JP6960837B2 - Multi-layer structure and products using it - Google Patents

Description

The present invention relates to a multilayer structure having excellent barrier properties and a product using the same.

The multilayer structure that prevents the permeation of gas and water vapor is used for applications such as food, industry, and medical fields to prevent the contents from being exposed to gas and water vapor. Patent Document 1 describes a thin film layer made of an inorganic oxide. A multilayer structure having a gas barrier property obtained by a method of forming on a base material by a vapor deposition method is described. However, in the thin-film deposition method, since it is necessary to uniformly deposit the thin film layer on the substrate under high vacuum, the shape and material of the substrate are greatly limited, and the thickness of the vapor deposition layer is also limited.

On the other hand, as a laminate using a manufacturing method other than the vapor deposition method, Patent Document 2 describes the gas barrier property obtained by applying a coating liquid containing alumina particles and a phosphorus compound on a substrate, and then drying and heat-treating. The laminated body to have is described. In the case of such a manufacturing process, the shape and material of the base material that can be used are not limited as compared with the vapor deposition method, and the coating liquid can be applied with a desired thickness.

Japanese Unexamined Patent Publication No. 2004-106443 International Publication 2011/122030

The coating liquid is basically hydrophilic, and a polyester film is often used as a base material on which the coating liquid is applied. Among them, a polyethylene terephthalate film (hereinafter, abbreviated as "PET") which is inexpensive and has high strength. In some cases) is often used.

However, since the PET surface is hydrophobic, the water contact angle is high, and when a manufacturing process by coating a hydrophilic coating liquid is included, the PET surface is surface-treated such as a high-energy hydrophilic treatment in order to improve the coatability. Is required, which may contribute to an increase in the manufacturing cost of the multilayer structure.

An object of the present invention is to provide a multilayer structure having excellent barrier properties and a product using the same, which reduces the energy used in the surface treatment step or eliminates the need for the surface treatment step.

According to the present invention, the above object is
[1] A multilayer structure including a base material (X) and a layer (Y), wherein the base material (X) contains a polyester (C) having a heterocyclic structure (C1), and the layer (Y) is A multilayer structure containing a reaction product (R) of a metal oxide (A) containing aluminum and an inorganic phosphorus compound (BI);
[2] The multilayer structure of [1] in which the heterocyclic structure (C1) is contained in the main chain of the polyester (C);
[3] As the monomer unit constituting the polyester (C), it has a diol unit having a heterocyclic structure (C1), a monocarboxylic acid monool unit having a heterocyclic structure (C1), or a heterocyclic structure (C1). [1] or [2] multilayer structure containing a dicarboxylic acid unit;
[4] The content of the monomer unit having a heterocyclic structure (C1) is 25 to 50 mol% with respect to all the monomer units constituting the polyester (C), [1] to [3]. One of the multilayer structures;
[5] The multilayer structure according to any one of [1] to [4], wherein the heterocyclic structure (C1) has at least one polar atom selected from the group consisting of an oxygen atom, a nitrogen atom and a sulfur atom;
[6] The multilayer structure of [5] in which the heterocyclic structure (C1) is a furan ring structure;
[7] The multilayer structure of [6], wherein the monomer unit having a heterocyclic structure (C1) is 2,5-furandicarboxylic acid;
[8] The multilayer structure according to any one of [1] to [7], wherein the polyester (C) is a polyester having an aliphatic diol unit;
[9] The aliphatic diol unit contains at least one aliphatic diol unit selected from the group consisting of ethylene glycol units, diethylene glycol units, 1,3-propanediol units and 1,4-butanediol units [8]. ] Multi-layer structure;
[10] The multilayer structure of [8] or [9], wherein the content of the aliphatic diol unit is 25 to 50 mol% with respect to all the monomer units constituting the polyester (C);
[11] The multilayer structure according to any one of [1] to [10], wherein the base material (X) and the layer (Y) are adjacent to each other via the adhesive layer (I);
[12] The multilayer structure according to any one of [1] to [10], wherein the base material (X) and the layer (Y) are directly laminated;
[13] The multilayer structure according to any one of [1] to [12], wherein the water contact angle on the surface of the base material (X) is 10 ° to 78 °;
[14] A product containing the multilayer structure according to any one of [1] to [13];
[15] The product 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 container lid material, an in-mold label container, a vacuum insulator, or an electronic device. The product of [14];
Is achieved by providing.

Since the multilayer structure of the present invention uses a hydrophilic base material, the hydrophilic coating liquid has good coatability, and the energy used in the surface treatment step of the base material is reduced or the surface treatment step itself is omitted. be able to. That is, according to the present invention, it is possible to provide a multilayer structure having excellent barrier properties and a product using the same, which reduces the energy used in the surface treatment step or does not require the surface treatment step.

It is the schematic of the vertical bag filling seal bag which concerns on one Embodiment of this invention. It is the schematic of the flat pouch which concerns on one Embodiment of this invention. It is a schematic diagram which shows an example of the infusion bag which concerns on one Embodiment of this invention. It is a schematic diagram which shows an example of the in-mold label container which concerns on one Embodiment of this invention. It is a 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. It is a schematic diagram which shows an example of the vacuum insulation body which concerns on one Embodiment of this invention. It is a schematic diagram which shows another example of the vacuum insulation body which concerns on one Embodiment of this invention. It is a partial cross-sectional view of the electronic device which concerns on one Embodiment of this invention.

Hereinafter, embodiments of the present invention will be described. In the following description, a specific material (compound or the like) may be exemplified as a material exhibiting a specific function, but the present invention is not limited to the mode in which such a material is used. Further, unless otherwise specified, the exemplified substances may be used alone or in combination of two or more.

[Multi-layer structure]
The multilayer structure of the present invention includes a base material (X) and a layer (Y). The base material (X) contains a polyester (C) having a heterocyclic structure (C1) (hereinafter, may be abbreviated as "polyester (C)"), and the layer (Y) is a metal oxide (A) containing aluminum. ) (Hereinafter, it may be abbreviated as "metal oxide (A)") and the reaction product (R) of the inorganic phosphorus compound (BI). In the following description, unless otherwise noted, the phrase "multilayer structure" means a multi-layer structure that includes a substrate (X) and a layer (Y).

[Base material (X)]
The base material (X) contains a polyester (C) having a heterocyclic structure (C1). When the base material (X) contains the polyester (C), the hydrophilicity of the base material (X) is increased, and the affinity between the coating liquid (S) described later and the base material (X) is improved. As a result, it is possible to reduce the energy used or eliminate the need for a surface treatment step in the surface treatment step performed when a normal PET is used as a base material.

The base material (X) is preferably in a layered form such as a film or a sheet from the viewpoint of improving coatability.

From the viewpoint of improving the coatability of the base material (X), the content of the polyester (C) in the base material (X) is preferably 65% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more. It may be 100% by mass.

[Polyester (C) having a heterocyclic structure (C1)]
The heterocyclic structure (C1) may be contained in the main chain or the side chain in the polyester (C), but is preferably contained in the main chain from the viewpoint of reducing the manufacturing cost.

As a means for producing the polyester (C), a diol having a heterocyclic structure (C1), a monocarboxylic acid monool having a heterocyclic structure (C1), or a dicarboxylic acid having a heterocyclic structure (C1) is used as a raw material and is heavy. General means such as a method of performing condensation can be selected. When producing the polyester (C), one type of monomer unit having a heterocyclic structure (C1) may be used alone, or two or more types may be mixed and used. By using the monomer unit as a raw material, a base material (X) having good coatability can be produced while suppressing the production cost.

From the viewpoint of improving coatability, the content of the monomer unit having a heterocyclic structure (C1) is preferably 25 to 50 mol% with respect to all the monomer units constituting the polyester (C). 30 to 50 mol% is more preferable, and 35 to 50 mol% is further preferable.

The heterocyclic structure (C1) is preferably a 5- to 7-membered ring structure from the viewpoint of the stability of the ring structure.

The heterocyclic structure (C1) more preferably has at least one polar atom selected from the group consisting of oxygen atoms, nitrogen atoms and sulfur atoms, and at least one polar atom selected from the group consisting of oxygen atoms and nitrogen atoms. It is more preferable to have an oxygen atom, and it is particularly preferable to have an oxygen atom. When the polyester (C) has the polar atom, the hydrophilicity of the base material (X) can be further enhanced.

The heterocyclic structure (C1) is an oxygen-containing heterocyclic structure such as a furan ring structure, a tetrahydrofuran ring structure, a pyran ring structure, a tetrahydropyran ring structure, a dioxane ring structure, an oxycycloheptatriene ring structure, or a hexamethylene oxide ring structure. A nitrogen-containing heterocyclic structure such as a pyrrol ring structure, a pyrrolidine ring structure, an imidazole ring structure, a pyrazole ring structure, an imidazoline ring structure, a pyridine ring structure, a piperidine ring structure, a pyrazine ring structure, an azetropyridene ring structure, and a hexamethyleneimine ring structure; Sulfur-containing heterocyclic structures such as thiophene ring structure, tetrahydrothiophene ring structure, thiapyran ring structure, tetrahydrothiopyran ring structure, thiotropyridene ring structure, hexamethylene sulfide ring structure; oxazole ring structure, thiazole ring structure, morpholin ring structure, thiazine ring. Examples thereof include a heterocyclic structure containing two or more types of heteroatoms such as a structure, which comprises a furan ring structure, a tetrahydrofuran ring structure, a pyrrole ring structure, a pyrrolidine ring structure, a tetrahydropyran ring structure, a pyridine ring structure and a piperidine ring structure. It preferably has at least one ring structure selected from the group. Having the above-mentioned specific ring structure is preferable because the hydrophilicity of the base material (X) is further increased. Further, from the viewpoint of inexpensive production, the heterocyclic structure (C1) is preferably a furan ring structure.

