JP5801744B2 - Multilayer structure, product using the same, and method for producing multilayer structure - Google Patents

Description

  The present invention relates to a multilayer structure, a product using the multilayer structure, and a method for manufacturing the multilayer structure.

  A laminate in which a film comprising aluminum and its oxide, alumina, as a constituent component is formed on a plastic film has been well known in the past, and is a gas barrier for protecting foods and other articles that are easily altered by oxygen. It is used as a packaging material having properties. Many of these gas barrier coatings are formed on plastic films by dry processes such as vacuum deposition, sputtering, ion plating, and chemical vapor deposition (CVD). Aluminum vapor deposited films have light shielding properties in addition to gas barrier properties, and are mainly used as packaging materials for dry foods. On the other hand, transparent alumina vapor-deposited film has the visibility of the contents, taking advantage of the features such as foreign object inspection with a metal detector and microwave heating, etc., and a wide range of applications including retort food packaging It is used as a packaging material.

  Further, a transparent gas barrier coating composed of aluminum atoms, oxygen atoms, and sulfur atoms is known (Patent Document 1: Japanese Patent Application Laid-Open No. 2003-251732). Japanese Patent Laid-Open No. 2003-251732 discloses a method of forming a transparent film having a gas barrier property on a plastic film by a reactive sputtering method using aluminum as a target and a mixed gas of hydrogen sulfide and oxygen as a reactive gas. Is disclosed.

  Further, a transparent gas barrier coating composed of a reaction product of alumina particles and a phosphorus compound has been disclosed by the present inventors (Patent Document 2: International Publication No. WO2011-122036). International Publication No. WO2011-122036 discloses a method of forming a transparent film having gas barrier properties on a plastic film by applying a coating liquid containing alumina particles and a phosphorus compound, followed by drying and heat treatment.

JP 2003-251732 A International publication WO2011-122036

  However, although the above conventional gas barrier coating has excellent initial gas barrier properties, defects such as cracks and pinholes may occur when subjected to physical stress such as deformation or impact. In some cases, sex was insufficient. For example, when it is used as a food packaging material, it is subjected to various physical stresses at each stage of printing, laminating, bag making, food filling, transportation, display, and consumption. Therefore, there is a demand for a multilayer structure that can maintain high gas barrier properties even under such physical stress.

  Therefore, one of the objects of the present invention is to provide a multilayer structure that has excellent gas barrier properties and can maintain the gas barrier properties at a high level even when subjected to physical stress such as deformation or impact, and a method for manufacturing the same. Is to provide. Another object of the present invention is to provide a product including the multilayer structure.

  As a result of intensive studies to achieve the above object, the present inventors have excellent gas barrier properties by laminating a layer containing aluminum atoms and a layer containing a polymer having a plurality of phosphorus atoms adjacent to each other, It has been found that a multilayer structure capable of maintaining gas barrier properties at a high level even when subjected to physical stress such as deformation or impact can be obtained. That is, by laminating a layer containing a polymer having a plurality of phosphorus atoms not having gas barrier properties adjacent to a layer having aluminum atoms having gas barrier properties, the bending resistance of the resulting multilayer structure is greatly increased. I was able to improve. The present inventors have completed the present invention by further studying based on this new knowledge.

  That is, the multilayer structure of the present invention is a multilayer structure having at least one substrate (X), layer (Y) and layer (Z), wherein the layer (Y) contains aluminum atoms, The layer (Z) includes a polymer (E) having a plurality of phosphorus atoms, and at least one set of the layer (Y) and the layer (Z) is laminated adjacently.

  In the multilayer structure of the present invention, at least one set of the substrate (X), the layer (Y), and the layer (Z) includes the substrate (X) / the layer (Y) / the layer (Z ) May be stacked in this order.

  In the multilayer structure of the present invention, the polymer (E) may be a homopolymer or copolymer of a (meth) acrylic acid ester containing a phosphate group, and the terminal is a phosphate group. It may contain a side chain.

