenzylphosphinic acid; phosphorylated starch and the like. The polymer (BOa) may be a homopolymer of a monomer having a functional group containing at least one phosphorus atom, or may be a copolymer of two or more kinds of monomers. Further, as the polymer (BOa), two or more kinds of polymers composed of a single monomer may be used in combination. Among them, a polymer of phosphono (meth) acrylic acid esters and a polymer of vinyl phosphonic acids are preferable, and a polymer of vinyl phosphonic acids is more preferable. That is, as the polymer (BOa), poly (vinyl phosphonic acid) is preferable. The polymer (BOa) can also be obtained by hydrolyzing a vinyl phosphonic acid derivative such as a vinyl phosphonic acid halide or a vinyl phosphonic acid ester alone or after copolymerization.

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

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

The molecular weight of the polymer (BOa) is not particularly limited, but the number average molecular weight is preferably in the range of 1,000 to 100,000. When the number average molecular weight is in this range, the effect of improving the bending resistance by laminating the layers (Y) and the viscosity stability of the coating liquid (T) when the coating liquid (T) described later is used can be obtained. , Compatible at a high level.

In the layer of the multilayer structure (Y), if it contains inorganic phosphorus compound (BI) organic phosphorus compound and (BO), a layer organophosphorus compound in the (Y) Weight W _BO and inorganic phosphorus compounds (BO) (BI) It is preferable that the ratio W _BO / W _BI of the mass W _BI satisfies the relationship of 0.01 / 99.99 ≤ W _BO / W _BI <6.00 / 94.00, and the barrier performance is excellent. It is more preferable that the relationship of 10 / 99.90 ≦ W _BO / W _BI <4.50 / 95.50 is satisfied, and 0.20 / 99.80 ≦ W _BO / W _BI <4.00 / 96.00. Those satisfying the relationship are more preferable, and those satisfying the relationship of 0.50 / 99.50 ≦ W _BO / W _BI <3.50 / 96.50 are particularly preferable. That is, W _BO is preferably used in a small amount of 0.01 or more and less than 6.00, whereas W _BI is preferably used in a large amount of more than 94.00 and 99.99 or less. Even when the inorganic phosphorus compound (BI) and / or the organic phosphorus compound (BO) is reacting in the layer (Y), the inorganic phosphorus compound (BI) and / or the organic phosphorus compound (BO) constituting the reaction product is reacted. ) Is regarded as an inorganic phosphorus compound (BI) and / or an organic phosphorus compound (BO). In this case, the mass of the inorganic phosphorus compound (BI) and / or the organophosphorus compound (BO) used to form the reaction product (the mass of the inorganic phosphorus compound (BI) and / or the organophosphorus compound (BO) before the reaction). ), Is included in the mass of the inorganic phosphorus compound (BI) and / or the organic phosphorus compound (BO) in the layer (Y).

[Compound (Ab)]
The reaction product (D) contained in the compound (Ab) is obtained by the reaction of the metal oxide (Aa) with the inorganic phosphorus compound (BI). Here, the reaction product (D) also includes a compound produced by the reaction of the metal oxide (Aa), the inorganic phosphorus compound (BI), and another compound. The compound (Ab) may partially contain a metal oxide (Aa) and / or an inorganic phosphorus compound (BI) that are not involved in the reaction.

In the compound (Ab), the molar ratio of the metal atom constituting the metal oxide (Aa) to the phosphorus atom derived from the inorganic phosphorus compound (BI) is [metal atom constituting the metal oxide (Aa)]: [ A phosphorus atom derived from an inorganic phosphorus compound (BI)] = preferably in the range of 1.0: 1.0 to 3.6: 1.0, and 1.1: 1.0 to 3.0: 1. It is more preferably in the range of 0. Outside this range, the gas barrier performance deteriorates. The molar ratio of the compound (Ab) can be adjusted by the mixing ratio of the metal oxide (Aa) and the inorganic phosphorus compound (BI) in the coating liquid for forming the compound (Ab). The molar ratio of compound (Ab) is usually the same as that of the coating solution.

In the infrared absorption spectrum of the layer (Y), the maximum absorption wave number in the region of 800～1,400Cm ^-1 is preferably in the range of 1,080~1,130cm ^-1. In the process of reacting the metal oxide (Aa) with the inorganic phosphorus compound (BI) to form the reaction product (D), the metal atom (M) derived from the metal oxide (Aa) and the inorganic phosphorus compound (BI) The phosphorus atom (P) derived from the above forms a bond represented by MOP via an oxygen atom (O). As a result, a characteristic absorption band derived from the bond is generated in the infrared absorption spectrum of the reaction product (D). As a result of the study by the present inventors, when the characteristic absorption band based on the bond of MOP ^{is found 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 sex. ^{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 the bond between various atoms and oxygen atoms is generally observed, the obtained multilayer structure is obtained. 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 an inorganic phosphorus compound (BI) are mixed in advance and then hydrolyzed and condensed, a metal atom derived from the metal compound and an inorganic phosphorus compound (BI) are obtained. A complex is obtained in which the derived phosphorus atom is mixed almost uniformly and reacted. In that case, in the infrared absorption spectrum, the maximum absorption wave number in the region of 800～1,400Cm ^-1 comes to deviate from the scope of 1,080~1,130cm ^-1.

In the infrared absorption spectrum of the layer (Y), the half-value width of the maximum absorption band in the region of 800～1,400Cm ^-1 from gas barrier property aspect of the resulting multilayer structure, 200 cm ^-1 or less is preferable, 150 cm ^-1 The following is more preferable, 100 cm ^-1 or less is further preferable, and 50 cm ^-1 or less is particularly preferable.

The infrared absorption spectrum of layer (Y) can be measured by the method described in Examples. However, if the measurement cannot be performed by the method described in the examples, the reflection measurement such as the reflection absorption method, the external reflection method, the attenuation total reflection method, the scraping of the layer (Y) from the multilayer structure, the Nujor method, the tablet method, etc. It may be measured by a method called transmission measurement, but the measurement is not limited to these.

[Inorganic vapor deposition layer, compound (Ac), compound (Ad)]
The multilayer structure may further include an inorganic thin-film deposition layer. The inorganic vapor deposition layer can be a metal (eg, aluminum), a metal oxide (eg, silicon oxide, aluminum oxide), a metal nitride (eg, silicon nitride), a metal nitride oxide (eg, silicon oxynitride), or a metal carbide. It may be formed of a nitride (for example, silicon carbide) or the like. The layer (Y) in the multilayer structure of the present invention may include an inorganic vapor-deposited layer containing aluminum. For example, the layer (Y) may include an aluminum vapor deposition layer (Ac) and / or an aluminum oxide vapor deposition layer (Ad).

The method for forming the inorganic vapor deposition layer is not particularly limited, and is a vacuum vapor deposition method (for example, resistance heating vapor deposition, electron beam deposition, molecular beam epitaxy method, etc.), a physical vapor deposition method such as a sputtering method or an ion plating method; Chemical Vapor Deposition (eg, Catalytic Chemical Vapor Deposition), Photochemical Vapor Deposition, Plasma Chemical Vapor Deposition (eg, Capacitive Bonded Plasma, Induced Bonded Plasma, Surface Wave Plasma, Electron Cyclotron Resonance, Dual Magnetron, Chemical vapor deposition methods such as atomic layer deposition method) and organic metal vapor deposition method can be used.

The thickness of the inorganic thin-film deposition layer varies depending on the type of the components constituting the inorganic thin-film deposition layer, but is preferably 0.002 to 0.5 μm, more preferably 0.005 to 0.2 μm, and preferably 0.01 to 0.1 μm. More preferred. Within this range, a thickness that improves the barrier properties and mechanical properties of the multilayer structure may be selected. If the thickness of the inorganic thin-film deposition layer is less than 0.002 μm, the reproducibility of the barrier property development of the inorganic vapor-filming layer against oxygen and water vapor tends to decrease, and when the inorganic thin-film deposition layer does not exhibit sufficient barrier property. There is also. Further, when the thickness of the inorganic thin-film deposition layer exceeds 0.5 μm, the barrier property of the inorganic-deposited layer tends to decrease when the multilayer structure is pulled or bent.

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

Examples of the polymer compound (F) include polyethylene glycol; polyvinyl alcohol, modified polyvinyl alcohol containing 1 to 50 mol% of α-olefin units having 4 or less carbon atoms, and polyvinyl alcohols such as polyvinyl acetal (polyvinyl butyral, etc.). Polymers; polysaccharides such as cellulose and starch; (meth) acrylic acid-based polymers such as polyhydroxyethyl (meth) acrylate, poly (meth) acrylic acid, ethylene-acrylic acid copolymers; ethylene-maleic anhydride Examples thereof include a polymer hydrolyzate, a styrene-maleic anhydride copolymer hydrolyzate, and a maleic acid-based polymer such as an isobutylene-maleic anhydride copolymer hydrolyzate. Of these, polyethylene glycol and polyvinyl alcohol-based polymers are preferable. As the polymer compound (F), two or more kinds of polymer compounds (F) may be mixed and used.

The molecular weight of the polymer compound (F) is not particularly limited, but the number average of the polymer compound (F) is obtained in order to obtain a multilayer structure having better gas barrier properties and mechanical properties (drop impact strength, etc.). The molecular weight 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 compound (F) is not particularly limited, and is, for example, 1,500,000 or less.

When the layer (Y) contains the polymer compound (F), the content thereof is preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably 30% by mass or less based on the weight of the layer (Y). , 20% by mass or less. The polymer compound (F) may or may not react with other components in the layer (Y).

The layer (Y) can further contain other components. Such other components include, for example, inorganic acid metal salts such as carbonates, hydrochlorides, nitrates, hydrogen carbonates, sulfates, hydrogen sulfates, borates; oxalates, acetates, tartrates, stearic acids. Organic acid metal salts such as salts; metal complexes such as cyclopentadienyl metal complex (eg, titanosen), cyano metal complex (eg, Prussian blue); layered clay compound; cross-linking agent; high other than polymer compound (F) Molecular 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, further preferably 10% by mass or less, and particularly preferably 5% by mass or less. It may be 0% by mass (does not contain 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. , More preferably in the range of 0.1 μm to 2.0 μm. By thinning the layer (Y), it is possible to suppress a dimensional change of the multilayer structure during processing such as printing or laminating. The thickness of the layer (Y) can be measured by observing the cross section of the multilayer structure with a scanning electron microscope or a transmission electron microscope.