When the heterocyclic structure (C1) has a furan ring structure, it is preferable to use furan having a functional group capable of polycondensation at the 2- and 5-positions of the furan ring structure as a monomer unit from the viewpoint of enhancing heat resistance. .. At that time, the 3-position and 4-position of the furan ring structure may have a substituent other than hydrogen, for example, an alkyl group having 1 to 10 carbon atoms, an aromatic group having 1 to 18 carbon atoms, a halogen, and carbon. It may have a substituent such as an alkoxy group of several 1 to 10. From the viewpoint of reducing the production cost, hydrogen is preferable as the substituent at the 3-position and 4-position of the furan ring structure.

Examples of the monomer unit having a heterocyclic structure (C1) include 2,5-dihydroxyfuran, which is a diol having a heterocyclic structure (C1), and monool, a monocarboxylic acid having a heterocyclic structure (C1). -Hydroxyfuran-5-carboxylic acid, 2,5-furandicarboxylic acid which is a dicarboxylic acid having a heterocyclic structure (C1), derivatives thereof and the like can be used. Examples of the derivative include an esterified product in which a hydroxyl group and a carboxylic acid group are esterified, and for example, an alkyl ester having 1 to 4 carbon atoms can be used. When the esterified product is used, methyl ester, ethyl ester, n-propyl ester and isopropyl ester are preferable, and methyl ester is more preferable. As the monomer unit having the heterocyclic structure (C1), it is preferable to use 2,5-furandicarboxylic acid from the viewpoint of obtaining polyester (C) having excellent heat resistance at low cost.

Examples of the raw material that can be copolymerized with the raw material having the heterocyclic structure (C1) include aliphatic diols, aromatic dihydroxy compounds, bisphenols, aliphatic dicarboxylic acids, aromatic dicarboxylic acids, hydroxycarboxylic acids, and derivatives thereof. In particular, aliphatic diols, aliphatic dicarboxylic acids and esters thereof, and aromatic dicarboxylic acids and esters thereof are preferable, and aliphatic diols are more preferable.

Examples of copolymerizable aliphatic dicarboxylic acids and derivatives thereof include oxalic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, dimer acid, dodecanedioic acid, 1,6-cyclohexanedicarboxylic acid, and their acids. Examples thereof include anhydrides and lower alkyl esters. Of these, succinic acid, glutaric acid, sebacic acid, dimer acid and dodecanedioic acid, and lower alkyl (for example, alkyl having 1 to 4 carbon atoms) ester derivatives thereof are preferable, and in particular, lower alkyl ester derivatives of succinic acid and succinic acid, or The mixture is preferred. These may be used alone or in combination of two or more.

Examples of copolymerizable aromatic dicarboxylic acids and derivatives thereof include terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid and diphenyldicarboxylic acid, acid anhydrides thereof, lower alkyl esters and the like. Of these, terephthalic acid and isophthalic acid, and their lower alkyl (for example, alkyl having 1 to 4 carbon atoms) ester derivatives are preferable, and methyl ester derivatives of terephthalic acid and terephthalic acid, or mixtures thereof are particularly preferable. These may be used alone or in combination of two or more.

Examples of the copolymerizable aliphatic diol include ethylene glycol, diethylene glycol, triethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,5-pentanediol, and 1, , 6-Hexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, isosorbide and the like. Of these, ethylene glycol, diethylene glycol, 1,3-propanediol and 1,4-butanediol are preferable from the viewpoint of the physical characteristics of the obtained thermoplastic resin.

Examples of copolymerizable hydroxycarboxylic acids and derivatives thereof include lactic acid, glycolic acid, 2-hydroxy-n-butyric acid, 2-hydroxycaproic acid, 6-hydroxycaproic acid, 2-hydroxy-3,3-dimethylbutyric acid. , 2-Hydroxy-3-methylbutyric acid, 2-hydroxyisocaproic acid, mandelic acid, salicylic acid, and esters, acidified products, acid anhydrides and the like thereof. These may be used alone or in combination of two or more.

The polyester (C) is preferably a polyester having a diol unit and a dicarboxylic acid unit. The diol unit is preferably an aliphatic diol unit, more preferably ethylene glycol. Further, as the dicarboxylic acid unit, a dicarboxylic acid unit having a heterocyclic structure (C1) is preferable, a dicarboxylic acid unit having a furan ring structure is more preferable, and a 2,5-furandicarboxylic acid unit is further preferable. That is, the polyester (C) is preferably a polyester having an ethylene glycol unit and a 2,5-furandicarboxylic acid unit. By having the above-mentioned structure, the content of polar groups is increased as compared with PET, the affinity between the coating liquid (S) and the base material (X), which will be described later, is improved, and the coatability is improved. ..

When the polyester (C) has 2,5-furandicarboxylic acid units, the content of the 2,5-furandicarboxylic acid units is preferably 25 mol% or more, preferably 30 mol% or more, based on all the monomer units of the polyester (C). Is more preferable, and 35 mol% or more is further preferable. The content of 2,5-furandicarboxylic acid units is usually 50 mol% or less. When the 2,5-flangecarboxylic acid unit is 25 mol% or more, excellent coatability due to the polar group tends to be exhibited.

When the polyester (C) has an aliphatic diol unit, the content thereof is preferably 25 mol% or more, more preferably 30 mol% or more, still more preferably 35 mol% or more, based on all the monomer units of the polyester (C). The content of the aliphatic diol unit is usually 50 mol% or less.

When the polyester (C) has a 2,5-furandicarboxylic acid unit and an aliphatic diol unit, the content of the other monomer units is preferably 50 mol% or less, preferably 30 mol% or less, based on the total monomer units of the polyester (C). More preferably, 10 mol% or less is further preferable, 5 mol% or less is particularly preferable, and 0 mol% may be used. The content of the other monomer unit is preferably 50 mol% or less from the viewpoint of heat resistance and moldability.

The polyester (C) may have a polyfunctional compound having three or more carboxyl groups or hydroxyl groups as a monomer unit, for example, trimellitic acid, pyromellitic acid, trimesic acid, trimethylolpropane, pentaerythritol. And their ester derivatives and the like. The melt tension can be increased by having a trace amount of the polyfunctional compound, and it can be used to adjust the melt moldability. The content of the polyfunctional compound unit in the polyester is preferably 1 mol% or less, more preferably 0.5 mol% or less. When the content of the polyfunctional compound unit is 1 mol% or less, gelation tends to be suppressed.

The polyester (C) may have a monofunctional compound having only one carboxyl group or a hydroxyl group as a monomer unit, for example, benzoic acid, 2,4,6-trimethoxybenzoic acid, 2-naphthoic acid. , Stearic acid and derivatives thereof. These may be added to function as a sealing monomer unit, to seal the molecular chain end groups in the polyester, and to prevent excessive cross-linking and gel formation in the polyester. The content of the monofunctional compound unit in the polyester (C) is preferably 1 mol% or less, more preferably 0.5 mol% or less. When the ratio of the monofunctional compound unit is 1 mol% or less, it tends to be possible to suppress the occurrence of excessive cross-linking and gelation while maintaining the polymerization rate of the polyester.

Examples of the polyester (C) include polymethylene furanoate, polydimethylene furanoate, polytrimethylene furanoate, polyethylene furanoate, polypropylene furanoate, polybutylene furanoate and the like. Of these, polyethylene furanoate is preferable from the viewpoint of high efficiency and low cost.

As a method for producing the polyester (C), a method of melt-polycondensing the above-mentioned raw material of the polyester (C) or a method of solid-phase polymerization after the melt-polycondensation is preferable.

The method of melt polycondensation will be described below. First, the above-mentioned raw materials are heated to proceed with an esterification reaction or a transesterification reaction to obtain an oligomer. The esterification reaction or transesterification reaction is preferably carried out under a pressure of about 0.3 MPa or less at an absolute pressure or under a normal pressure at a temperature of 180 to 300 ° C. while distilling off the produced water or alcohol. The ratio of raw materials in the esterification reaction or transesterification reaction is preferably such that the molar ratio (diol component / dicarboxylic acid component) is in the range of 1.1 to 2.5.

If necessary, additives such as the above-mentioned raw materials, polycondensation catalyst and anticoloring agent are added to the obtained polyester oligomer, and the desired viscosity is obtained at a temperature of 200 to 300 ° C. under a reduced pressure of 1 kPa or less. It is preferable to carry out the melt polycondensation reaction until the polyester (C) of the above is obtained. The melt polycondensation reaction can be carried out by using, for example, a tank-type batch-type polycondensation device, a continuous polycondensation device including a biaxial rotary horizontal reactor, or the like.