  In the multilayer structure of the present invention, the polymer (E) may be a homopolymer of acid phosphooxyethyl methacrylate.

In the multilayer structure of the present invention, the layer (Y) may be a layer (YA) containing the reaction product (R). The reaction product (R) is a reaction product obtained by a reaction between a metal oxide (A) containing aluminum and a phosphorus compound (B). The infrared absorption spectrum of the layer (YA) is 800 to 1400 cm ^{−. The} wave number (n ¹ ) that maximizes infrared absorption in the range of ¹ may be in the range of 1080 to 1130 cm ⁻¹ .

The multilayer structure of the present invention, in the infrared absorption spectrum of the layer (YA), the absorbance at the wave number (n ¹⁾ and (A ^1), the absorbance at the wave number (n ²⁾ and (A ^2), but the absorbance (A ² ) / absorbance (A ¹ ) ≦ 0.2 may be satisfied. The wave number (n ² ) is a wave number that maximizes infrared absorption based on stretching vibration of hydroxyl groups in the range of 2500 to 4000 cm ⁻¹ in the infrared absorption spectrum of the layer (YA).

In the multilayer structure of the present invention, the half-value width of the absorption peak of the wave number (n ¹ ) may be 200 cm ⁻¹ or less.

In the multilayer structure of the present invention, the metal oxide (A) may be a hydrolysis condensate of a compound (L) containing a metal atom (M) to which a hydrolyzable characteristic group is bonded, The compound (L) may include at least one compound (L ¹ ) represented by the following formula (I).
AlX ¹ _m R ¹ _(3-m) (I)
[In Formula (I), X ¹ is selected from F, Cl, Br, I, R ² O—, R ³ C (═O) O—, (R ⁴ C (═O)) ₂ CH— and NO _3. Selected from the group of R ¹ , R ² , R ³ and R ⁴ are each selected from the group consisting of an alkyl group, an aralkyl group, an aryl group and an alkenyl group. In Formula (I), when a plurality of X ¹ are present, these X ¹ may be the same as or different from each other. In the formula (I), when a plurality of R ¹ are present, these R ¹ may be the same or different from each other. In the formula (I), when a plurality of R ² are present, these R ² may be the same or different from each other. In the formula (I), when a plurality of R ³ are present, these R ³ may be the same or different from each other. In the formula (I), when a plurality of R ⁴ are present, these R ⁴ may be the same as or different from each other. m represents an integer of 1 to 3. ]

In the multilayer structure of the present invention, the compound (L ¹ ) may be at least one compound selected from aluminum triisopropoxide and aluminum tris-butoxide.

  In the multilayer structure of the present invention, the phosphorus compound (B) may be at least one compound selected from the group consisting of phosphoric acid, polyphosphoric acid, phosphorous acid, phosphonic acid, and derivatives thereof.

The multilayer structure of the present invention, in the layer (YA), a number of moles N _M of the metal atom (M) constituting the metal oxide (A), moles of phosphorus atoms derived from the phosphorus compound (B) The number N _P may satisfy the relationship of 1.0 ≦ (the number of moles N _M ) / (the number of moles N _P ) ≦ 3.6.

  In the multilayer structure of the present invention, the layer (Y) may be an aluminum deposition layer or an aluminum oxide deposition layer.

  In the multilayer structure of the present invention, the substrate (X) may include at least one layer selected from the group consisting of a thermoplastic resin film layer, a paper layer, and an inorganic vapor deposition layer.

The multilayer structure of the present invention may have an oxygen permeability of 2 ml / (m ² · day · atm) or less at 20 ° C. and 85% RH.

The multilayer structure of the present invention has an oxygen permeability of 4 ml / (m under the condition of 20 ° C. and 85% RH after being held for 5 minutes in a stretched state of 5% under the conditions of 23 ° C. and 50% RH. ² · day · atm) or less.

  The product of the present invention is a product including the multilayer structure of the present invention, and the multilayer structure may be used for a packaging material, a solar cell member, or a display member.