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

As a method for producing a multilayer structure of the present invention, for example, a coating liquid (R) containing a phosphorus compound (BH) and a solvent is applied onto a substrate (X), and then the solvent is removed to form a layer (Z). In the step (I) of forming the reaction product (D), a coating liquid (S) containing an aluminum-containing compound (A), an inorganic phosphorus compound (BI) and a solvent is applied onto the layer (Z). ) A step (II) of forming a layer (Y) precursor layer containing a precursor, and a step (Y) of forming a layer (Y) containing a reaction product (D) by heat-treating the layer (Y) precursor layer. Examples thereof include a production method including (III). Further, in the above-mentioned production method, the coating liquid (S) used in the step (II) may contain an organic phosphorus compound (BO), and the coating liquid (S) used in the step (II) contains the organic phosphorus compound (BO). In the case of not containing, the step (II') of applying the organic phosphorus compound (BO) -containing coating liquid (T) to the surface of the precursor layer obtained in the step (II) may be included. The compound (A), the inorganic phosphorus compound (BI), the organic phosphorus compound (BO), and their mass ratios are as described above, and redundant description will be omitted in the production method.

[Step (I)]
In the step (I), the layer (Z) is formed by applying a coating liquid (R) containing a phosphorus compound (BH) and a solvent onto the base material (X). The coating liquid (R) is obtained by mixing a phosphorus compound (BH) and a solvent.

The solvent used for the coating liquid (R) is not particularly limited, but preferably water is the main component and may be a mixed solvent of alcohols such as methanol, ethanol and isopropanol and water, or water alone. Good.

The solid content concentration of the coating liquid (R) is preferably 0.1 to 20% by mass, more preferably 0.5 to 10% by mass, from the viewpoint of storage stability of the coating liquid and coatability on the substrate. 1 to 5% by mass is more preferable. The solid content concentration can be calculated, for example, by dividing the mass of the solid content remaining after distilling off the solvent of the coating liquid (R) by the mass of the coating liquid (R) subjected to the treatment.

The coating of the coating liquid (R) is not particularly limited, and for example, a casting method, a dipping method, a roll coating method, a gravure coating method, a screen printing method, a reverse coating method, a spray coating method, a kiss coating method, a die coating method, and a metering method. Known coating methods such as a bar coating method, a chamber doctor combined coating method, a curtain coating method, and a bar coating method can be adopted.

The thickness of the layer (Z) formed after coating the coating liquid (R) on the base material (X) can be controlled by the solid content concentration of the coating liquid (R) or the coating method. For example, in the case of the gravure coating method, it can be controlled by changing the cell volume of the gravure roll.

Usually, in step (I), the layer (Z) is formed by removing the solvent in the coating liquid (R). The method for removing the solvent is not particularly limited, and for example, a known drying method such as a hot air drying method, a hot roll contact method, an infrared heating method, or a microwave heating method can be applied.

[Step (II)]
In the step (II), a coating liquid (S) containing an aluminum-containing compound (A), an inorganic phosphorus compound (BI) and a solvent is applied onto the layer (Z) to obtain a reaction product (D). A layer containing a precursor (Y) A precursor layer is formed. The coating liquid (S) is obtained by mixing the compound (A) containing aluminum, the phosphorus compound (B) and a solvent. When the layer (Y) includes an aluminum vapor deposition layer (Ac) or an aluminum oxide vapor deposition layer (Ad), these layers can be formed by the above-mentioned general vapor deposition method. Hereinafter, as a preferred embodiment, an embodiment using a metal oxide (Aa), an inorganic phosphorus compound (BI), and a solvent will be described.

In a preferred embodiment, the coating liquid (S) can be prepared by mixing a metal oxide (Aa) and an inorganic phosphorus compound (BI) in a solvent and reacting them. Specifically, the coating liquid (S) is a method of mixing a dispersion liquid of a metal oxide (Aa) and a solution containing an inorganic phosphorus compound (BI); an inorganic phosphorus compound in a dispersion liquid of the metal oxide (Aa). It can be prepared by a method of adding (BI) and mixing. The temperature at the time of mixing these 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, polymer compound (F) (preferably excluding polyvinyl alcohol-based polymer)), and acetic acid, hydrochloric acid, nitrate, and trichloroacetic acid, hydrochloric acid, trichloroacetic acid, and trichloroacetic acid, if necessary. It may contain at least one acid compound (Q) selected from the group consisting of fluoroacetic acid and trichloroacetic acid.

The dispersion liquid of the metal oxide (Aa) is prepared by mixing, for example, the compound (E), water, and, if necessary, an acid catalyst or an organic solvent according to the method adopted in the known sol-gel method. It can be prepared by condensing or hydrolyzing E). When a dispersion liquid of the metal oxide (Aa) is obtained by condensing or hydrolyzing the compound (E), a specific treatment (the acid compound (Q)) is applied to the obtained dispersion liquid, if necessary. (Glue, etc. in the presence of) may be performed. The solvent used for preparing the dispersion liquid of the metal oxide (Aa) is not particularly limited, but alcohols such as methanol, ethanol and isopropanol; water; or a mixed solvent thereof is preferable.

The solution containing the inorganic phosphorus compound (BI) can be prepared by dissolving the inorganic phosphorus compound (BI) in a solvent. The solvent may be appropriately selected depending on the type of the inorganic phosphorus compound (BI), but preferably contains water. The solvent may contain an organic solvent (for example, alcohols such as methanol) as long as it does not interfere with the dissolution of the inorganic phosphorus compound (BI).

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

The coating liquid (S) has a viscosity measured by a Brookfield type viscometer (SB type viscometer: rotor No. 3, rotation speed 60 rpm) of 3,000 mPa · s or less at the temperature at the time of coating. Is more preferable, and it is more preferably 2,500 mPa · s or less, and further 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 better 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 atom to phosphorus atom is not particularly limited, but may be in the range of aluminum atom: phosphorus atom = 1.0: 1.0 to 3.6: 1.0. It is preferably in the range of 1.1: 1.0 to 3.0: 1.0, and particularly preferably 1.11: 1.00 to 1.50: 1.00. The molar ratio of aluminum atoms to phosphorus atoms can be calculated by performing fluorescent X-ray analysis of the dry matter of the coating liquid (S).

The coating of the coating liquid (S) is not particularly limited, and for example, a casting method, a dipping method, a roll coating method, a gravure coating method, a screen printing method, a reverse coating method, a spray coating method, a kiss coating method, a die coating method, and a metering method. Known methods such as a bar coat method, a chamber doctor combined coat method, a curtain coat method, and a bar coat method can be adopted.

Usually, in step (II), the layer (Y) precursor layer is formed by removing the solvent in the coating liquid (S). The method for removing the solvent is not particularly limited, and for example, a known drying method such as a hot air drying method, a hot roll contact method, an infrared heating method, or a microwave heating method can be applied. It is essential that the solvent content after drying and the average particle size of the reaction product (D) precursor are within a specific range in order for the obtained multilayer structure to have excellent gas barrier properties even after retort treatment.

The solvent content of the layer (Y) precursor layer after the drying treatment 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 a stricter 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) precursor can be reduced, and the layer (Y) obtained in the subsequent heat treatment step (III) can be reduced. ), The average particle size of the reaction product (D) becomes smaller, and better barrier performance can be obtained. The lower limit of the solvent content is not particularly limited, but is usually preferably 0.01% by mass or more from the viewpoint of manufacturing cost.

The average particle size of the reaction product (D) precursor of the layer (Y) precursor layer after the drying treatment is preferably less than 5 nm, and more preferably less than 4 nm from the viewpoint of showing excellent barrier performance even after a stricter retort treatment. Less than 3 nm is more preferable. When the average particle size of the reaction product (D) precursor of the layer (Y) precursor layer after the drying treatment is within the above range, the average particle size of the reaction product (D) in the obtained layer (Y) is It becomes smaller and better barrier performance can be obtained. The lower limit of the average particle size of the reaction product (D) precursor 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) precursor, the average particle size of the reaction product (D) contained in the layer (Y) of the obtained multilayer structure is 50 nm or less. And better barrier performance can be obtained.

The ratio of the addition, in the infrared absorption spectrum of the layer (Y) precursor, a local maximum value A _P absorbance in the region of the maximum value A _R and 850～950Cm ^-1 absorbance in the range 1,080～1,130Cm ^-1 preferably A _R / A _P is 2.0 or less, more preferably 1.4 or less. The maximum value A _R of the absorbance in the range 1,080～1,130Cm ^-1 based on the binding of M-O-P as described above, the maximum value A _P absorbance in the range 850~950cm ^-1 M- Based on OM binding. That the ratio A _R / A _P can be thought of as an index representing the reaction of the metal oxide containing aluminum reaction product of (Aa) to (D). In the present invention, in the layer (Y) precursor after the drying step, the reaction of the metal oxide (Aa) with the reaction product (D) is suppressed to a certain amount or less, which has good barrier performance. It is considered to be effective for obtaining a multi-layer structure. Therefore, if the ratio A _R / _AP is larger than the above range, the barrier performance of the obtained multilayer structure may be insufficient.

The drying temperature is preferably lower than the flow start temperature of the base material (X). The drying temperature of the coating liquid (S) after coating may be, for example, about 80 to 180 ° C., but in order to satisfy the solvent content and the average particle size of the reaction product (D) precursor, the coating is applied. The drying temperature of the liquid (S) after coating is preferably less than 140 ° C., more preferably 60 ° C. or higher and lower than 140 ° C., further preferably 70 ° C. or higher and lower than 130 ° C., and particularly preferably 80 ° C. or higher and lower than 120 ° C. The drying time is not particularly limited, but is preferably 1 second or more and less than 1 hour, more preferably 5 seconds or more and less than 15 minutes, and further preferably 5 seconds or more and 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 5 seconds or more and less than 3 minutes. preferable. When the drying temperature is lower than 100 ° C. (for example, 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 further preferably 8 minutes or more and less than 25 minutes.