When a polycondensation catalyst is used in the above-mentioned melt polycondensation reaction, a compound containing a germanium element, an antimony element, and a titanium element is preferable. Antimony trioxide, antimony chloride, antimony acetate and the like are used as the compound containing the antimony element, and germanium dioxide, germanium tetrachloride, germanium tetraethoxydo and the like are used as the compound containing the germanium element, and the titanium element is used. As the compound contained, an organic titanium compound such as tetraisopropyl titanate or tetrabutyl titanate, or an inorganic titanium compound such as titanium oxide or a composite particle of hydrotalcite and titanium dioxide is used. When a polycondensation catalyst is used, the amount added is preferably in the range of 0.002 to 0.8% by mass based on the mass of the unit having the heterocyclic structure (C1).

When an antioxidant is used in the above melt polycondensation reaction, for example, phosphorous acid, phosphoric acid, trimethylphosphine, triphenylphosphine, tridecylphosphite, trimethylphosphate, tridecylphosphine, triphenylphosphine Phosphoric compounds such as fate can be used. These phosphorus compounds may be used alone or in combination of two or more. When the anticoloring agent composed of the phosphorus compound is used, it is preferably in the range of 0.001 to 0.5% by mass based on the mass of the unit having the heterocyclic structure (C1). Further, in order to suppress coloring of the polyester (C) due to thermal decomposition, a cobalt compound having a weight of 0.001 to 0.5% by mass of a unit having a heterocyclic structure (C1), for example, cobalt acetate or the like can be added.

The obtained polyester (C) may be further solid-phase polymerized. By performing solid phase polymerization, a polyester having a higher degree of polymerization can be obtained. The intrinsic viscosity of the polyester to be subjected to solid phase polymerization is preferably in the range of 0.4 to 0.85 dl / g.

Polyester (C) obtained by melt polycondensation is extruded into a strand shape, a sheet shape, etc., cooled, and then cut with a strand cutter, a sheet cutter, etc. to form a columnar shape, an elliptical columnar shape, a disk shape, a die shape, etc. Intermediate pellets in the shape of can be produced. The cooling after extrusion can be performed by, for example, a water cooling method using a water tank, a method using a cooling drum, an air cooling method, or the like. By heating the obtained intermediate pellets before solid-phase polymerization and crystallizing them in advance, sticking of the pellets during solid-phase polymerization can be prevented. The crystallization temperature is preferably 100 to 180 ° C. As a method of crystallization, it may be crystallized in a vacuum tumbler or heated in an air circulation type heating device to crystallize. The time required for crystallization is usually about 30 minutes to 24 hours.

The temperature of solid-phase polymerization is preferably 170 to 250 ° C., and the time of solid-phase polymerization is usually about 5 to 70 hours. Further, the catalyst used in the melt polycondensation during solid phase polymerization may coexist. Further, the solid phase polymerization is preferably carried out under reduced pressure or in an inert gas such as nitrogen gas. Further, it is preferable to carry out solid-phase polymerization while moving the pellets by an appropriate method such as a rolling method or a gas fluidized bed method so that sticking between the pellets does not occur. The pressure when solid-phase polymerization is carried out under reduced pressure is preferably 1 kPa or less. The intrinsic viscosity of the polyester after solid phase polymerization is preferably in the range of 0.8 to 1.3 dL / g.

The base material (X) may contain additives as long as it does not impair the effects of the present invention. For example, colorants such as dyes and pigments, stabilizers such as ultraviolet absorbers, antistatic agents, Examples thereof include flame retardants, flame retardant aids, lubricants, plasticizers, inorganic fillers, inorganic layered compounds, and organically treated inorganic layered compounds. These can be added to the polyester (C) during film formation. The content of these additives is preferably 10% by mass or less, more preferably 2% by mass or less.

When the base material (X) is a film, the base material (X) may be a stretched film or a non-stretched film. The film forming method and stretching method of the film are illustrated below.

Examples of the polyester (C) film forming method include a method of extrusion molding by a T-die method, an inflation method, or the like. The intrinsic viscosity of the polyester (C) used for extrusion molding is preferably in the range of 0.6 to 1.3 dl / g in the T-die method, and preferably in the range of 0.8 to 1.3 dl / g in the inflation method. Examples of the extruder used for extrusion molding of polyester (C) include a single-screw extruder, a twin-screw extruder, a vent extruder, a tandem extruder and the like. The temperature of the polyester (C) during extrusion molding is preferably set to a temperature within the range of (melting point of polyester (C) + 10 ° C.) to (melting point of polyester (C) + 80 ° C.). It is preferable to obtain an unstretched film by extruding the molten polyester (C) into a film and then quenching and solidifying it using a cooling drum or the like. As a result, crystallization of the polyester in the obtained film is suppressed. The temperature of the cooling drum is preferably in the range of (glass transition point of polyester (C) −30 ° C.) to (glass transition point of polyester (C) + 10 ° C.). Scraps such as trim generated during film production can be collected and reused.

Examples of the method for stretching the unstretched film thus obtained include a tenter stretching method, a tubular stretching method, and a roll stretching method. The temperature at the time of stretching is preferably in the range of (glass transition point of polyester (C) + 5 ° C.) to (glass transition point of polyester (C) + 40 ° C.).

When the base material (X) is a film or a sheet, the thickness thereof is preferably 1 to 1000 μm, more preferably 5 to 500 μm, from the viewpoint of improving the mechanical strength and workability of the obtained multilayer structure. 9 to 200 μm is more preferable.

The water contact angle of the surface of the base material (X) is preferably 10 ° or more, more preferably 15 ° or more, and even more preferably 20 ° or more. The water contact angle on the surface of the base material (X) is preferably 78 ° or less, more preferably 75 ° or less, and even more preferably 70 ° or less. If the water contact angle on the surface of the base material (X) is larger than 78 °, the coatability tends to deteriorate. Further, in order to make the water contact angle smaller than 10 °, the energy required for the hydrophilic treatment tends to be enormous, which is not preferable. From the viewpoint of reducing the energy required for the hydrophilic treatment, the water contact angle of the base material (X) may be 30 ° or more, or 35 ° or more.

By applying a hydrophilic treatment to the surface of the base material (X), the hydrophilicity of the base material (X) is improved and the water contact angle is lowered, so that the coatability is improved. It is preferable not to reduce the amount of energy to be applied or to perform surface treatment. Examples of the hydrophilic treatment method include corona treatment and plasma treatment.

[Layer (Y)]
The layer (Y) contains a reaction product (R) of a metal oxide (A) containing aluminum and an inorganic phosphorus compound (BI).

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

The ratio of aluminum atoms to the metal atoms (M) is preferably 50 mol% or more, and may be in the range of 60 to 100 mol% or 80 to 100 mol%. Examples of the metal oxide (A) include metal oxides produced by methods such as a liquid phase synthesis method, a gas phase synthesis method, and a solid pulverization method.

The metal oxide (A) may be a 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 [I] described later. The hydrolyzed condensate of compound (E) can be regarded as substantially the metal oxide (A). Therefore, in the present specification, the hydrolyzed condensate of compound (E) may be referred to as "metal oxide (A)". That is, in the present specification, "metal oxide (A)" can be read as "hydrolyzed condensate of compound (E)", and "hydrolyzed condensate of compound (E)" can be read as "metal oxidation". It can also be read as "thing (A)".

[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 [I]. It is preferable to contain at least one kind.

Al (R ¹ ) _k (R ² ) _3-k [I]
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 6 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. If R ² there are a plurality, R ² may be the being the same or different.

The compound (E) may contain at least one compound (Eb) represented by the following general formula [II] in addition to the compound (Ea).
M ¹ (R ³ ) _m (R ⁴ ) _nm [II]
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 6 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 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. 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 the being the same or different. When a ^{plurality of R 4s} are present, the R ^4s may be the same or different from each other.

Examples of the alkoxy group having 1 to 9 carbon atoms which may have the substituent 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 and an isobutoxy group. Group, sec-butoxy group, tert-butoxy group, benzyloxy group, diphenylmethoxy group, trityloxy group, 4-methoxybenzyloxy group, methoxymethoxy group, 1-ethoxyethoxy group, benzyloxymethoxy group, 2-trimethylsilylethoxy group , 2-trimethylsilylethoxymethoxy group and the like.

Examples of the aryloxy group having 6 to 9 carbon atoms which may have the substituent represented by R ¹ and R ^{3 include a phenoxy group and a 4-methoxyphenoxy group.}

Examples of the asyloxy group having 2 to 9 carbon atoms which may have the substituent represented by R ¹ and R ³ include an acetoxy group, an ethylcarbonyloxy group, an n-propylcarbonyloxy group, an isopropylcarbonyloxy group and n. -Butylcarbonyloxy group, isobutylcarbonyloxy group, sec-butylcarbonyloxy group, tert-butylcarbonyloxy group, n-octylcarbonyloxy group and the like can be mentioned.

Examples of the alkenyloxy group having 3 to 9 carbon atoms which may have the substituent represented by R ¹ and R ³ include an allyloxy group, a 2-propenyloxy group, a 2-butenyloxy group and a 1-methyl-2-. Propenyloxy group, 3-butenyloxy group, 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 Examples thereof include -3-butenyloxy group, 1-vinyl-2-propenyloxy group, 5-hexenyloxy group and the like.