  The production method of the present invention is a method for producing a multilayer structure having one or more base materials (X), layers (Y) and layers (Z), and the layer (Y) contains aluminum atoms, The layer (Z) includes a polymer (E) having a plurality of phosphorus atoms, and at least one layer (Y) and a layer (Z) are laminated adjacent to each other, and a polymer (E) having a plurality of phosphorus atoms is laminated. Step (IV) of forming the layer (Z) by applying a coating liquid (V) containing

  In the production method of the present invention, the polymer (E) may be a homopolymer or copolymer of a (meth) acrylic acid ester containing a phosphate group, and the terminal is a phosphate group. It may contain certain side chains.

  In the production method of the present invention, the polymer (E) may be a homopolymer of acid phosphooxyethyl methacrylate.

In the production method of the present invention, the layer (Y) may be a layer (YA) containing a reaction product (R), and the reaction product (R) is a metal oxide (A) containing aluminum. And a reaction product obtained by reacting the phosphorus compound (B). In this case, the production method of the present invention comprises mixing the metal oxide (A), at least one compound containing a site capable of reacting with the metal oxide (A), and a solvent. A step (I) of preparing a coating liquid (U) containing the metal oxide (A), the at least one compound and the solvent;
(II) forming a precursor layer of the layer (YA) on the substrate (X) by applying the coating liquid (U) on the substrate (X);
The method may further include a step (III) of forming the layer (YA) by heat-treating the precursor layer of the layer (YA) at a temperature of 140 ° C. or higher. The at least one compound may contain the phosphorus compound (B). In the coating liquid (U), the number of moles N _M of metal atoms (M) constituting the metal oxide (A) and the number of moles N _{P of} phosphorus atoms contained in the phosphorus compound (B) are 1 The relationship of 0.0 ≦ (the number of moles N _M ) / (the number of moles N _P ) ≦ 3.6 may be satisfied.

  In the production method of the present invention, the step (IV) may be performed after the step (III).

  In the production method of the present invention, the layer (Y) may be an aluminum deposition layer or an aluminum oxide deposition layer.

  ADVANTAGE OF THE INVENTION According to this invention, the multilayer structure which is excellent in gas barrier property and can maintain gas barrier property at a high level also when receiving physical stress, such as a deformation | transformation and an impact, is obtained. Moreover, according to the manufacturing method of this invention, the said multilayer structure can be manufactured easily.

  In the present specification, the property of maintaining the gas barrier property at a high level even when subjected to physical stress such as deformation or impact may be expressed as “bending resistance”. Further, in this specification, “gas barrier property after holding for 5 minutes in a stretched state of 5% under the conditions of 23 ° C. and 50% RH” was adopted as an index for evaluating the bending resistance. This is an evaluation condition that is severer than the physical stress that can occur under normal practical conditions, and a multilayer structure showing a good evaluation result with this index can be expected to show good performance even in actual use.

  Hereinafter, embodiments of the present invention will be described. In the following description, specific materials (compounds and the like) may be exemplified as materials that exhibit a specific function, but the present invention is not limited to an embodiment using such materials. Moreover, as long as there is no description in particular, the material illustrated may be used individually by 1 type, and may use 2 or more types together.

[Multilayer structure]
The multilayer structure of the present invention is a multilayer structure having at least one substrate (X), layer (Y) and layer (Z), wherein the layer (Y) contains aluminum atoms and the layer (Z) Includes a polymer (E) having a plurality of phosphorus atoms, and at least one layer (Y) and layer (Z) are laminated adjacent to each other. Such a multilayer structure is obtained by the method of the present invention for producing a multilayer structure.

[Layer (Y)]
The layer (Y) of the multilayer structure of the present invention is a layer (YA) containing a reaction product (R) formed by a reaction of at least an aluminum-containing metal oxide (A) and a phosphorus compound (B). May be. Alternatively, the layer (Y) is a layer that is an aluminum deposition layer (hereinafter may be referred to as “layer (YB)”) or an aluminum oxide deposition layer (hereinafter may be referred to as “layer (YC)”). Hereinafter, these will be described in order.