[Step (III)]
In the step (III), the layer (Y) precursor layer formed in the step (II) is heat-treated at a temperature of 140 ° C. or higher to form the layer (Y). In the present invention, it is important to heat-treat the layer (Y) precursor having the above-mentioned specific solvent content and average particle size at a temperature of 140 ° C. or higher in order to obtain better barrier performance. The heat treatment temperature in step (III) is preferably higher than the drying temperature in step (II).

In step (III), the reaction produced by the reaction product (D) proceeds. In order to allow the reaction to proceed sufficiently, the heat treatment temperature is 140 ° C. or higher, preferably 170 ° C. or higher, more preferably 180 ° C. or higher, still more preferably 190 ° C. or higher. If the heat treatment temperature is low, it takes a long time to obtain a sufficient reaction rate, which causes a decrease in productivity. The temperature of the heat treatment is not particularly limited because it differs depending on the type of the base material (X) and the like, but may be 270 ° C. or lower. For example, when a thermoplastic resin film made of a polyamide resin is used as the base material (X), the heat treatment temperature is preferably 270 ° C. or lower. When a thermoplastic resin film made of a polyester resin is used as the base material (X), the heat treatment temperature is preferably 240 ° C. or lower. The heat treatment may be carried out in an air atmosphere, a nitrogen atmosphere, an argon atmosphere or the like. The heat treatment time is preferably 1 second to 1 hour, more preferably 1 second to 15 minutes, and even more preferably 5 to 300 seconds.

The heat treatment is preferably carried out in two or more steps by changing the treatment temperature in order to satisfy the solvent content and the average particle size of the reaction product (D) precursor. That is, the 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, second heat treatment) is preferably higher than the temperature of the first stage heat treatment (hereinafter, first heat treatment), and the temperature of the first heat treatment. It is more preferably 15 ° C. or higher, further preferably 25 ° C. or higher, and particularly preferably 35 ° C. or higher.

Further, the heat treatment temperature of the step (III) (in the case of a heat treatment of two or more steps, the temperature of the first heat treatment) is 30 higher than the drying temperature of the step (II) because a multilayer structure having good characteristics can be obtained. It is preferably higher than ° C., more preferably 50 ° C. or higher, further preferably 55 ° C. or higher, and particularly preferably 60 ° C. or higher.

When the heat treatment in step (III) is performed in two or more steps, 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 less than 200 ° C., and the temperature of the second heat treatment is high. It is preferably 180 ° C. or higher and 270 ° C. or lower, the temperature of the second heat treatment is 15 ° C. or higher 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 more preferably 180 ° C. or higher and 270 ° C. or lower, the temperature of the second heat treatment is 25 ° 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 second heat treatment It is more preferable that the temperature of the temperature is 180 ° C. or higher and 270 ° C. or lower. 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, still 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, still more preferably 10 seconds to 5 minutes.

[Step (II')]
When the organic phosphorus compound (BO) is used in the production method and the coating liquid (S) used in the step (II) does not contain the organic phosphorus compound (BO), the organic phosphorus is contained in the step (II'). The coating liquid (T) (second coating liquid) obtained by mixing the compound (BO) and the solvent may be applied onto the layer (Y) obtained in the step (III). In the step (II'), the coating liquid (T) (second coating liquid) obtained by mixing the organic phosphorus compound (BO) and the solvent is applied after the first heat treatment step (III-1) of the step (III). It is preferable that after coating on the layer (Y), it is subsequently subjected to the second heat treatment step (III-2) of the step (III).

The step (II') includes a step (II') of applying a coating liquid (T) containing an organic phosphorus compound (BO) on the layer (Y) obtained in the step (III).

The coating liquid (T) can be prepared by mixing an organic phosphorus compound (BO) and a solvent. The obtained coating liquid (T) is applied onto the layer (Y) obtained in the step (III).

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

The concentration of the solid content in the coating liquid (T) is preferably 0.01 to 60% by mass, more preferably 0.1 to 50% by mass, and 0.2 to 40% from the viewpoint of storage stability and coatability of the solution. Mass% is more preferred. The solid content concentration can be determined by the same method as described for the coating liquid (S). Further, as long as the effect of the present invention can be obtained, the coating liquid (T) may contain other components (for example, the polymer compound (F)) contained in the above-mentioned layer (Y).

Similar to the coating of the coating liquid (S), the method of applying the coating liquid (T) is not particularly limited, and a known method can be adopted.

After applying the coating liquid (T), the solvent is removed. The method for removing the solvent of the coating liquid (T) is not particularly limited, and for example, a known drying method such as a hot air drying method, a hot roll contact method, an infrared heating method, or a microwave heating method can be applied. The drying temperature is preferably 0 to 15 ° C. or more lower than the flow start temperature of the base material (X). The drying temperature of the coating liquid (T) after coating may be, for example, about 90 to 240 ° C., preferably 100 to 200 ° C.

Step (III) can use the same heating equipment that is continuous with step (II) or can change the heating temperature stepwise. Further, step (III) can precede step (II').

In a preferred embodiment of the method for producing a multilayer structure of the present invention, after coating the coating liquid (S) in step (II), a drying treatment is performed to form a layer (Y) precursor layer, and further step (III). ) Is heat-treated. At this time, the temperature of the heat treatment is preferably 30 ° C. or higher, more preferably 50 ° C. or higher, higher than the temperature of the drying treatment.

When the production method includes step (II'), in another preferred embodiment of the method for producing a multilayer structure of the present invention, the coating liquid (S) of step (II) is applied and dried. After forming the layer (Y) precursor layer, the first heat treatment step (III-1) of the step (III) is performed. Subsequently, the coating liquid (T) of the step (II') is applied, dried, and then the second heat treatment step (III-2) of the step (III) is further performed. At this time, the temperature of the first heat treatment is preferably 30 ° C. or higher, more preferably 50 ° C. or higher, higher than the temperature of the drying treatment in step (II). Further, it is preferable that the temperature of the second heat treatment is higher than the temperature of the first heat treatment.

[Adhesive layer (I)]
In the multilayer structure of the present invention, the adhesive layer (I) may be used to enhance the adhesiveness between the layer (Y) and another member (for example, another layer (J)). The adhesive layer (I) may be made of an adhesive resin. As the adhesive resin, a two-component reaction type polyurethane adhesive in which a polyisocyanate component and a polyol component are mixed and reacted is preferable. Further, by adding a small amount of additive such as a known silane coupling agent to the anchor coating agent or adhesive, the adhesiveness may be further enhanced. Examples of the silane coupling agent include, but are not limited to, a silane coupling agent having a reactive group such as an isocyanate group, an epoxy group, an amino group, a ureido group, and a mercapto group. By adhering the layer (Y) to another member, deterioration of gas barrier property or appearance can be more effectively suppressed when the multilayer structure of the present invention is processed such as printing or laminating, and further. , The drop strength of the packaging material using the multilayer structure of the present invention can be increased. The thickness of the adhesive layer (I) is preferably 0.01 to 10.0 μm, more preferably 0.03 to 5.0 μm.

[Other layer (J)]
The multilayer structure of the present invention may contain another layer (J) in order to improve various properties (for example, heat-sealing property, barrier property, mechanical property). In such a multilayer structure of the present invention, for example, after laminating a layer (Y) on a base material (X) via a layer (Z), the other layer (J) is directly or an adhesive layer is formed. It can be manufactured by adhering or forming through. Examples of the other layer (J) include, but are not limited to, an ink layer; a polyolefin layer, a thermoplastic resin layer such as an ethylene-vinyl alcohol copolymer resin layer, and the like.

The multilayer structure of the present invention may include an ink layer for printing a trade 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 (for example, titanium dioxide) is dispersed in a solvent, but a polyurethane resin containing no pigment or an ink containing another resin as a main component is used. A dry film may be used as the resin for forming the electronic circuit wiring. Examples of the ink layer coating method include a gravure printing method and various coating methods such as a wire bar, a spin coater, and a die coater. The thickness of the ink layer is preferably 0.5 to 10.0 μm, more preferably 1.0 to 4.0 μm.

By forming the outermost surface layer of the multilayer structure of the present invention as a polyolefin layer, it is possible to impart heat-sealing properties to the multilayer structure and improve the mechanical properties of the multilayer structure. From the viewpoint of improving heat sealability and mechanical properties, the polyolefin is preferably polypropylene or polyethylene. Further, 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 a hydroxyl group-containing polymer. From the viewpoint of improving mechanical properties, polyethylene terephthalate is preferable as the polyester, nylon-6 is preferable as the polyamide, and ethylene-vinyl alcohol copolymer is preferable as the hydroxyl group-containing polymer. If necessary, an anchor coat layer or a layer made of an adhesive may be provided between the layers.

[Extruded coat laminate]
In the multilayer structure of the present invention, for example, after laminating a layer (Y) on a base material (X) via a layer (Z), another layer (J) is extruded and coated directly or via an adhesive layer. It can be formed by a laminating method and further have a layer formed by such an extruded coat laminate. The extruded coat laminating method is not particularly limited, and a known method can be applied. In a typical extrusion coat laminating method, a laminated film is produced by sending a molten thermoplastic resin to a T-die and cooling the thermoplastic resin taken out from a flat slit of the T-die.

An example of the most common single laminating method among the extruded coat laminating methods will be described below with reference to the drawings. FIG. 5 shows an example of the apparatus used in the single laminating method. Note that FIG. 5 is a diagram schematically showing only the main part of the device, which is different from the actual device. The device 50 of FIG. 5 includes an extruder 51, a T-die 52, a cooling roll 53, and a rubber roll 54. The cooling roll 53 and the rubber roll 54 are arranged so that their roll surfaces are in contact with each other.