Examples of the β-diketonato group having 5 to 15 carbon atoms which may have the substituent represented by R ¹ and R ^{3 include a 2,4-pentandionato group and 1,1,1-trifluoro-2.} , 4-Pentandionato group, 1,1,1,5,5,5-hexafluoro-2,4-Pentandionato group, 2,2,6,6-tetramethyl-3,5-Heptandionato group, Examples thereof include a 1,3-butandionato group, a 2-methyl-1,3-butandionato group, a 2-methyl-1,3-butandionato group and a benzoylacetonato group.

Examples of the acyl group of the diacylmethyl group having an acyl group having 1 to 9 carbon atoms which may have the substituent represented by R ¹ and R ^{3 include a formyl group, an acetyl group, a propionyl group (propanoyl group), and the like.} Examples thereof include an aliphatic acyl group having 1 to 6 carbon atoms such as a butyryl group (butanoyl group), a valeryl group (pentanoyl group) and a hexanoyl group; and an aromatic acyl group (aroyl group) such as a benzoyl group and a toluoil group.

Examples of the alkyl group having 1 to 9 carbon atoms which may have the substituent 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 and an isobutyl group. , Se-butyl group, tert-butyl group, pentyl group, isopentyl group, n-hexyl group, isohexyl group, 3-methylpentyl group, 2-methylpentyl group, 1,2-dimethylbutyl group, cyclopropyl group, cyclopentyl Groups, cyclohexyl groups and the like can be mentioned.

Examples of the aralkyl group having 7 to 10 carbon atoms which may have the substituent represented by R ² and R ^{4 include a benzyl group and a phenylethyl group (phenethyl group).}

Examples of the alkenyl group having 2 to 9 carbon atoms which may have the substituent represented by R ² and R ⁴ include a vinyl group, a 1-propenyl group, a 2-propenyl group, an isopropenyl group and a 3-butenyl group. , 2-butenyl group, 1-butenyl group, 1-methyl-2-propenyl group, 1-methyl-1-propenyl group, 1-ethyl-1-ethenyl group, 2-methyl-2-propenyl group, 2-methyl Examples thereof include -1-propenyl group, 3-methyl-2-butenyl group, 4-pentenyl group and the like.

Examples of the aryl group having 6 to 10 carbon atoms which may have the substituent 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 [I] 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 [II] 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, for example, preferably 20 mol% or less, more preferably 10 mol% or less, still more preferably 5 mol% or less. It may be 0 mol%.

When the compound (E) is hydrolyzed, at least a part of the hydrolyzable characteristic groups of the compound (E) is converted into a hydroxyl group. 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 (A) 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 (A). 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 (A) 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 (A).

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 partially hydrolyzed product of compound (E), a completely hydrolyzed product of compound (E), a compound obtained by partially hydrolyzing and condensing compound (E), and compound (E). ) Can be used at least one selected from the group consisting of compounds formed by condensing a part of the complete hydrolyzate.

The metal oxide (A) to be mixed with the inorganic phosphorus compound (BI) -containing substance (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 the compound.

[Inorganic phosphorus compound (BI)]
The inorganic phosphorus compound (BI) contains a site capable of reacting with the metal oxide (A), and typically contains a plurality of such sites, preferably 2 to 20. Such a site includes a site capable of a condensation reaction with a functional group (for example, a hydroxyl group) existing on the surface of the metal oxide (A), 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 (A) is usually bonded to a metal atom (M) constituting the metal oxide (A).

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. Phosphoric oxo acids such as acids, salts thereof (eg, sodium phosphate), and derivatives thereof (eg, halides (eg, phosphoryl chloride), dehydrated products (eg, diphosphorus pentoxide)) and the like. Be done.

These inorganic phosphorus compounds (BI) may be used alone or in combination of two or more. 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.

[Reaction product (R)]
The reaction product (R) is obtained by reacting the metal oxide (A) with the inorganic phosphorus compound (BI). The reaction product (R) also includes a compound produced by the reaction of the metal oxide (A), the inorganic phosphorus compound (BI), and another compound.

In the infrared absorption spectrum of the layer (Y), the maximum absorption wave number in the region of 800～1400Cm ^-1 is preferably in the range of 1080~1130cm ^-1. For example, in the process of reacting the metal oxide (A) with the inorganic phosphorus compound (BI) to form the reaction product (R), the metal atom (M) derived from the metal oxide (A) and the inorganic phosphorus compound (B) A phosphorus atom (P) derived from BI) 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 (R). As a result of the study by the present inventors, when the characteristic absorption band based on the bond of M-OP ^{is found in the region of 1080 to 1130 cm-1} , the obtained multilayer structure exhibits excellent gas barrier properties. I understand. In particular, when the characteristic absorption band is the strongest absorption in the region of ^{800 to 1400 cm -1} where absorption generally derived from the bond between various atoms and oxygen atoms is observed, the obtained multilayer structure is further enhanced. It was found that it exhibits excellent 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, the metal atom derived from the metal compound and the 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 800～1400Cm ^-1 comes to deviate from the scope of 1080~1130cm ^-1.

In the infrared absorption spectrum of the layer (Y), the half-value width of the maximum absorption band in the region of 800～1400Cm ^-1 from gas barrier property aspect of the resulting multi-layer structure is preferably 200 cm ^-1 or less, is 150 cm ^-1 or less More preferably, 100 cm ^-1 or less is further preferable, and 50 cm ^-1 or less is particularly preferable.

The infrared absorption spectrum of the layer (Y) can be measured by an attenuated total reflection method using a Fourier transform infrared spectrophotometer (Spectrum One manufactured by PerkinElmer Co., Ltd.) ^{with a measurement region of 800 to 1400 cm -1.} However, if the measurement cannot be performed by the above method, a method of reflection measurement such as reflection absorption method, external reflection method, attenuation total reflection method, or transmission measurement such as Nujol method or tablet method by scraping the layer (Y) from the multilayer structure. However, the measurement is not limited to these.

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

In the layer (Y), the molar ratio of the metal atom constituting the metal oxide (A) to the phosphorus atom derived from the inorganic phosphorus compound (BI) is [metal atom constituting the metal oxide (A)]: [ 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. Excellent gas barrier performance can be obtained within this range. The molar ratio in the layer (Y) can be adjusted by the mixing ratio of the metal oxide (A) and the inorganic phosphorus compound (BI) in the coating liquid (S) for forming the layer (Y). The molar ratio in the layer (Y) is usually the same as the ratio in the coating liquid (S).

[Organophosphorus compound (BO)]
The layer (Y) may contain an organic phosphorus compound (BO). By containing the organic phosphorus compound (BO), the interlayer adhesion and bending resistance can be improved.

The organic phosphorus compound (BO) is preferably a polymer (BOa) having a plurality of phosphorus atoms or an organic phosphorus compound (BOb) described later.

[Polymer with multiple phosphorus atoms (BOa)]
Examples of the functional group containing a phosphorus atom contained in the polymer (BOa) 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. Functional groups (for example, salts, (partial) ester compounds, halides (for example, chlorides), dehydrated products) and the like are mentioned, and among them, a phosphoric acid group and a phosphonic acid group are preferable, and a phosphonic acid group is more preferable.

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; polymers of vinyl phosphinic acids such as vinyl phosphinic acid and 4-vinylbenzyl phosphinic acid; phosphorylated starch and the like. The polymer (BOa) may be a homopolymer of a monomer having a functional group containing at least one kind of 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 preferable.

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 1000 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 (S) when the coating liquid (S) described later is used can be obtained. , Compatible at a high level.

In the layer of the multilayer structure (Y), the mass of the inorganic phosphorus compound (BI) and the polymer (BOa) if it contains a layer weight W _BI and polymers of inorganic phosphorus compound in the (Y) (BI) (BOa ) preferably has the ratio W _BOa / W _BI of W _BOa satisfies the relation of _{0.01 / 99.99 ≦ W BOa / W} BI <6.00 / 94.00, from the viewpoint of excellent barrier performance, 0.10 / It is more preferable that the relationship of 99.90 ≦ W _BOa / W _BI <4.50 / 95.50 is satisfied, and the relationship of 0.20 / 99.80 ≦ W _BOa / W _BI <4.00 / 96.00 is satisfied. Those satisfying the above are more preferable, _{and those satisfying the relationship of 0.50 / 99.50 ≦ W BOa} / W _BI <3.50 / 96.50 are particularly preferable. That is, while W _BOa is a trace amount of 0.01 or more and less than 6.00, 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 (BOa) is reacting in the layer (Y), the inorganic phosphorus compound (BI) and / or the organic phosphorus compound (BOa) constituting the reaction product is reacted. ) Is regarded as an inorganic phosphorus compound (BI) and / or an organic phosphorus compound (BOa). In this case, the mass of the inorganic phosphorus compound (BI) and / or the organophosphorus compound (BOa) used for forming the reaction product (the mass of the inorganic phosphorus compound (BI) and / or the organophosphorus compound (BOa) before the reaction). ), Is included in the mass of the inorganic phosphorus compound (BI) and / or the organic phosphorus compound (BOa) in the layer (Y).