[Layer (YA)]
When the layer (Y) of the multilayer structure of the present invention is the layer (YA), in the infrared absorption spectrum of the layer (YA), the wave number (maximum infrared absorption in the range of 800 to 1400 cm ⁻¹ ( n ¹ ) may be in the range of 1080 to 1130 cm ⁻¹ .

Hereinafter, the wave number (n ¹ ) may be referred to as “maximum absorption wave number (n ¹ )”. The metal oxide (A) usually reacts with the phosphorus compound (B) in the form of particles of the metal oxide (A).

  Typically, the layer (YA) included in the multilayer structure of the present invention has a structure in which particles of the metal oxide (A) are bonded to each other via a phosphorus atom derived from the phosphorus compound (B). The form bonded via a phosphorus atom includes the form bonded via an atomic group containing a phosphorus atom, for example, bonded via an atomic group containing a phosphorus atom and not containing a metal atom. Are included.

  In the layer (YA) of the multilayer structure of the present invention, the number of moles of metal atoms that are bonded to the metal oxide (A) particles and are not derived from the metal oxide (A) is metal. It is preferably in the range of 0 to 1 times the number of moles of phosphorus atoms bonding the particles of the oxide (A) (for example, in the range of 0 to 0.9 times), for example, 0.3 times or less, It may be 0.05 times or less, 0.01 times or less, or 0 times.

  The layer (YA) included in the multilayer structure of the present invention may partially contain a metal oxide (A) and / or a phosphorus compound (B) that is not involved in the reaction.

In general, a metal atom and a phosphorus compound react to react a metal atom (M) constituting the metal compound and a phosphorus atom (P) derived from the phosphorus compound bonded via an oxygen atom (O). When a bond represented by is generated, a characteristic peak occurs in the infrared absorption spectrum. Here, the characteristic peak shows an absorption peak at a specific wave number depending on the environment or structure around the bond. As a result of the study by the present inventors, when the absorption peak based on the M—O—P bond is located in the range of 1080 to 1130 cm ⁻¹ , excellent gas barrier properties are expressed in the obtained multilayer structure. I understood. In particular, when the absorption peak appears as an absorption peak of the maximum absorption wave number in the region of 800 to 1400 cm ⁻¹ where absorption derived from bonds between various atoms and oxygen atoms is generally observed, in the obtained multilayer structure Furthermore, it turned out that the outstanding gas-barrier property is expressed.

In addition, although this invention is not limited at all, the metal oxide (A) particle | grains are via the phosphorus atom derived from a phosphorus compound (B), and the metal atom which does not originate in a metal oxide (A) And a metal atom (M) constituting the metal oxide (A) and a phosphorus atom (P) which are bonded via an oxygen atom (O). In the infrared absorption spectrum of the layer (YA), the absorption peak based on the M—O—P bond is 1080 due to the relatively fixed environment of the surface of the metal oxide (A) particles. It is thought that it appears as an absorption peak of the maximum absorption wave number in the region of 800-1400 cm ^{−1 in} the range of ˜1130 cm ⁻¹ .

In contrast, when a metal compound not forming a metal oxide such as a metal alkoxide or metal salt and a phosphorus compound (B) are mixed in advance and then hydrolyzed and condensed, the metal atom derived from the metal compound and A complex in which phosphorus atoms derived from the phosphorus compound (B) are mixed almost uniformly and reacted is obtained, and in the infrared absorption spectrum, the maximum absorption wave number (n ¹ ) in the range of 800 to 1400 cm ⁻¹ is 1080 to 1130 cm ^−. Beyond the range of ¹ .

The maximum absorption wave number (n ¹ ) is preferably in the range of 1085 to 1120 cm ⁻¹ , and more preferably in the range of 1090 to 1110 cm ⁻¹ , because a multilayer structure having excellent gas barrier properties is obtained.