The thermoplastic resin is heated and melted in the extruder and extruded from the flat slit of the T-die 52 to form the resin film 502. On the other hand, the laminated body 501 is fed from the sheet feeding device (not shown) and sandwiched between the cooling roll 53 and the rubber roll 54 together with the resin film 502. A laminated film (multilayer structure) in which the laminated body 501 and the resin film 502 are integrated by being sandwiched between the cooling roll 53 and the rubber roll 54 in a state where the laminated body 501 and the resin film 502 are laminated. 503 is manufactured.

Examples of the extrusion coat laminating method other than the single laminating method include a sandwich laminating method and a tandem laminating method. The sandwich laminating 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 (unwinding machine) and bonded to each other to prepare a laminated body. The tandem laminating method is a method of connecting two single laminating machines to produce a laminated body having a five-layer structure at a time.

By using the above-mentioned laminate, a multilayer structure that maintains high barrier performance even after extrusion coat lamination and has a small decrease in light transmission can be obtained.

[Structure of multi-layer structure]
Specific examples of the configuration of the multilayer structure of the present invention are shown below. The multilayer structure may have members other than the base material (X), the layer (Z), and the layer (Y) (for example, the adhesive layer (I) and the other layer (J)). In the specific example of, the description of the layer (Z) and other members is omitted. The layer (Z) is laminated on the base material (X), and the layer (Y) is laminated on the layer (Z). Further, the following specific examples may be laminated or combined in a plurality of layers.
(1) Layer (Y) / polyester layer,
(2) Layer (Y) / Polyester layer / Layer (Y),
(3) Layer (Y) / Polyamide layer,
(4) Layer (Y) / Polyamide layer / Layer (Y),
(5) Layer (Y) / polyolefin layer,
(6) Layer (Y) / polyolefin layer / layer (Y),
(7) Layer (Y) / hydroxyl group-containing polymer layer,
(8) Layer (Y) / hydroxyl group-containing polymer layer / layer (Y),
(9) Layer (Y) / Paper layer,
(10) Layer (Y) / Paper layer / Layer (Y),
(11) Layer (Y) / Inorganic vapor deposition layer / Polyester layer,
(12) Layer (Y) / Inorganic vapor deposition layer / Polyamide layer,
(13) Layer (Y) / Inorganic vapor deposition layer / Polyolefin layer,
(14) Layer (Y) / Inorganic vapor deposition layer / Hydroxyl group-containing polymer layer,
(15) Layer (Y) / Polyester layer / Polyamide layer / Polyolefin layer,
(16) Layer (Y) / Polyester layer / Layer (Y) / Polyamide layer / Polyolefin layer,
(17) Polyester layer / layer (Y) / polyester layer / layer (Y) / inorganic vapor deposition layer / hydroxyl group-containing polymer layer / polyolefin layer,
(18) Polyester layer / layer (Y) / polyamide layer / polyolefin layer,
(19) Layer (Y) / Polyamide layer / Polyester layer / Polyolefin layer,
(20) Layer (Y) / Polyamide layer / Layer (Y) / Polyester layer / Polyolefin layer,
(21) Polyamide layer / layer (Y) / polyester layer / polyolefin layer,
(22) Layer (Y) / Polyolefin layer / Polyamide layer / Polyolefin layer,
(23) Layer (Y) / Polyolefin layer / Layer (Y) / Polyamide layer / Polyolefin layer,
(24) Polyolefin layer / layer (Y) / polyamide layer / polyolefin layer,
(25) Layer (Y) / polyolefin layer / polyolefin layer,
(26) Layer (Y) / Polyolefin layer / Layer (Y) / Polyolefin layer,
(27) Polyethylene layer / layer (Y) / polyolefin layer,
(28) Layer (Y) / Polyester layer / Polyolefin layer,
(29) Layer (Y) / Polyester layer / Layer (Y) / Polyolefin layer,
(30) Polyester layer / layer (Y) / polyolefin layer,
(31) Layer (Y) / Polyamide layer / Polyolefin layer,
(32) Layer (Y) / Polyamide layer / Layer (Y) / Polyolefin layer,
(33) Polyamide layer / layer (Y) / polyolefin layer,
(34) Layer (Y) / Polyester layer / Paper layer,
(35) Layer (Y) / Polyamide layer / Paper layer,
(36) Layer (Y) / polyolefin layer / paper layer,
(37) Polyolefin layer / paper layer / polyolefin layer / layer (Y) / polyester layer / polyolefin layer,
(38) Polyolefin layer / paper layer / polyolefin layer / layer (Y) / polyamide layer / polyolefin layer,
(39) Polyolefin layer / paper layer / polyolefin layer / layer (Y) / polyolefin layer,
(40) Paper layer / polyolefin layer / layer (Y) / polyester layer / polyolefin layer,
(41) Polyolefin layer / paper layer / layer (Y) / polyolefin layer,
(42) Paper layer / layer (Y) / polyester layer / polyolefin layer,
(43) Paper layer / layer (Y) / polyolefin layer,
(44) Layer (Y) / Paper layer / Polyolefin layer,
(45) Layer (Y) / Polyester layer / Paper layer / Polyolefin layer,
(46) Polyolefin layer / paper layer / polyolefin layer / layer (Y) / polyolefin layer / hydroxyl group-containing polymer layer,
(47) Polyolefin layer / paper layer / polyolefin layer / layer (Y) / polyolefin layer / polyamide layer,
(48) Polyolefin layer / paper layer / polyolefin layer / layer (Y) / polyolefin layer / polyester layer,
(49) Inorganic vapor deposition layer / layer (Y) / polyester layer,
(50) Inorganic vapor deposition layer / layer (Y) / polyester layer / layer (Y) / inorganic vapor deposition layer,
(51) Inorganic vapor deposition layer / layer (Y) / polyamide layer,
(52) Inorganic vapor deposition layer / layer (Y) / polyamide layer / layer (Y) / inorganic vapor deposition layer,
(53) Inorganic vapor deposition layer / layer (Y) / polyolefin layer,
(54) Inorganic vapor deposition layer / layer (Y) / polyolefin layer / layer (Y) / inorganic vapor deposition layer

According to the present invention, it is possible to obtain a multilayer structure having an ^{oxygen permeability of 2.0 mL / (m 2} · day · atm) or less under the conditions of 20 ° C. and 85% RH before and after the retort treatment. Is possible. The oxygen permeability of the multilayer structure of the present invention ^{is preferably 0.5 mL / (m 2} · day · atm) or less, preferably 0.3 mL / (m ² · day · atm) or less, before and after the retort treatment. More preferred. The conditions for the retort treatment, the method for measuring the oxygen permeability, and the measurement conditions are as described in Examples described later.

Further, according to the present invention, a multilayer structure having a ^{moisture permeability of 2.0 g / (m 2} · day) or less under the conditions of 40 ° C. and 90/0% RH is obtained before and after the retort treatment. It is possible. The moisture permeability of the multilayer structure of the present invention ^{is preferably 1.0 g / (m 2} · day) or less, more preferably 0.5 g / (m ² · day) or less before and after the retort treatment. The conditions for the retort treatment, the method for measuring the moisture permeability, and the measurement conditions are as described in Examples described later.

Further, the multilayer structure of the present invention preferably has a peel strength of more than 100 g / 15 mm between the layer (Y) after the retort treatment and the adhesive layer (I) or another layer (for example, an ink layer), preferably 110 g /. Those having a thickness of 15 mm or more are more preferable. The conditions for the retort treatment, the method for measuring the peel strength, and the measurement conditions are as described in Examples described later.

[Use]
The multilayer structure of the present invention and the packaging material using the same have high adhesion at the film bent portion during the retort treatment. Further, the multilayer structure of the present invention and the packaging material using the same are excellent in gas barrier property and water vapor barrier property, and also in excellent retort resistance. Therefore, the multilayer structure of the present invention and the packaging material using the same can be applied to various uses.

[Packaging material]
The packaging material of the present invention is a multilayer structure including a base material (X), a layer (Z) laminated on the base material (X), and a layer (Y) laminated on the layer (Z). including. 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 a multilayer structure and other members. The packaging material of the present invention preferably has a layer formed by the extrusion-coated laminate described above.

Packaging materials according to preferred embodiments of the present invention include inorganic gases (eg hydrogen, helium, nitrogen, oxygen, carbon dioxide), natural gas, water vapor and organic compounds that are liquid at room temperature and pressure (eg ethanol, gasoline vapor). Has a barrier property against.

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

The packaging material of the present invention can be produced by various methods. For example, a container (packaging material) is produced by joining a sheet-shaped multilayer structure or a film material containing the multilayer structure (hereinafter, simply referred to as “film material”) and molding the container into a predetermined container shape. You may. Examples of the molding method include thermoforming, injection molding, extrusion blow molding and the like. Further, a container (packaging material) may be produced by forming a layer (Z) and a layer (Y) on a base material (X) formed into a predetermined container shape. Containers manufactured as described above may be referred to as "packaging containers" in the present specification.

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

Further, the packaging material containing the multilayer structure of the present invention can be used by secondary processing into various molded products. Such molded products can be vertical bag-filled seal bags, vacuum packaging bags, pouches, laminated tube containers, infusion bags, paper containers, strip tape, container lids, in-mold label containers, vacuum insulation, or electronic devices. It may be. Heat sealing may be performed on these molded articles.

[Vertical bag filling seal bag]
The packaging material containing the multilayer structure of the present invention may be a vertical bag-filled seal bag. An example is shown in FIG. The vertical bag filling seal bag 10 shown in FIG. 1 is formed by sealing the multilayer structure 11 of the present invention on three sides of two end portions 11a and a body portion 11b. The vertical bag filling seal bag 10 can be manufactured by a vertical bag filling machine. Various methods are applied to bag making with a vertical bag filling machine, but in each method, the contents are supplied from the upper opening of the bag to the inside of the bag, and then the opening is sealed. A vertical bag filling seal bag is manufactured. The vertical bag filling seal bag is composed of, for example, a single film material that is heat-sealed at the upper end, the lower end, and the side portion. The vertical bag-filled seal bag as a packaging container according to the present invention has high adhesion at the film bent portion during retort treatment. Further, the vertical bag-filled seal bag as a packaging container according to the present invention has excellent gas barrier properties and water vapor barrier properties, and the barrier performance is maintained even after retort treatment. Therefore, according to the vertical bag-filled seal bag, the contents Deterioration of product quality can be suppressed for a long period of time.