[Organophosphorus compound (BOb)]
The organophosphorus compound (BOb) has a phosphorus atom having at least one hydroxyl group bonded to a polar group via an alkylene chain or a polyoxyalkylene chain having 3 to 20 carbon atoms. Organophosphorus compounds (BObs) have lower surface free energy than metal oxides (A), inorganic phosphorus compounds (BI), and their reaction products (R), and in the process of forming precursors of layer (Y). Segregate on the surface side. The organic phosphorus compound (BOb) is a phosphorus atom having at least one hydroxyl group capable of reacting with a component contained in the layer (Y) and another member (for example, an adhesive layer (I), another layer (L) (for example,). Since it has a polar group that can react with the ink layer)), the adhesion is improved and the interlayer adhesive force can be maintained even after the retort treatment, so that it is possible to suppress appearance defects such as delamination.

The organic phosphorus compound (BOb) is, for example, the following general formula [III].
U ¹ −R ⁵ −U ² [III]
(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 3 to 20 carbon atoms, and U ² is polar. Represents a group.). ^{The linear or branched alkylene group or polyoxyalkylene group of R 5} of the general formula [III] has a smaller surface free energy than the other components of the layer (Y) and is soluble in the solvent used. From the viewpoint of goodness, the number of carbon atoms is 3 or more and 20 or less, preferably 4 or more and 18 or less carbon atoms, and more preferably 6 or more and 14 or less carbon atoms.

Examples of a phosphorus atom-containing group having at least one hydroxyl group represented by U ^{1 (U 1} of the general formula [III]) include a phosphoric acid group, a phosphonic 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 the ink layer and the 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 organic phosphorus compound (BOb) include 3-hydroxypropylphosphonic acid, 4-hydroxybutylphosphonic acid, 5-hydroxypentylphosphonic acid, 6-hydroxyhexylphosphonic acid, 7-hydroxyhepsylphosphonic acid, and 8-hydroxyhepsylphosphonic acid. Hydroxyoctylphosphonic acid, 9-hydroxynonylphosphonic acid, 10-hydroxydecylphosphonic acid, 11-hydroxyundecylphosphonic acid, 12-hydroxydodecylphosphonic acid, 13-hydroxydotridecylphosphonic acid, 14-hydroxytetradecylphosphonic acid , 15-Hydroxypentadecylphosphonic acid, 16-hydroxyhexadecylphosphonic acid, 17-hydroxyheptadecylphosphonic acid, 18-hydroxyoctadecylphosphonic acid, 19-hydroxynonadesylphosphonic acid, 20-hydroxyicosylphosphonic acid, 3- Hydroxypropyl dihydrogen phosphate, 4-hydroxybutyl dihydrogen phosphate, 5-hydroxypentyl dihydrogen phosphate, 6-hydroxyhexyl dihydrogen phosphate, 7-hydroxyhepsyldihydrogen phosphate, 8-hydroxyoctyl dihydro Genphosphate, 9-hydroxynonyldihydrogenphosphate, 10-hydroxydecyldihydrogenphosphate, 11-hydroxyundecyldihydrogenphosphate, 12-hydroxydodecyldihydrogenphosphate, 13-hydroxydotridecyldihydrogenphosphate , 14-Hydroxytetradecyldihydrogen phosphate, 15-hydroxypentadecyldihydrogen phosphate, 16-hydroxyhexadecyldihydrogen phosphate, 17-hydroxyheptadecyldihydrogen phosphate, 18-hydroxyoctadecyldihydrogen phosphate, 19-Hydroxynonadesildihydrogen phosphate, 20-hydroxyicosyldihydrogen phosphate, 3-carboxypropylphosphonic acid, 4-carboxybutylphosphonic acid, 5-carboxypentylphosphonic acid, 6-carboxyhexylphosphonic acid, 7- Carboxyhepsylphosphonic acid, 8-carboxyoctylphosphonic acid, 9-carboxynonylphosphonic acid, 10-carboxydecylphosphonic acid, 11-carboxyundecylphosphonic acid, 12-carboxy Dodecylphosphonic acid, 13-carboxydotridecylphosphonic acid, 14-carboxytetradecylphosphonic acid, 15-carboxypentadecylphosphonic acid, 16-carboxyhexadecylphosphonic acid, 17-carboxyheptadecylphosphonic acid, 18-carboxyoctadecylphosphonic acid Acids, 19-carboxynonadesylphosphonic acid, 20-carboxyicosylphosphonic acid and the like can be mentioned. These may be used alone or in combination of two or more.

In the layer of the multilayer structure (Y), an organic phosphorus compound (BOB) number of moles M _BOB and inorganic phosphorus compound (BI) ratio M _BOb / M _BI is 1.0 × 10 ^-4 ≦ of the moles M _BI of It is preferable that the relationship of M _BOb / M _BI ≤ 2.0 × 10 ⁻² is satisfied, and from the viewpoint of better adhesion, 3.5 × 10 ^-4 ≤ M _BOb / M _BI ≤ 1.0 × 10 ^{Those satisfying the relationship of -2} are more preferable, and those satisfying the relationship of 5.0 × 10 ^-4 ≤ M _BOb / M _BI ≤ 6.0 × 10 ^{-3 from the viewpoint of better adhesion and barrier performance.} Is particularly preferable. Incidentally, the number of moles M _BI inorganic phosphorus compound (BI) in M _BOb / M _BI refers inorganic phosphorus compound used to form the reaction product (R) and (BI).

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

[Polymer (F)]
The polymer (F) is a polymer having at least one functional group selected from the group consisting of a carbonyl group, a hydroxyl group, a carboxy group, a carboxylic acid anhydride group, and a salt of a carboxy group, and is composed of a hydroxyl group and a carboshiki group. It is preferable that the polymer has at least one functional group selected from the above group.

Examples of the polymer (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 alcohol-based polymers such as polyvinyl acetal (polyvinyl butyral, etc.); Polysaccharides such as cellulose and starch; (meth) acrylic acid-based polymers such as polyhydroxyethyl (meth) acrylate, poly (meth) acrylic acid, ethylene-acrylic acid copolymer; ethylene-maleic anhydride copolymer Examples thereof include a hydrolyzate, a hydrolyzate of a styrene-maleic anhydride copolymer, and a maleic acid-based polymer such as a hydrolyzate of an isobutylene-maleic anhydride copolymer. Of these, polyethylene glycol and polyvinyl alcohol-based polymers are preferable.

The polymer (F) may be a homopolymer of a monomer having a polymerizable group (for example, vinyl acetate or acrylic acid), or may be a copolymer of two or more kinds of monomers. Alternatively, it may be a copolymer of a monomer having a hydroxyl group and / or a carboxyl group and a monomer having no such group. As the polymer (F), two or more kinds of polymers (F) may be mixed and used.

The molecular weight of the polymer (F) is not particularly limited, but in order to obtain a multilayer structure having better gas barrier properties and mechanical strength, the weight average molecular weight of the polymer (F) is preferably 5000 or more, preferably 8000 or more. More preferably, 10,000 or more is further preferable. The upper limit of the weight average molecular weight of the polymer (F) is not particularly limited, and is, for example, 1500,000 or less.

From the viewpoint of maintaining a good appearance of the multilayer structure, the content of the polymer (F) in the layer (Y) is preferably 50% by mass or less, more preferably 20% by mass or less, based on the mass of the layer (Y). It is preferable, and 10% by mass or less is more preferable. The polymer (F) may or may not react with the components in the layer (Y).

The layer (Y) contained in the multilayer structure of the present invention may further contain other components. Other components that can be contained in the layer (Y) include, for example, inorganic acid metal salts such as carbonates, hydrochlorides, nitrates, hydrogen carbonates, sulfates, hydrogen sulfates, borates, oxalates, acetic acid. Organic acid metal salts such as salts, tartrates and stearate, metal complexes such as cyclopentadienyl metal complex (eg titanosen), cyanometal complex (eg Prussian blue), layered clay compounds, cross-linking agents, polymers (F), plasticizers, antioxidants, ultraviolet absorbers, flame retardants and the like can be mentioned. The content of the other component in the layer (Y) in the multilayer structure is preferably 50% by mass or less, more preferably 20% by mass or less, 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 0.05 to 4.0 μm, and is 0.1. ~ 2.0 μm is more preferable. By thinning the layer (Y), the dimensional change of the multilayer structure during processing such as printing and laminating can be suppressed to a low level. In addition, since the flexibility of the multilayer structure is increased, its mechanical properties can be brought closer to those of the base material itself. When the multilayer structure of the present invention has two or more layers (Y), the thickness per layer (Y) is preferably 0.05 μm or more from the viewpoint of gas barrier properties. The thickness of the layer (Y) can be controlled by the concentration of the coating liquid (S) used for forming the layer (Y), which will be described later, or the coating method thereof. The thickness of 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.

When the multilayer structure of the present invention contains an organophosphorus compound (BO) and at least one component selected from the other components, these may be mixed in the layer (Y) or alone in a layer (Y). Z) may be formed. When forming the layer (Z), the layer (Z) may be composed of one kind of component or may be a mixture of two or more kinds of components, but other members (for example, an adhesive layer (for example, an adhesive layer) From the viewpoint of improving the adhesion to I) and other layers (L)), it is preferable to contain the polymer (BOa) alone or the polymer (BOa) and the polymer (F).