In the infrared absorption spectrum of the layer (YA) of the multilayer structure of the present invention, absorption of stretching vibrations of hydroxyl groups bonded to various atoms may be observed in the range of 2500 to 4000 cm ⁻¹ . Examples of hydroxyl groups that are absorbed in this range include hydroxyl groups that exist on the surface of the metal oxide (A) portion and have the form of M-OH, and are bonded to phosphorus atoms (P) derived from the phosphorus compound (B). And a hydroxyl group having a P—OH form, a hydroxyl group having a C—OH form derived from the polymer (C) described later, and the like. The amount of the hydroxyl group present in the layer (YA) can be correlated with the absorbance (A ² ) at the maximum absorption wave number (n ² ) based on the stretching vibration of the hydroxyl group in the range of 2500 to 4000 cm ⁻¹ . Here, the wave number (n ² ) is a wave number that maximizes infrared absorption based on the stretching vibration of hydroxyl groups in the range of 2500 to 4000 cm ⁻¹ in the infrared absorption spectrum of the layer (YA). Hereinafter, the wave number (n ² ) may be referred to as “maximum absorption wave number (n ² )”.

As the amount of hydroxyl groups present in the layer (YA) increases, the density of the layer (YA) decreases, and as a result, gas barrier properties tend to decrease. In the infrared absorption spectrum of the layer (YA) of the multilayer structure of the present invention, the ratio between the absorbance (A ¹ ) and the absorbance (A ² ) at the maximum absorption wave number (n ¹ ) [absorbance (A ² ) / Absorbance (A ¹ )] is smaller, it is considered that the particles of the metal oxide (A) are more effectively bonded via the phosphorus atom derived from the phosphorus compound (B). Therefore, the ratio [absorbance (A ² ) / absorbance (A ¹ )] is preferably 0.2 or less, and preferably 0.1 or less, from the viewpoint of highly expressing the gas barrier property of the resulting multilayer structure. It is more preferable. The multilayer structure in which the layer (YA) has the above ratio [absorbance (A ² ) / absorbance (A ¹ )] is the number of moles of metal atoms (N _M ) constituting the metal oxide (A) described later. And the ratio of the number of moles of phosphorus atoms derived from the phosphorus compound (B) (N _P ), heat treatment conditions, and the like. Although not particularly limited, in the infrared absorption spectrum of the precursor layer for later layers (YA), maximum absorbance in the range 800～1400Cm ^-1 and (A ¹ '), 2500~4000cm ^-1 In some cases, the maximum absorbance (A ² ′) based on the stretching vibration of the hydroxyl group in the range satisfies the relationship of absorbance (A ² ′) / absorbance (A ¹ ′)> 0.2.

In the infrared absorption spectrum of the layer (YA) of the multilayer structure of the present invention, the half width of the absorption peak having a maximum at the maximum absorption wave number (n ¹ ) is 200 cm ⁻ from the viewpoint of gas barrier properties of the resulting multilayer structure. preferably ¹ or less, more preferably 150 cm ^-1 or less, more preferably 130 cm ^-1 or less, more preferably 110 cm ^-1 or less, further not more 100 cm ^-1 or less It is particularly preferably 50 cm ⁻¹ or less. Although this invention is not limited at all, when the particles of the metal oxide (A) are bonded to each other via a phosphorus atom, the particles of the metal oxide (A) are phosphorous derived from the phosphorus compound (B). Metal atoms (M) and phosphorus atoms (P) constituting the metal oxide (A) are bonded with oxygen atoms (O) through atoms and without metal atoms not derived from the metal oxide (A). When the bond represented by M-O-P is formed through the metal oxide (A), the maximum absorption wave number (n ¹ ) is maximized due to the relatively fixed environment of the surface of the metal oxide (A) particles. It is considered that the half width of the absorption peak having a value falls within the above range. In this specification, the half width of the absorption peak of the maximum absorption wave number (n ¹ ) is the wave number of two points having an absorbance (absorbance (A ¹ ) / 2) that is half of the absorbance (A ¹ ) at the absorption peak. It can be obtained by calculating the difference.