[Pouch]
The packaging material containing the multilayer structure of the present invention may be a pouch. An example is shown in FIG. The flat pouch 20 of FIG. 2 is formed by joining two multilayer structures 11 to each other at a peripheral edge portion 11c thereof. As used herein, the term "pouch" means a container with a film material as a wall member, which mainly contains food, daily necessities or pharmaceuticals. Examples of the pouch include a pouch with a spout, a pouch with a zipper seal, a flat pouch, a stand-up pouch, a horizontal bag-filled seal pouch, a retort pouch, and the like, depending on the shape and use thereof. The pouch may be formed by laminating a multilayer structure and at least one other layer (J). The pouch as a packaging container according to the present invention has high adhesion at the film bent portion during retort treatment. Further, the pouch as a packaging container according to the present invention is excellent in gas barrier property and water vapor barrier property, and its barrier performance is maintained even after retort treatment. Therefore, by using the pouch, it is possible to prevent deterioration of the contents even after transportation or long-term storage. Further, in one example of the pouch, since the transparency can be maintained well, it is easy to confirm the contents and the deterioration of the contents due to deterioration.

[Infusion bag]
The packaging material containing the multilayer structure of the present invention may be an infusion bag. The infusion bag is a container containing the infusion preparation as its content, and includes a film material (multilayer structure of the present invention) as a partition wall separating the inside and the outside for accommodating the infusion preparation. An example is shown in FIG. As shown in FIG. 3, the infusion bag 401 may include a spout member 432 on the peripheral edge portion 412 of the bag main body 431 in addition to the bag main body 431 that houses the contents. The spout member 432 functions as a route for taking out the infusion solution contained in the bag body 431. Further, the infusion bag may be provided with a hanging hole 433 in the peripheral edge portion 411 on the opposite side of the peripheral edge portion 412 to which the spout member 432 is attached in order to suspend the bag. The bag body 431 is formed by joining two film materials 410a and 410b to each other at peripheral portions 411, 421, 413, and 414 thereof. The film materials 410a and 410b function as a partition wall 420 that separates the inside of the bag from the outside of the bag in the central portion surrounded by the peripheral edges 411, 421, 413, and 414 of the bag body 431. The infusion bag as a packaging container according to the present invention has high adhesion at the film bent portion during retort treatment. Further, the infusion bag as a packaging container according to the present invention has excellent gas barrier properties, and the gas barrier properties are maintained even after heat treatment such as hot water treatment. Therefore, according to the infusion bag, it is possible to prevent the filled liquid drug from being denatured even before the heat sterilization treatment, during the heat sterilization treatment, after the heat sterilization treatment, after transportation, and after storage.

[In-mold label container]
The packaging material containing the multilayer structure of the present invention may be an in-mold label container. The in-mold label container includes a container body and a multilayer label (multilayer structure) of the present invention arranged on the surface of the container body. The container body is formed by injecting molten resin into the mold. The shape of the container body is not particularly limited, and may be cup-shaped, bottle-shaped, or the like.

An example of the method of the present invention for manufacturing a container is the first step of arranging the multilayer label of the present invention in the cavity between the female mold part and the male mold part, and injecting the molten resin into the cavity. This includes a second step of simultaneously molding the container body and attaching the multilayer label of the present invention to the container body. Each step can be performed in a known manner, except that the multilayer label of the present invention is used.

A cross-sectional view of an example of the container of the present invention is shown in FIG. The container 360 includes a cup-shaped container body 370 and a multilayer label 361 to 363 attached to the surface of the container body 370. Multi-layer labels 361-363 are multi-layer labels of the present invention. The container body 370 includes a flange portion 371, a body portion 372, and a bottom portion 373. The flange portion 371 has a convex portion 371a projecting vertically at its tip. The multilayer label 361 is arranged so as to cover the outer surface of the bottom 373. A through hole 361a for injecting resin during in-mold label molding is formed in the center of the multilayer label 361. The multilayer label 362 is arranged so as to cover the outer surface of the body portion 372 and the lower surface of the flange portion 371. The multilayer label 363 is arranged so as to cover a part of the inner surface of the body portion 372 and the upper surface of the flange portion 371. The multilayer labels 361 to 363 are fused to the container body 370 by the in-mold label molding method and are integrated with the container body 360. As shown in FIG. 4, the end face of the multilayer label 363 is fused to the container body 360 and is not exposed to the outside.

[Vacuum insulation]
The product of the present invention using at least a part of the above-mentioned packaging material may be a vacuum insulation body. The vacuum heat insulating body is a heat insulating body including a covering material and a core material arranged inside surrounded by the covering material, and the inside where the core material is arranged is depressurized. Vacuum insulation makes it possible to achieve insulation properties equivalent to those of urethane foam insulation with thinner and lighter insulation. The vacuum heat insulating body of the present invention is a heat insulating material for home appliances such as refrigerators, hot water supply facilities and rice cookers; a residential heat insulating material used for walls, ceilings, attics, floors, etc., vehicle roofing materials, automatic sales. Insulation panel for machines, etc .; Can be used for heat transfer equipment such as heat storage equipment and heat pump application equipment. The multilayer structure of the present invention used as a coating material preferably includes an ethylene-vinyl alcohol copolymer resin layer and an inorganic vapor-deposited layer, for example, a polyester layer / layer (Y) / polyester layer / layer (Y) /. It may have a structure of an inorganic vapor deposition layer / an ethylene-vinyl alcohol copolymer layer / a polyolefin layer.

An example of the vacuum insulation body of the present invention is shown in FIG. The vacuum heat insulating body 601 of FIG. 6 includes a particulate core material 651 and two multilayer structures 631, 632 of the present invention as a covering material for covering the core material 651. The two multilayer structures 631,632 are joined to each other at the peripheral edge portion 611. The internal space formed by the two multilayer structures 631 and 632 is filled with the core material 651, and the internal space thereof is depressurized. The multilayer structure 631, 632 functions as a partition wall 620 that separates the inside and the outside in which the core material 651 is housed, and is in close contact with the core material 651 due to the pressure difference between the inside and the outside of the vacuum heat insulating body 601. The inside where the core material 651 is arranged is depressurized.

Another example of the vacuum insulation body of the present invention is shown in FIG. The vacuum heat insulating body 602 has the same configuration as the vacuum heat insulating body 601 except that the core material 652 is integrally formed instead of the core material 651. The core material 652, which is a molded product, is typically a resin foam.

The material and shape of the core material are not particularly limited as long as they are suitable for heat insulation. Examples of the core material include pearlite powder, silica powder, precipitated silica powder, diatomaceous earth, calcium silicate, glass wool, rock wool, artificial (synthetic) wool, resin foam (for example, styrene foam, urethane foam) and the like. Can be mentioned. As the core material, a hollow container molded into a predetermined shape, a honeycomb structure, or the like can also be used.

[Electronic device]
The packaging material containing the multilayer structure of the present invention can also be used for electronic devices. A partial cross-sectional view of an example of the electronic device of the present invention is shown in FIG. The electronic device 40 of FIG. 8 includes an electronic device main body 41, a sealing material 42 for sealing the electronic device main body 41, and a protective sheet (multilayer structure) 43 for protecting the surface of the electronic device main body 41. , Equipped with. The sealing material 42 covers the entire surface of the electronic device main body 41. The protective sheet 43 is arranged on one surface of the electronic device main body 41 via a sealing material 42. The protective sheet 43 may also be arranged on the surface opposite to the surface on which the protective sheet 43 is arranged. In that case, the protective sheet arranged on the surface on the opposite side may be the same as or different from the protective sheet 43. The protective sheet 43 may be arranged on the electronic device main body 41 via another member such as a sealing material 42, or may be arranged directly on the surface of the electronic device main body 41.

The electronic device main body 41 is not particularly limited, and examples thereof include a photoelectric conversion device such as a solar cell; an information display device such as an organic EL display, a liquid crystal display, and an electronic paper; and a lighting device such as an organic EL light emitting element. The sealing material 42 is an arbitrary member that is appropriately added depending on the type and application of the electronic device main body 41. Examples of the sealing material 42 include ethylene-vinyl acetate copolymer and polyvinyl butyral.

A preferred example of the electronic device body 41 is a solar cell. Examples of the solar cell include a silicon-based solar cell, a compound semiconductor solar cell, an organic thin-film solar cell, and the like. Examples of the silicon-based solar cell include a single crystal silicon solar cell, a polycrystalline silicon solar cell, an amorphous silicon solar cell, and the like. Examples of the compound semiconductor solar cell include a III-V group compound semiconductor solar cell, an II-VI group compound semiconductor solar cell, and an I-III-VI group compound semiconductor solar cell. Further, the solar cell may be an integrated solar cell in which a plurality of unit cells are connected in series, or may not be an integrated solar cell.

The multilayer structure of the present invention and the packaging material containing the same are display members such as LCD substrate films, organic EL substrate films, electronic paper substrate films, electronic device encapsulation films, and PDP films; IC tag films. , A solar cell module, a back sheet for a solar cell, a protective film for a solar cell, and the like. When the multilayer structure is used as a member of a display, it is used, for example, as a low-reflection film. In any case, when the translucency of the multilayer structure is required, the translucent layer (Y) is used as the layer (Y).

Depending on the type of the electronic device main body 41, the electronic device main body 41 can be manufactured by a so-called roll-to-roll method. In the roll-to-roll method, a flexible substrate (for example, a stainless steel substrate, a resin substrate, etc.) wound on a delivery roll is sent out, and an element is formed on this substrate to manufacture an electronic device main body 41. The electronic device body 41 is taken up by a take-up roll. In this case, the protective sheet 43 may also be prepared in the form of a long sheet having flexibility, more specifically, in the form of a wound body of the long sheet. In one example, the protective sheet 43 delivered from the delivery roll is laminated on the electronic device main body 41 before being wound on the take-up roll, and is wound together with the electronic device main body 41. In another example, the electronic device main body 41 wound on the winding roll may be sent out from the roll again and laminated with the protective sheet 43. In a preferred example of the present invention, the electronic device itself has flexibility.