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

The production method according to the multilayer structure of the present invention may include steps (I), (II) and (III). In the step (I), the coating liquid (S) is prepared by mixing the metal oxide (A), the inorganic phosphorus compound (BI) and the solvent. In the step (II), the coating liquid (S) is applied onto the base material (X) to form a precursor layer of the layer (Y) on the base material (X). In the step (III), the precursor layer is heat-treated at a temperature of 140 ° C. or higher to form a layer (Y) on the base material (X). The details of the steps (I) to (III) will be described below. Since the compound (A) containing aluminum, the inorganic phosphorus compound (BI), the organic phosphorus compound (BO), and their mass ratios have been described above, redundant description will be omitted in the production method. The coating liquid (S) is a highly polar (hydrophilic) coating liquid containing a metal oxide (A), an inorganic phosphorus compound (BI) and a solvent.

[Step (I)]
In the step (I), the coating liquid (S) is prepared by mixing at least the metal oxide (A), the inorganic phosphorus compound (BI) and the solvent. In one aspect, in step (I), the metal oxide (A) and the inorganic phosphorus compound (BI) are reacted in a solvent.

When mixing the metal oxide (A), the inorganic phosphorus compound (BI) and the solvent, other compounds (for example, organic phosphorus compound (BO), polymer (F), etc.) may coexist, and it is necessary. Depending, it may contain at least one acid compound (Q) selected from the group consisting of acetic acid, hydrochloric acid, nitric acid, trifluoroacetic acid, and trichloroacetic acid.

The step (I) preferably includes the following steps (I-1) to (I-3).
Step (I-1): A step of preparing a dispersion liquid (J) containing a metal oxide (A).
Step (I-2): A step of preparing a solution (K) containing an inorganic phosphorus compound (BI).
Step (I-3): A step of mixing the dispersion liquid (J) obtained in steps (I-1) and (I-2) with the solution (K) to prepare the coating liquid (S).

The step (I-2) may be performed before the step (I-1), at the same time as the step (I-1), or after the step (I-1). good.

[Step (I-1)]
In the step (I-1), a dispersion liquid (J) containing the metal oxide (A) is prepared. The dispersion liquid (J) may be a dispersion liquid of the metal oxide (A). The dispersion liquid (J) is prepared by mixing, for example, the compound (E) -based component, water, and, if necessary, an acid catalyst or an organic solvent, according to a method adopted in a known sol-gel method, and then compound (E). It can be prepared by condensing or hydrolyzing the system components. The dispersion liquid of the metal oxide (A) obtained by condensing or hydrolyzing the compound (E) -based component can be used as it is as the dispersion liquid (J) containing the metal oxide (A), but if necessary. Then, the dispersion liquid (J) may be subjected to a specific treatment (such as defibration in the presence of the acid compound (Q) and adjustment of a solvent for controlling the concentration). The solvent used in the step (I-1) is not particularly limited, but alcohols such as methanol, ethanol and isopropanol, water and a mixed solvent thereof are preferable.

Examples of the acid catalyst used for hydrolysis condensation include hydrochloric acid, sulfuric acid, nitric acid, carbonic acid, formic acid, acetic acid, lactic acid, butyric acid, oxalic acid, maleic acid, benzoic acid, p-toluenesulfonic acid and the like. , Sulfuric acid, nitric acid, acetic acid, lactic acid and butyric acid are preferred, and nitric acid and acetic acid are more preferred. When an acid catalyst is used during hydrolysis condensation, it is preferable to use an amount suitable for the type of acid so that the pH before hydrolysis condensation is in the range of 2.0 to 4.0.

[Step (I-2)]
In step (I-2), a solution (K) containing an inorganic phosphorus compound (BI) is prepared. The solution (K) is prepared by dissolving the inorganic phosphorus compound (BI) in a solvent. When the solubility of the inorganic phosphorus compound (BI) is low, the dissolution may be promoted by performing heat treatment or ultrasonic treatment.

The solvent used for preparing the solution (K) may be appropriately selected depending on the type of the inorganic phosphorus compound (BI), but preferably contains water. Solvents include methanol, ethanol, tetrahydrofuran, 1,4-dioxane, trioxane, dimethoxyethane, acetone, methyl ethyl ketone, ethylene glycol, propylene glycol, methyl cellosolve, ethyl cellosolve, as long as they do not interfere with the dissolution of the inorganic phosphorus compound (BI). It may contain an organic solvent such as n-butyl cellosolve, glycerin, acetonitrile, N, N-dimethylformamide, dimethyl sulfoxide, and sulfolane.

[Step (I-3)]
In the step (I-3), the dispersion liquid (J) and the solution (K) are mixed to prepare the coating liquid (S). The dispersion liquid (J) and the solution (K) are preferably mixed under stirring. At this time, the solution (K) may be added to the stirred dispersion (J), or the dispersion (J) may be added to the stirred solution (K). By continuing stirring for about 30 minutes from the time when the mixing is completed, the coating liquid (S) having excellent storage stability tends to be obtained.

The temperature of the dispersion liquid (J) and the solution (K) at the time of mixing in the step (I-3) is preferably 50 ° C. or lower, more preferably 30 ° C. or lower, still more preferably 20 ° C. or lower.

The coating liquid (S) may contain an organic phosphorus compound (BO) and / or a polymer (F). Further, the coating liquid (S) may contain at least one acid compound selected from acetic acid, hydrochloric acid, nitric acid, trifluoroacetic acid, and trichloroacetic acid, if necessary.

The solution obtained in step (I-3) can be used as it is as a coating liquid (S). In this case, the solvent contained in the dispersion liquid (J) or the solution (K) is usually the solvent for the coating liquid (S). Further, the solution obtained in the step (I-3) may be subjected to treatments such as addition of an organic solvent, pH adjustment, addition of additives, etc. as the coating liquid (S).

An organic solvent may be added to the solution obtained in the step (I-3) as long as the stability of the obtained coating liquid (S) is not impaired. By adding the organic solvent, the coating of the coating liquid (S) on the base material (X) in the step (II) may be facilitated. The organic solvent is preferably one that is uniformly mixed in the obtained coating liquid (S). Examples of the organic solvent include methanol, ethanol, tetrahydrofuran, 1,4-dioxane, trioxane, dimethoxyethane, acetone, methyl ethyl ketone, ethylene glycol, propylene glycol, methyl cellosolve, ethyl cellosolve, n-butyl cellosolve, glycerin, acetonitrile, N, N-dimethylformamide, dimethyl sulfoxide, sulfolane and the like can be used.

The solid content concentration of the coating liquid (S) is in the range of 1 to 20% by mass from the viewpoint of the storage stability of the coating liquid (S) and the coatability of the coating liquid (S) to the base material (X). Is more preferable, and it is more preferably in the range of 2 to 15% by mass, and further preferably in the range of 3 to 10% by mass. The solid content concentration of the coating liquid (S) 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.

From the viewpoint of the storage stability of the coating liquid (S) and the barrier property of the vacuum heat insulating material, the pH of the coating liquid (S) is preferably in the range of 0.1 to 6.0, and is 0.2 to 5.0. It is more preferable that it is in the range of 0.5 to 4.0, and it is further preferable that it is in the range of 0.5 to 4.0. The pH of the coating liquid (S) can be adjusted by a known method, for example, by adding an acidic compound or a basic compound.

As long as the effects of the present invention can be obtained, the coating liquid (S) may be, for example, an inorganic acid metal salt such as a carbonate, a hydrochloride, a nitrate, a hydrogen carbonate, a sulfate, a hydrogen sulfate, or a borate; , Organic acid metal salts such as acetates, tartrates, stearate; metal complexes such as cyclopentadienyl metal complexes (eg, titanosen), cyanometal complexes (eg, Prussian blue); layered clay compounds; cross-linking agents; It may contain other substances mentioned above such as a polymer compound; a plastic agent; an antioxidant; an ultraviolet absorber; a flame retardant.

[Step (II)]
In the step (II), the coating liquid (S) is applied onto the base material (X) to form a precursor layer of the layer (Y) on the base material (X). The coating liquid (S) may be applied directly onto at least one surface of the base material (X), or the surface of the base material (X) is known before the coating liquid (S) is applied. An adhesive layer (I) is formed on the surface of the base material (X) by treating with the anchor coating agent of No. 1 or applying a known adhesive to the surface of the base material (X). May be good.

The coating liquid (S) may be degassed and / or defoamed, if necessary. For example, there are methods such as depressurization, heating, centrifugation, ultrasonic waves, etc., but a method including decompression is preferable.

The coating liquid (S) when coated in the step (II) has a viscosity measured by a Brookfield type rotational viscometer (SB type viscometer: rotor No. 3, rotational speed 60 rpm) at the time of coating. The temperature is preferably 3000 mPa · s or less, more preferably 2000 mPa · s or less. When the viscosity is 3000 mPa · s or less, the leveling property of the coating liquid (S) is improved, and a multilayer structure having a more excellent appearance can be obtained. The viscosity of the coating liquid (S) at the time of coating in the step (II) can be adjusted by the concentration, the temperature, the stirring time after mixing in the step (I-3), and the stirring strength. For example, the viscosity may be lowered by long-term stirring after mixing in step (I-3).

The method of applying the coating liquid (S) onto the base material (X) 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, and a spray coating method. , Kiss coat method, die coat method, metering bar coat method, chamber doctor combined coat method, curtain coat method, bar coat method and the like can be used.

Usually, in the step (II), the precursor layer of the layer (Y) is formed by removing the solvent in the coating liquid (S). The method for removing the solvent is not particularly limited, and a known drying method can be applied. Examples of the drying method include a hot air drying method, a hot roll contact method, an infrared heating method, and a microwave heating method. The drying temperature is preferably 0 to 15 ° C. or more lower than the flow start temperature of the base material (X). When the coating liquid (S) contains the polymer (F), the drying temperature is preferably 15 to 20 ° C. or more lower than the thermal decomposition start temperature of the polymer (F). The drying temperature is preferably in the range of 70 to 200 ° C, more preferably in the range of 80 to 180 ° C, and even more preferably in the range of 90 to 160 ° C. The removal of the solvent may be carried out under normal pressure or reduced pressure. Further, the solvent may be removed by the heat treatment in the step (III) described later.

In an example of laminating the layer (Y) on both sides of the layered base material (X), first, the coating liquid (S) is applied to one surface of the base material (X), and then the solvent is removed. To form the first layer (precursor layer of the first layer (Y)). Next, the coating liquid (S) is applied to the other surface of the base material (X), and then the solvent is removed to form a second layer (precursor layer of the second layer (Y)). .. The composition of the coating liquid (S) to be applied to each surface may be the same or different.

[Step (III)]
In the step (III), the precursor layer of the layer (Y) 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 in which the reaction product (R) is produced proceeds. In order to allow the reaction to proceed sufficiently, the heat treatment temperature is 140 ° C. or higher, preferably 170 ° C. or higher, and more preferably 180 ° 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. If the heat treatment temperature is high, the base material melts, which leads to a decrease in film forming property and an increase in cost. 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.

[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 in the step (II') The coating liquid (T) (second coating liquid) obtained by mixing the compound (BO) and the solvent was obtained in the layer (Y) precursor layer obtained in the step (II) or the layer (Y) obtained in the step (III). ) May be coated on top.

In the step (II'), a coating liquid (T) containing an organic phosphorus compound (BO) is applied onto the layer (Y) precursor layer obtained in the step (II) or the layer (Y) obtained in the step (III). The step of coating (II') is included.

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) precursor layer obtained in the step (II) or the layer (Y) obtained in the step (III).

In the step (II'), since sufficient heat can be applied in a later step, it is preferable to apply the coating on the layer (Y) precursor layer obtained in the step (II).

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

[Adhesive layer (I)]
In the multilayer structure of the present invention, the layer (Y) may be laminated so as to be in direct contact with the base material (X), but is arranged between the base material (X) and the layer (Y). The layer (Y) may be laminated on the base material (X) via the adhesive layer (I). According to this configuration, the adhesiveness between the base material (X) and the layer (Y) may be improved. The adhesive layer (I) is not particularly limited as long as it has a high affinity with the base material (X) and the layer (Y), but a layer made of a hydrophilic adhesive enhances the interlayer adhesive strength. Preferred from the point of view.

When the adhesive layer (I) is arranged between the base material (X) and the layer (Y), the thickness thereof is preferably in the range of 0.03 to 0.18 μm. The thickness of the adhesive layer (I) is more preferably in the range of 0.04 to 0.14 μm, and even more preferably in the range of 0.05 to 0.10 μm.

[Extruded coat laminate]
The multilayer structure of the present invention is formed by, for example, laminating a layer (Y) on a base material (X) and then forming another layer (L) directly or via an adhesive layer by an extrusion coat laminating method. , Can further have a layer formed by an extruded coat laminate. The extrusion coat laminating method that can be used in the present invention is not particularly limited, and a known method may be used. 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, a multilayer structure 501 is fed from a 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 multilayer structure 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 multilayer structure 501 and the resin film 502 are laminated. Body) 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, a second base material is supplied from another unwinder (unwinder), and the second base material is bonded to each other to produce a multilayer structure. The tandem laminating method is a method of connecting two single laminating machines to produce a multi-layer structure having a five-layer structure at a time.

By using the above-mentioned multi-layer structure, it is possible to obtain a multi-layer structure that maintains high barrier performance even after extrusion coating laminating and has a small decrease in light transmission.

[Other layer (L)]
The multilayer structure of the present invention may include another layer (L) for imparting various properties (for example, heat-sealing property, barrier property, mechanical property). In such a multilayer structure of the present invention, for example, after laminating the layer (Y) directly on the base material (X) or via the adhesive layer (I), the other layer (L) is directly or directly or It can be manufactured by adhering or forming through an adhesive layer (I). Examples of the other layer (L) include, but are not limited to, an ink layer, a polyolefin layer, 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. A dried film of the resin for forming the electronic circuit wiring may be used. 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.

[Use]
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. 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 includes a multilayer structure including a base material (X) and a layer (Y) laminated on the base material (X). 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". Further, typically, "packaging material" can be read as "packaging". The packaging material may be composed of a multilayer structure and other members.

The packaging material according to the preferred embodiment of the present invention is an inorganic gas (for example, hydrogen, helium, nitrogen, oxygen, carbon dioxide), a natural gas, water vapor and an organic compound in a liquid state at normal temperature and pressure (for example, 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 sheet-like multilayer structure or a film material containing the multilayer structure (hereinafter, simply referred to as “film material”) is joined to form a predetermined container shape. A container (packaging material) may be produced by molding into. 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 (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 may be vertical bag-filled seal bags, vacuum packaging bags, pouches, laminated tube containers, infusion bags, paper containers, strip tapes, container lids, in-mold label containers or vacuum insulation. good. 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. Vertical bag filling Seal bags are 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 (L). 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 main 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 portion and the male mold portion, 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 361-363 of the present invention attached to the surface of the container body 370. 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 base material (X) / layer (Y) / base material (X). It may have a structure of / layer (Y) / inorganic vapor deposition layer / ethylene-vinyl alcohol copolymer layer / 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 covering the particulate 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 decompressed.

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 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 according to 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 group III-V compound semiconductor solar cell, a group II-VI compound semiconductor solar cell, and a group I-III-VI 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 wound 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. Alternatively, the protective sheet 43 may include a multilayer structure and other members (for example, another layer (L)) laminated on the multilayer structure. The protective sheet 43 is a layered multilayer structure suitable for protecting the surface of an electronic device, and the thickness and material thereof are not particularly limited as long as the protective sheet 43 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 made in the art within the technical idea of the present invention. It is possible by a person with ordinary knowledge. The films used in the following examples and comparative examples and analytical evaluations were carried out as follows.

(1) Film and adhesive used 1) PET12: Biaxially stretched polyethylene retephthalate film; manufactured by Toray Industries, Inc., "Lumirror (registered trademark) P60", thickness 12 μm, non-corona surface used 2) ONY15: Biaxial Stretched nylon film; manufactured by Unitika Ltd., "Emblem (registered trademark) ONBC", thickness 15 μm
3) CPP50: Unstretched polypropylene film; manufactured by Mitsui Chemicals Tohcello Co., Ltd., "RXC-22", thickness 50 μm
4) Two-component adhesive: "Takelac (registered trademark) A-520"; manufactured by Mitsui Chemicals, Inc. and "Takenate (registered trademark) A-50"; manufactured by Mitsui Chemicals, Inc.

(2) Measurement of Thickness of Each Layer The multilayer structure obtained in Examples and Comparative Examples was cut using a focused ion beam (FIB) to prepare a section for cross-section 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) Hydrophilic treatment The surface of the base material used in Examples and Comparative Examples was subjected to hydrophilic treatment using the following device. The table speed scale and the output setting of the high frequency power supply were appropriately adjusted, and the hydrophilic treatment strengths shown in Tables 1 and 2 were calculated.
Equipment: Corona processing equipment manufactured by Kasuga Electric Co., Ltd. XEM-KL-5900

(4) Evaluation of water contact angle of base material The base materials used in Examples and Comparative Examples were placed on a sample table. A drop of ion-exchanged water was dropped onto the substrate under the following conditions, and the water contact angle was measured under the conditions of 20 ° C. and 70% RH. This operation was repeated 10 times, and the average value was evaluated as the water contact angle.
Equipment: Drop Master DM-500 manufactured by Kyowa Interface Science Co., Ltd.
Droplet: 2.0 μL
Waiting time: 2.0 seconds

(5) Evaluation of coatability The presence or absence of white spots or circular drying marks that may occur during drying of the multilayer structure obtained in Examples and Comparative Examples is visually confirmed, and if it does not exist on the entire surface, it is marked with "A" and the edge. The case where it exists only in a part is designated as "B", and the case where it exists in the entire surface is designated as "C". It should be noted that such dry marks are generated when the coatability of the coating liquid (S) on the substrate is low, and it is preferable that such dry marks do not exist.