The protective sheet 43 includes the multilayer structure of the present invention. The protective sheet 43 may be composed of only the multilayer structure, or may include the multilayer structure and other members (for example, another layer (J)) laminated on the multilayer structure. The thickness and material of the protective sheet 43 are not particularly limited as long as the protective sheet 43 is a layered laminate suitable for protecting the surface of the electronic device and includes the multilayer structure.

The protective sheet 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 resin that is not easily scratched is preferable. Further, the surface protective layer of a device such as a solar cell that may be used outdoors is preferably made of a resin having high weather resistance (for example, light resistance). Further, when protecting a surface that needs to transmit light, a surface protective layer having high translucency is preferable. Examples of the material of the surface protective layer (surface protective film) include poly (meth) acrylic acid ester, polycarbonate, polyethylene terephthalate, polyethylene-2,6-naphthalate, polyvinyl fluoride (PVF), polyvinylidene fluoride (PVDF), and the like. Polytetrafluoroethylene (PTFE), polychlorotrifluoroethylene (PCTFE), ethylene-tetrafluoroethylene copolymer (ETFE), ethylene-chlorotrifluoroethylene copolymer (ECTFE), tetrafluoroethylene-perfluoroalkyl vinyl ether Examples thereof include a copolymer (PFA) and a tetrafluoroethylene-hexafluoropropylene copolymer (FEP). An example of a protective sheet comprises a poly (meth) acrylic acid ester layer disposed on one surface.

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

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

Details of the films used in Examples and Comparative Examples are shown.
1) PET12: Biaxially stretched polyethylene lethalate film; manufactured by Toray Industries, Inc., "Lumirror P60" (trade name), thickness 12 μm
2) ONY15: Biaxially stretched nylon film; manufactured by Unitika Ltd., "emblem ONBC" (trade name), thickness 15 μm
3) CPP60: Unstretched polypropylene film; manufactured by Mitsui Chemicals Tohcello Co., Ltd., "RXC-22" (trade name), thickness 60 μm
4) CPP100: Unstretched polypropylene film; manufactured by Mitsui Chemicals Tohcello Co., Ltd., "RXC-22" (trade name), thickness 100 μm

(1) Measurement of Infrared Absorption Spectrum The infrared absorption spectrum of the layer (Y) of the multilayer structure was measured by the attenuation total reflection method using a Fourier transform infrared spectrophotometer. The measurement conditions were as follows.
Equipment: Spectrum One manufactured by PerkinElmer Co., Ltd.
Measurement mode: Attenuated total reflection method Measurement area: 800 to 1,400 cm ^-1

(2) Measurement of thickness of each layer A multilayer structure was cut using a focused ion beam (FIB) to prepare a section (thickness 0.3 μm) for cross-sectional observation. The prepared section was fixed to a sample pedestal with carbon tape, and platinum ion sputtering was performed at an acceleration voltage of 30 kV for 30 seconds. The 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.
Equipment: JEM-2100F manufactured by JEOL Ltd.
Acceleration voltage: 200kV
Magnification: 250,000 times

(3) Measurement of oxygen permeability of the multilayer structure The multilayer structure was attached to the oxygen permeability measuring device so that the layer of the base material faces the carrier gas side, and the oxygen permeability was measured by the isobaric method. The measurement conditions were as follows.
Equipment: MOCON OX-TRAN2 / 21 manufactured by Modern Controls
Temperature: 20 ° C
Humidity on the oxygen supply side: 85% RH
Humidity on the carrier gas side: 85% RH
Oxygen pressure: 1.0 atm
Carrier gas pressure: 1.0 atm

(4) Measurement of moisture permeability of the multilayer structure The multilayer structure was attached to the water vapor transmission rate measuring device so that the layer of the base material faces the carrier gas side, and the moisture permeability (water vapor transmission rate) was measured by the isobaric method. The measurement conditions were as follows.
Equipment: MOCON PERMATRAN W3 / 33 manufactured by Modern Controls
Temperature: 40 ° C
Humidity on the steam supply side: 90% RH
Humidity on the carrier gas side: 0% RH

(5) Measurement of Delamination Occurrence Rate by Retort Bending Test An adhesive layer is formed on a multilayer structure coated in the order of base material (X) / layer (Z) / layer (Y), and ONY is applied on the adhesive layer. A laminate was obtained by laminating. Next, after forming an adhesive layer on the ONY of the laminated body, CPP60 was laminated on the adhesive layer and allowed to stand at 40 ° C. for 5 days for aging. Each of the two adhesive layers is a two-component adhesive (Mitsui Chemicals, Inc.'s "Takelac" (registered trademark) "A-520" (registered trademark) using a bar coater so that the thickness after drying is 3 μm. It was formed by coating (brand) and "A-50" (brand) of "Takenate" (registered trademark) manufactured by Mitsui Chemicals, Inc. and drying. Two base materials (X) / layer (Z) / layer (Y) / adhesive layer / ONY / adhesive layer / CPP60 thus obtained were laminated with CPP60 as a contact surface and heat-laminated at 130 ° C. Next, a strip of 160 mm × 40 mm was cut out, and holes with a diameter of 6 mm were made in a total of 14 places with a feeling of 20 mm. The strip was wound in the long direction with a radius of curvature of 8.5 mm, and the end was stapled to form a cylinder. Subsequently, the obtained cylinder was subjected to retort treatment (hot water storage type) under the following conditions.
Retort processing equipment: Flavor Ace RSC-60 manufactured by Hisaka Works, Ltd.
Temperature: 125 ° C
Time: 30 minutes Pressure: 0.17 MPaG
Four similar perforated cylinders were prepared for each sample, and the number of holes in which delamination occurred after the retort treatment was counted and divided by the total number of holes (56 locations) to calculate the delamination rate (%).

<Synthesis example of phosphorus compound (BH-1)>
Under a nitrogen atmosphere, 5.0 parts by mass of 11-bromoundecanol and 2.0 parts by mass of triethylamine were mixed with 5.0 parts by mass of dichloromethane and cooled to 0 ° C. A solution of 1.9 parts by mass of acetyl chloride mixed with 2.0 parts by mass of dichloromethane was added dropwise to this solution, and the mixture was stirred at 0 ° C. for 2 hours. The solution was washed with water until pH 6 and then the dichloromethane layer was isolated and dried over sodium sulfate. By distilling off the solvent, 5.5 parts by mass of 11-bromoundecyl acetate was obtained.

3.0 parts by mass of the obtained 11-bromoundecyl acetate and 4.0 parts by mass of triethylphosphite were mixed, and the mixture was stirred at 150 ° C. for 15 hours. Subsequently, excess triethylphosphite was distilled off under reduced pressure to obtain 3.3 parts by mass of diethyl (11-acetoxyundecyl) phosphonate.

3.3 parts by mass of the obtained diethyl (11-acetoxyundecyl) phosphonate was dissolved in 5.0 parts by mass of dioxane, 2.4 parts by mass of concentrated hydrochloric acid was added, and the mixture was stirred at 100 ° C. for 3 days. After cooling, diethyl ether was added to isolate the aqueous layer, and the aqueous layer was neutralized with 0.1% by mass aqueous sodium hydroxide solution until the pH of the aqueous layer reached 7. The precipitate was collected by filtration and reprecipitated with water and methanol to obtain 3.0 parts by mass of a sodium salt of 11-hydroxyundecylphosphonic acid. This was desalted with an ion exchange resin to obtain a phosphorus compound (BH-1). The phosphorus compound (BH-1) is 11-hydroxyundecylphosphonic acid (11-HUPA).

<Synthesis example of phosphorus compound (BH-2)>
2-Hydroxyethylphosphonic acid (2-HEPA) was obtained in the same manner as in the synthesis example of the phosphorus compound (BH-1) except that 2-bromoethanol was used instead of 11-bromoundecanol.

<Synthesis example of phosphorus compound (BH-3)>
20-Hydroxyeicosylphosphonic acid (20-HEPA) was obtained in the same manner as in the synthetic example of the phosphorus compound (BH-1) except that 20-bromoeicosanol was used instead of 11-bromoundecanol. It was.

<Production example of coating liquid (R-1)>
The phosphorus compound (BH-1) obtained in the synthesis example was dissolved in a mixed solvent of water and methanol (water: methanol = 7: 3 by mass ratio) at 25 ° C., and a coating solution having a solid content concentration of 1.0% by mass was dissolved. (R-1) was obtained.

<Production examples of coating liquids (R-2) and (R-3)>
The phosphorus compound (BH-1) obtained in the synthesis example was dissolved in a mixed solvent of water and methanol (water: methanol = 7: 3 by mass ratio) at 25 ° C., and a coating liquid having a solid content concentration of 8.0% by mass was dissolved. (R-2) and a coating liquid (R-3) having a solid content concentration of 12.0% by mass were obtained.

<Production examples of coating liquids (R-4) to (R-7) and (CR-1) to (CR-2)>
The coating liquids (R-4) to (R-7) and (CR-1) were prepared in the same manner as the coating liquid (R-1) except that the type with the phosphorus compound (BH) was changed as shown in Table 1. )-(CR-2) were prepared. In the preparation of the coating liquid (R-6), CHEMOS GmbH & Co. 4-Hydroxybutyl dihydrogen phosphate (4-HBDP) manufactured by KG was used. In the preparation of the coating liquid (R-7), 10-carboxydecylphosphonic acid (10-CDPA) manufactured by Dojin Chemical Laboratory Co., Ltd. was used as the phosphorus compound (BH-5). In the preparation of the coating liquid (CR-1), dodecylphosphonic acid manufactured by Wako Chemical Co., Ltd. was used instead of the phosphorus compound (BH-1). In the preparation of the coating liquid (CR-2), 1-dodecanol manufactured by Tokyo Chemical Industry Co., Ltd. was used instead of the phosphorus compound (BH-1).

<Production example of coating liquid (CR-3)>
As the main agent, a polyurethane resin having a silanol group in the resin skeleton [“Takelac WS-5000” manufactured by Mitsui Chemicals Co., Ltd. (hereinafter, may be abbreviated as “WS-5000”)] and an isocyanate-based curing agent [Mitsui Chemicals] "Takenate WD-725" manufactured by Co., Ltd. (hereinafter, may be abbreviated as "WD-725")] so as to have WS-5000 / WD-725 = 10/1 and a solid content concentration of 3.0% by mass. Was diluted with a mixed solvent of water and methanol (water: methanol = 7: 3 by mass ratio).

<Production example of coating liquid (S-1)>
The temperature was raised to 70 ° C. with stirring 230 parts by mass of distilled water. 88 parts by mass of triisopropoxyaluminum was added dropwise to the distilled water over 1 hour, the liquid temperature was gradually raised to 95 ° C., and the generated isopropanol was distilled off to carry out hydrolysis condensation. To the obtained liquid, 4.0 parts by mass of a 60% by mass nitric acid aqueous solution was added, and the mixture was stirred at 95 ° C. for 3 hours to deflocce the aggregates of the particles of the hydrolyzed condensate. Then, the liquid was concentrated so that the solid content concentration was 10% by mass in terms of aluminum oxide to obtain a solution. To 22.50 parts by mass of the solution thus obtained, 54.29 parts by mass of distilled water and 18.80 parts by mass of methanol were added and stirred so as to be uniform to obtain a dispersion liquid. Subsequently, 4.41 parts by mass of an 85% by mass phosphoric acid aqueous solution was added dropwise while stirring the dispersion while maintaining the liquid temperature at 15 ° C. Further, 18.80 parts by mass of a methanol solution was added dropwise, and stirring was continued at 15 ° C. until the viscosity became 1,500 mPa · s to obtain a target coating liquid (S1-1). The molar ratio of aluminum atom to phosphorus atom in the coating liquid (S1-1) was aluminum atom: phosphorus atom = 1.15: 1.00.

<Synthesis example of organic phosphorus compound (BO-1)>
Under a nitrogen atmosphere, 10 g of vinyl phosphonic acid and 0.025 g of 2,2'-azobis (2-amidinopropane) dihydrochloride were dissolved in 5 g of water and stirred at 80 ° C. for 3 hours. After cooling, 15 g of water was added to the polymerization solution to dilute the solution, and the mixture was filtered using "Spectra / Por" (registered trademark) manufactured by Spectrum Laboratories, which is a cellulose film. After distilling off the water in the filtrate, the polymer (BO-1) was obtained by vacuum drying at 50 ° C. for 24 hours. The polymer (BO-1) is poly (vinyl phosphonic acid). As a result of GPC analysis, the number average molecular weight of the polymer was 10,000 in terms of polyethylene glycol.

<Production example of coating liquid (T-1)>
67% by mass of the organophosphorus compound (BO-1) obtained in the synthesis example, and 33% by mass of polyethylene glycol ("PEG-20000" manufactured by Sanyo Kasei Kogyo Co., Ltd.) having a weight average molecular weight of 20,000 as the polymer compound (F). A mixture containing% was prepared. This mixture was dissolved in a mixed solvent of water and methanol (water: methanol = 7: 3 in terms of mass ratio) to obtain a coating liquid (T-1) having a solid content concentration of 1% by mass. It was.

[Example 1]
<Example 1-1>
PET12 (base material (X-1)) was prepared as the base material (X). A coating liquid (R-1) was applied onto this substrate using a bar coater so that the thickness after drying was 0.010 μm. The coated film was dried at 140 ° C. for 1 minute to form a layer (Z-1-1) on the substrate. Subsequently, the coating liquid (S-1) was applied using a bar coater so that the thickness after drying was 0.3 μm. The coated film was dried at 120 ° C. for 3 minutes and then heat treated at 180 ° C. for 1 minute to form a layer (Y-1) precursor on the substrate. Then, the inorganic phosphorus compound (BI) Weight W _BI and the organic phosphorus compound (BO) ratio W _BO / W coating solution with a bar coater such that _BI = 1.10 / 98.90 mass W _BO of ( T-1) was applied and dried at 110 ° C. for 3 minutes. In this way, a structure having a structure of a base material (X-1) / layer (Z-1-1) / layer (Y-1) precursor was obtained. Subsequently, the structure was heat-treated at 220 ° C. for 1 minute to form a layer (Y-1). In this way, a multilayer structure (1-1) having a structure of a base material (X-1) / layer (Z-1-1) / layer (Y-1) was obtained.

Multilayer structure (1-1) Results of the infrared absorption spectrum was measured by the method (1), the maximum absorption wave number in the region of 800～1,400Cm ^-1 is 1,108Cm ^-1, said maximum absorption band The half-value width of was 37 cm ^-1 .

An adhesive layer was formed on the obtained multilayer structure (1-1), and ONY15 was laminated on the adhesive layer to obtain a laminated body. Next, after forming an adhesive layer on ONY15 of the laminated body, CPP60 was laminated on the adhesive layer and allowed to stand at 40 ° C. for 5 days for aging. In this way, a multilayer structure (1-2) having a structure of a base material (X) / layer (Z-1-1) / layer (Y-1) / adhesive layer / ONY15 / adhesive layer / CPP60 is obtained. It was. Each of the two adhesive layers was formed by applying a two-component adhesive using a bar coater so that the thickness after drying was 4 μm, and drying the adhesive layer. Two-component adhesives include "A-520" (brand) of "Takelac" (registered trademark) manufactured by Mitsui Chemicals, Inc. and "A-50" of "Takenate" (registered trademark) manufactured by Mitsui Chemicals, Inc. A two-component reaction type polyurethane adhesive consisting of (brand) was used. The oxygen permeability and moisture permeability of the multilayer structure (1-2) were measured by the methods (3) and (4) above. The results are shown in Table 2.

A pouch was prepared by heat-sealing the multilayer structure (1-2), and 100 g of water was filled in the pouch. 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 Works, Ltd.
Temperature: 125 ° C
Time: 30 minutes Pressure: 0.17 MPaG

Immediately after the hot water treatment, a measurement sample was cut out from the pouch, and the oxygen permeability and moisture permeability of the sample were measured by the methods (3) and (4) above. The results are shown in Table 2.

Using the multilayer structure (1-2), the delamination occurrence rate was measured by the retort bending test by the method (5) above. The results are shown in Table 2.

<Examples 1-2-1-7>
The multilayer structure is the same as that of the multilayer structure (1-1) of Example 1 except that the coating liquids (R-2) to (R-7) are used instead of the coating liquid (R-1). (2-1) to (7-1) were prepared. The multilayer structure is the same as that of the multilayer structure (1-2) of Example 1 except that the multilayer structures (2-1) to (7-1) are used instead of the multilayer structure (1-1). (2-2) to (7-2) were prepared and evaluated. The results are shown in Tables 1 and 2.

<Comparative Example 1-1>
Multilayer structures (C1-1) and (C1-2) were prepared and evaluated by the same method as in Example 1 except that the coating liquid (R-1) was not used. The results are shown in Tables 1 and 2.

<Comparative Examples 1-2 to 1-4>
The multilayer structure is the same as that of the multilayer structure (1-1) of Example 1 except that the coating liquids (CR-1) to (CR-3) are used instead of the coating liquid (R-1). (C2-1) to (C4-1) were prepared. The multilayer structure is the same as that of the multilayer structure (1-2) of Example 1 except that the multilayer structures (C2-1) to (C4-1) are used instead of the multilayer structure (1-1). (C2-2) to (C4-2) were prepared and evaluated. The results are shown in Tables 1 and 2.

[Example 2] Flat pouch <Example 2-1>
The multilayer structure (1-2) produced in Example 1-1 is cut into a width of 120 mm × 120 mm, the two multilayer structures are overlapped so that the CPP layer is on the inside, and the three sides of the rectangle are heat-sealed. By doing so, a flat pouch (2-1-3) was formed. The flat pouch was filled with 100 mL of water. As a result of performing a retort treatment (hot water storage type) on the obtained flat pouch under the same conditions as in Example 1-1, good appearance was maintained without occurrence of bag breakage and delamination.

[Example 3] Infusion bag <Example 3-1>
From the multilayer structure (1-2) produced in Example 1-1, two 120 mm × 100 mm multilayer structures were cut out. Subsequently, the two cut-out multilayer structures are superposed so that the CPP layer is on the inside, the peripheral edge is heat-sealed, and a polypropylene spout (spout member) is attached by heat-sealing. An infusion bag (3-1-3) having a similar structure was prepared. As a result of filling the infusion bag (3-1-3) with 100 mL of water and performing retort treatment (hot water storage type) under the same conditions as in Example 1-1, the appearance was good without bag breakage and delamination. Was held.

[Example 4] Container lid material <Example 4-1>
From the multilayer structure (1-2) produced in Example 1-1, a circular multilayer structure having a diameter of 100 mm was cut out and used as a lid material for a container. Further, as the container body, a container with a flange (manufactured by Toyo Seikan Co., Ltd., "Hiretflex" (registered trademark), "HR78-84" (trade name)) was prepared. This container has a cup shape with an upper surface diameter of 78 mm and a height of 30 mm. The upper surface of the container is open, and the width of the flange portion formed on the peripheral edge thereof is 6.5 mm. The container is composed of a three-layer laminate of an olefin layer / a steel layer / an olefin layer. Next, the container body was filled with water almost completely, and the lid material was heat-sealed to the flange portion to obtain a container with a lid (4-1-3). At this time, the CPP layer of the lid material was arranged so as to be in contact with the flange portion, and the lid material was heat-sealed. As a result of performing a retort treatment (hot water storage type) on the container with a lid (4-1-3) under the same conditions as in Example 1-1, the container was not damaged and delamination did not occur, and a good appearance was maintained. did.