(6) Measurement of Oxygen Permeability of Multilayer Structure The multi-layer structure was attached to the oxygen permeation 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 / 61 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

(7) Measurement of Moisture Permeability of Multilayer Structure A multi-layer structure was attached to a water vapor permeation measuring device so that the layer of the base material faces the carrier gas side, and the moisture permeation (water vapor permeability) was measured by an 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

<Example of producing a base material (X-1) polyethylene furanoate (PEF) film>
A slurry consisting of 100 parts by mass of 2,5-furandicarboxylic acid, 47.7 parts by mass of ethylene glycol, 0.012 parts by mass of germanium dioxide and 0.012 parts by mass of phosphorous acid was prepared, and the slurry was placed in an esterification tank for 2 hours. The oligomer was produced by heating to 190 ° C. under pressure (gauge pressure 0.25 MPa) while feeding to carry out an esterification reaction. The obtained oligomer was transferred to a polycondensation tank and subjected to melt polycondensation at 270 ° C. for 120 minutes at 0.1 kPa to obtain a copolymerized polyester having an intrinsic viscosity of 0.7 dL / g. The obtained copolymerized polyester is extruded into a strand shape from a nozzle, cooled in warm water at 30 ° C., and then cut into columns (diameter: about 2.5 mm, length: about 2.5 mm) to pellet the copolymerized polyester (about 2.5 mm in diameter and about 2.5 mm in length). Melt-polymerized pellets) were obtained.

The melt-polymerized pellets obtained as described above were put into a rolling vacuum solid-phase polymerization apparatus and pre-crystallized at 130 to 140 ° C. under 0.1 kPa for 3 hours.

After the pre-crystallization, the temperature was raised and solid-phase polymerization was carried out at 190 to 200 ° C. for 100 hours under 0.1 kPa to obtain solid-phase polymerization pellets. The intrinsic viscosity of the obtained copolymerized polyester was 0.9 dL / g. When the ratio of the monomer components constituting the obtained polyester was ^{confirmed by 1 1} H-NMR spectrum (device: "JNM-GX-500 type" manufactured by JEOL Ltd., solvent: trifluoroacetic acid dehydrogenated), 2 , 5-Flange Carboxylic Acid Unit: Ethylene Glycol Unit: Diethylene Glycol Unit = 50: 48.75: 1.25 (molar ratio). The glass transition temperature (Tg) of the obtained copolymerized polyester was 87 ° C. The ratio of the monomer components constituting the polyester and the glass transition temperature did not change before and after the solid phase polymerization.

The obtained solid-phase polymerized pellets are dried overnight in a dryer at 120 ° C., uniaxially kneaded (cylinder temperature: 260 to 280 ° C.), and then extruded from a T-die onto a cooling roll at 85 ° C. to obtain a thickness. A substrate (X-1) having a width of 100 μm and a width of 300 mm was prepared.

<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, while stirring the dispersion while maintaining the liquid temperature at 15 ° C., 4.41 parts by mass of an 85 mass% phosphoric acid aqueous solution was added dropwise, and the mixture was stirred at 15 ° C. until the viscosity reached 1500 mPa · s. Subsequently, the desired coating liquid (S-1) was obtained. The molar ratio of aluminum atom to phosphorus atom in the coating liquid (S-1) was aluminum atom: phosphorus atom = 1.15: 1.00.

<Example 1>
^{The base material (X-1) was subjected to hydrophilic treatment at an intensity of 150 W · min / m 2} according to the method described in (3) above, and then the water contact angle was measured according to the method described in (4) above. The measurement results are shown in Table 1. The coating liquid (S-1) is coated on the hydrophilic treated base material (X-1) using the bar coater No. 2, dried at 120 ° C. for 3 minutes, and then heat-treated at 180 ° C. for 1 minute. A film of a layer (Y-1) of the obtained multilayer structure (1-1) obtained by obtaining a multilayer structure (1-1) in which a layer (Y-1) is formed on a base material (X-1). The thickness, coatability, oxygen permeability, and humidity permeability were evaluated according to (2), (5), (6), and (7) described above. The results are shown in Table 1.

<Examples 2 to 4>
By changing the bar coater No. used to 4, 6 and 8, the layer (Y-1) was changed to a layer (Y-2) to a layer (Y-4) having a film thickness of 240 nm, 320 nm and 400 nm. Multilayer structures (1-2) to (1-4) were prepared and evaluated in the same manner as in the multilayer structure (1-1) of Example 1 except for the above. The results are shown in Table 1.

<Comparative example 1>
A multilayer structure (C1-1) was prepared and evaluated by the same method as in Example 1 except that the base material (X-1) was changed to PET12. The results are shown in Table 1.

The multilayer structures (1-1) to (1 to 4) had better coatability as compared with (C1-1), and showed good oxygen permeability and moisture permeability.

<Examples 5 to 7>
Multilayer structures (2-1) to (2-3) were prepared in the same manner as in Example 1 except that the hydrophilicity treatment strength was changed as shown in Table 2. The water contact angle and coatability of each base material after the hydrophilic treatment were evaluated based on the above (4) and (5). The evaluation results are shown in Table 2.

<Reference Examples 1 and 2, Comparative Example 2>
Multilayer structures (C2-1) to (C2-3) were prepared and evaluated in the same manner as in Examples 5 to 7 except that PET12 was used as the base material. The evaluation results are shown in Table 2.

From the comparison between Examples 5 and 6 and Reference Examples 1 and 2, when polyester (C) is used as the base material, the water contact angle is lower and the coating is performed at the same hydrophilic treatment strength as when polyester (C) is not used. It can be seen that the sex is good. Further, from Example 7 and Comparative Example 2, when the polyester (C) is not used as the base material, it is difficult to apply the coating liquid (S), whereas when the polyester (C) is used as the base material. It can be seen that the coatability of the coating liquid (S) is good even without the hydrophilic treatment. Therefore, by using a base material containing polyester (C) as the base material, the multilayer structure of the present invention can be produced without the hydrophilic treatment or by reducing the energy used in the hydrophilic treatment step.

<Example 8>
An adhesive layer was formed on the layer (Y-1) of the multilayer structure (2-3) of Example 7, and ONY15 was laminated on the adhesive layer. Next, after forming an adhesive layer on the ONY 15, CPP50 was laminated on the adhesive layer and allowed to stand at 40 ° C. for 5 days for aging. In this way, a multilayer structure (3-1) having a structure of a base material (X-1) / layer (Y-1) / adhesive layer / ONY15 / adhesive layer / CPP50 was obtained. Each of the two adhesive layers is coated with the two-component adhesive (Takelac (registered trademark) and Takenate (registered trademark)) using a bar coater so that the thickness after drying is 4 μm, and dried. Formed by

When the oxygen permeability and the moisture permeability of the multilayer structure (3-1) were measured by the above method, the oxygen permeability was 0.1 mL / m ² · day · atm, and the moisture permeability was 0.1 g / m ^2.・ It was day.

<Example 9>
The multi-layer structure (3-1) was laminated and the end portion was heat-sealed under heat-sealing conditions (manufactured by Fuji Impulse Co., Ltd., foot bag type sealer, scale 5) to form a bag. The bag was transparent and showed a good appearance.

10 Vertical filling seal bag 11 Multi-layer structure 11a End 11b Body 20 Flat pouch 11c Peripheral 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 Multi-layer structure 502 Resin film 503 Laminate film (multi-layer structure)
601, 602 Vacuum insulation 611 Peripheral part 620 Partition 631, 632 Multi-layer structure 651, 652 Core material 40 Electronic device 41 Electronic device body 42 Encapsulant 43 Protective sheet (multi-layer structure)

Claims (10)

A multilayer structure including a base material (X) and a layer (Y), wherein the base material (X) contains a polyester (C) having a heterocyclic structure (C1), and the layer (Y) contains aluminum. metal oxide (a) with the reaction product of an inorganic phosphorus compound (BI) (R) only containing, heterocyclic structure (C1) is a furan ring, a heterocyclic polyester (C) is a monomer unit It is a polyester having a dicarboxylic acid unit having a structure (C1) and an aliphatic diol unit, and the content of the dicarboxylic acid unit having the heterocyclic structure (C1) is relative to all the monomer units constituting the polyester (C). 25 to 50 mol%, and the content of the aliphatic diol unit is 25 to 50 mol% with respect to all the monomer units constituting the polyester (C) . The multilayer structure according to claim 1, wherein the heterocyclic structure (C1) is contained in the main chain of the polyester (C). The multilayer structure according to claim 1 or 2 , wherein the dicarboxylic acid unit having a heterocyclic structure (C1) is 2,5-furandicarboxylic acid. Claims 1 to 3 include the aliphatic diol unit including at least one aliphatic diol unit selected from the group consisting of ethylene glycol units, diethylene glycol units, 1,3-propanediol units and 1,4-butanediol units. The multilayer structure according to any one of. The multilayer structure according to any one of claims 1 to 4 , wherein the base material (X) and the layer (Y) are adjacent to each other via the adhesive layer (I). The multilayer structure according to any one of claims 1 to 5 , wherein the base material (X) and the layer (Y) are directly laminated. The multilayer structure according to any one of claims 1 to 6 , wherein the water contact angle of the surface of the base material (X) is 10 ° to 78 °. A product comprising the multilayer structure according to any one of claims 1 to 7. The product 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 container lid, an in-mold label container, a vacuum insulator, or an electronic device. The product according to claim 8. The multilayer structure according to any one of claims 1 to 7, wherein the base material (X) is not surface-treated.

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