[Example 5] In-mold label container <Example 5-1>
Each of the two CPP100s was coated with a two-component adhesive using a bar coater so that the thickness after drying was 3 μm, and dried. The two-component adhesive consists of "A-520" of "Takelac" (registered trademark) manufactured by Mitsui Chemicals, Inc. and "A-50" of "Takenate" (registered trademark) manufactured by Mitsui Chemicals, Inc. A two-component reactive polyurethane adhesive was used. Next, the two CPP100s and the multilayer structure (1-1) of Example 1-1 were laminated, allowed to stand at 40 ° C. for 5 days for aging, and then CPP100 / adhesive layer / substrate (X-). A multilayer label (5-1-2) having a structure of 1) / layer (Z-1-1) / layer (Y-1) / adhesive layer / CPP100 was obtained.

The multilayer label (5-1-2) was cut according to the shape of the inner wall surface of the female mold portion of the container molding mold, and attached to the inner wall surface of the female mold portion. Next, the male mold part was pushed into the female mold part. Next, molten polypropylene (“EA7A” of “Novatec” (registered trademark) manufactured by Japan Polypropylene Corporation) is injected into the cavity between the male and female molds at 220 ° C. for injection molding. This was carried out and the target container (5-1-3) was molded. The thickness of the container body was 700 μm, and the surface area was 83 cm ² . The entire outside of the container is covered with the multi-layer label (5-1-2), the joints are overlapped with the multi-layer label (5-1-2), and the multi-layer label (5-1-2) does not cover the outside of the container. There wasn't. The appearance of the container (5-1-3) was good.

[Example 6] Extruded coat laminate <Example 6-1>
After forming an adhesive layer on the layer (Y-1) on the multilayer structure (1-1) in Example 1-1, the polyethylene resin (density; 0.917 g / cm ³ , melt flow rate; 8 g / 10). Minutes) are extruded and coated-laminated on the adhesive layer at 295 ° C. so as to have a thickness of 20 μm, and the base material (X-1) / layer (Z-1-1) / layer (Y-1) / adhesive A laminated body (6-1-2) having a layer / polyethylene structure was obtained. The above-mentioned adhesive layer was formed by applying a two-component adhesive using a bar coater so that the thickness after drying was 0.3 μm, and drying the adhesive layer. This two-component adhesive consists of "Takelac" (registered trademark) "A-3210" manufactured by Mitsui Chemicals, Inc. and "Takenate" (registered trademark) "A-3070" manufactured by Mitsui Chemicals, Inc. A two-component reaction type polyurethane adhesive was used. As a result of performing a retort treatment (hot water storage type) on the laminated body (6-1-2) under the same conditions as in Example 1-1, delamination did not occur and a good appearance was maintained.

[Example 7] Effect of packing <Example 7-1>
The flat pouch (2-1-3) prepared in Example 2-1 was filled with 500 mL of a 1.5% ethanol aqueous solution, and 120 using a retort processing device (Flavor Ace RCS-60 manufactured by Hisaka Works). As a result of retort treatment in hot water at 2.5 atm for 30 minutes, no delamination occurred and a good appearance was maintained.

<Examples 7-2 to 7-9>
The retort treatment was carried out in the same manner as in Example 7-1, except that the flat pouch (2-1-3) was filled with 500 mL of another filling 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 fillings include 1.0% aqueous ethanol solution (Example 7-2), vinegar (Example 7-3), aqueous citric acid solution at pH 2 (Example 7-4), and cooking oil (Example 7-). 5), ketchup (Example 7-6), soy sauce (Example 7-7), and ginger paste (Example 7-8) were used. In each case, the oxygen permeability of the sample after the retort treatment was 0.2 mL / (m2 · day · atm). Further, the container with a lid (5-1-3) prepared in Example 5-1 was filled with mandarin orange syrup almost completely, and retort treatment was performed in the same manner as in Example 7-1 (Example 7-9). .. After the retort treatment, delamination did not occur 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 retort-packed with various foods.

[Example 8] Vacuum insulation <Example 8-1>
The two-component adhesive used in Example 5-1 was applied onto CPP60 so that the thickness after drying was 3 μm, and the adhesive layer was formed by drying. A laminate (8-1-1) was obtained by laminating this CPP with the PET layer of the multilayer structure (1-1-1) produced in Example 1-1. Subsequently, the two-component reaction type polyurethane adhesive was applied onto ONY so that the thickness after drying was 3 μm, and the adhesive layer was formed by drying. Then, by laminating this ONY and the laminated body (8-1-1), CPP / adhesive layer / base material (X-1) / layer (Z-1-1) / layer (Y-1) / A multilayer structure (8-1-2) having a structure of an adhesive layer / ONY was obtained.

The multilayer structure (8-1-2) was cut to obtain two laminated bodies having a size of 700 mm × 300 mm. The two laminated bodies were laminated so that the CPP layers were on the inner surface, and heat-sealed on three sides 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 using a vacuum packaging machine at 20 ° C. and an internal pressure of 10 Pa to form a vacuum insulation body (8-1- 3) was obtained. Silica fine powder was used as the heat insulating core material. After leaving the vacuum insulation body (8-1-3) at 40 ° C. and 15% RH for 360 days, the pressure inside the vacuum insulation body was measured using a Pirani vacuum gauge and found to be 37.0 Pa. It was.

[Example 9] Protective sheet <Example 9-1>
An adhesive layer was formed on the multilayer structure (1-1) produced 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) of the laminated body, PET50 is laminated, and PET / adhesive layer / base material (X-1) / layer (Z-1-1). ) / Layer (Y-1) / Adhesive layer / Acrylic resin film, a protective sheet (9-1-1) was obtained. Each of the two adhesive layers was formed by applying a two-component adhesive so that the thickness after drying was 3 μm and drying. The two-component adhesive consists of "Takelac" (registered trademark) "A-1102" manufactured by Mitsui Chemicals, Inc. and "Takenate" (registered trademark) "A-3070" manufactured by Mitsui Chemicals, Inc. A two-component reactive polyurethane adhesive was used.

Subsequently, as a durability test of the obtained protective sheet (9-1-1), a protective sheet was used for 1,000 hours under atmospheric pressure, 85 ° C., and 85% RH using a constant temperature and humidity tester. As a result of a test (dump heat test) in which the waste was stored, a good appearance was maintained without delamination.

The present invention can be used for a multilayer structure, a packaging material using the multilayer structure, and a method for producing the multilayer structure. According to the present invention, it is possible to obtain a multilayer structure having high interlayer adhesive strength (peeling strength) without causing appearance defects such as delamination while maintaining excellent barrier properties even after retort treatment. .. Further, by using the multilayer structure of the present invention, excellent packaging materials and electronic devices can be obtained.

10 Vertical filling seal bag 11 Multi-layer structure 11a End 11b Body 20 Flat pouch 11c Periphery 401 Infusion bag 410a, 410b Film material (multi-layer structure)
411, 421, 413, 414 Peripheral part 420 Partition 431 Bag body 432 Plug member 433 Hanging hole 360 Container 361, 362, 363 Multi-layer label 361a Through hole 370 Container body 371 Flange part 372 Body part 373 Bottom part 371a Convex part 50 Device 51 Extruder 52 T-die 53 Cooling roll 54 Rubber roll 501 Laminated body 502 Resin film 503 Laminated film (multilayer structure)
601 and 602 Vacuum insulation 611 Peripheral part 620 Partition 610, 631, 632 Multilayer structure 651, 652 Core material 40 Electronic device 41 Electronic device body 42 Encapsulant 43 Protective sheet (multilayer structure)

Claims (14)

A base material (X), a layer (Z) laminated on the base material (X), and a layer (Y) laminated on the layer (Z) are included.
The layer (Z) contains a phosphorus compound (BH) in which a polar group is bonded to a phosphorus atom having at least one hydroxyl group by an alkylene chain having 20 or less carbon atoms or a polyoxyalkylene chain.
The layer (Y) contains an aluminum-containing compound (A), and the aluminum-containing compound (A) is a reaction product (D) of an aluminum-containing metal oxide (Aa) and an inorganic phosphorus compound (BI). a compound containing an (Ab) seen including,
A multilayer structure in which the polar group of the phosphorus compound (BH) is a carboxyl group or a hydroxyl group. The phosphorus atom having at least one hydroxyl group of the phosphorus compound (BH) is selected from the group consisting of a phosphoric acid group, a phosphorous acid group, a phosphonic acid group, a phosphonic acid group, a phosphinic acid group, and a phosphinic acid group. The multilayer structure according to claim 1, which is at least one functional group. The multilayer structure according to claim 1 or 2 , wherein the oxygen permeability under the conditions of 20 ° C. and 85% RH is 2.0 mL / (m ² · day · atm) or less. The multilayer structure according to any one of claims 1 to 3 , wherein the moisture permeability under the conditions of 40 ° C. and 90/0% RH is 2.0 g / (m ² · day) or less. The multilayer structure according to any one of claims 1 to 4 , wherein the base material (X) contains at least one layer selected from the group consisting of a thermoplastic resin film and paper. The method for manufacturing a multilayer structure according to claim 1.
A coating liquid (BH) containing a phosphorus compound (BH) in which a phosphorus atom having at least one hydroxyl group and a polar group are bonded to a base material (X) by an alkylene chain having 20 or less carbon atoms or a polyoxyalkylene chain, and a solvent ( The step (I) of forming the layer (Z) by applying R) and
Step (II) of forming a layer (Y) precursor by applying a coating liquid (S) containing an aluminum-containing compound (A), an inorganic phosphorus compound (BI), and a solvent onto the layer (Z). When,
A production method comprising a step (III) of forming a layer (Y) by heat-treating the layer (Y) precursor. A packaging material comprising the multilayer structure according to any one of claims 1 to 5. The packaging material according to claim 7 , further comprising a layer formed by an extruded coat laminate. The packaging material according to claim 7 or 8 , which is a vertical bag filling 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. A product in which at least a part of the packaging material according to any one of claims 7 to 9 is used. The product according to claim 10 , wherein the product contains a content, the content is a core material, the inside of the product is depressurized, and the product functions as a vacuum heat insulating body. A protective sheet for an electronic device, comprising the multilayer structure according to any one of claims 1 to 5. The protective sheet for an electronic device according to claim 12 , which is a protective sheet for protecting the surface of a photoelectric conversion device, an information display device, or a lighting device. An electronic device having the protective sheet according to claim 12 or 13.

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