  The infrared absorption spectrum of the layer (YA) is measured by the ATR method (total reflection measurement method), or the layer (YA) is scraped from the multilayer structure and the infrared absorption spectrum is measured by the KBr method. Can be obtained.

  In the layer (YA) of the multilayer structure of the present invention, the shape of each particle of the metal oxide (A) is not particularly limited, and for example, a shape such as a spherical shape, a flat shape, a polyhedral shape, a fibrous shape, or a needle shape is used. A fibrous or needle-like shape is preferable because a multilayer structure having excellent gas barrier properties can be obtained. The layer (YA) may have only particles having a single shape, or may have particles having two or more different shapes. In addition, the size of the metal oxide (A) particles is not particularly limited, and examples include nanometer-size to submicron-size particles. The size of the particles (A) is preferably in the range of 1 to 100 nm as an average particle size.

  Note that the fine structure as described above in the layer (YA) of the multilayer structure of the present invention can be confirmed by observing a cross section of the layer (YA) with a transmission electron microscope (TEM). The particle size of each particle of the metal oxide (A) in the layer (YA) is the maximum length of the longest axis of each particle in the cross-sectional observation image of the layer (YA) obtained by a transmission electron microscope (TEM). The average particle size can be obtained as an average value of the maximum lengths of the particles on an axis perpendicular to the average, and the average particle size of ten particles arbitrarily selected in the cross-sectional observation image is obtained. Can do.

  In one example, the layer (YA) included in the multilayer structure of the present invention is derived from the metal oxide (A) in which the particles of the metal oxide (A) are interposed via the phosphorus atom derived from the phosphorus compound (B). It has a structure bonded without intervening metal atoms. That is, in one example, the metal oxide (A) particles may be bonded to each other via a metal atom derived from the metal oxide (A), but are not bonded to any other metal atom. Have Here, “the structure bonded through the phosphorus atom derived from the phosphorus compound (B) and not through the metal atom not derived from the metal oxide (A)” means the metal oxide (A) to be bonded. Means that the main chain of the bond between the particles has a phosphorus atom derived from the phosphorus compound (B) and does not have a metal atom not derived from the metal oxide (A). A structure having a metal atom in the side chain is also included. However, the layer (YA) of the multilayer structure of the present invention has a structure in which particles of the metal oxide (A) are bonded to each other through both phosphorus atoms and metal atoms derived from the phosphorus compound (B) ( The main chain of the bond between the particles of the metal oxide (A) to be bonded may partially have a structure having both a phosphorus atom and a metal atom derived from the phosphorus compound (B).

In the layer (YA) of the multilayer structure of the present invention, as the bonding form between each particle of the metal oxide (A) and the phosphorus atom, for example, the metal atom (M) constituting the metal oxide (A) and The form with which the phosphorus atom (P) was couple | bonded through the oxygen atom (O) can be mentioned. The particles of the metal oxide (A) may be bonded to each other via a phosphorus atom (P) derived from one molecule of the phosphorus compound (B), but phosphorus derived from two or more molecules of the phosphorus compound (B). It may be bonded via an atom (P). As a specific form of bonding between two bonded metal oxide (A) particles, a metal atom constituting one bonded metal oxide (A) particle is represented as (Mα), When the metal atom constituting the other metal oxide (A) particle is represented by (Mβ), for example, (Mα) -OPO- (Mβ) bond form; (Mα) -OP— [O—P] _n —O— (Mβ) bond form; (Mα) —O—P—Z—P—O— (Mβ) bond form; (Mα) —O—P—Z—P— [ O—P—Z—P] _n —O— (Mβ) and the like. In the example of the bonding form, n represents an integer of 1 or more, and Z represents a constituent atomic group existing between two phosphorus atoms when the phosphorus compound (B) has two or more phosphorus atoms in the molecule. And the description of other substituents bonded to the phosphorus atom is omitted. In the layer (YA) of the multilayer structure of the present invention, it is possible to obtain a multilayer structure in which one metal oxide (A) particle is bonded to a plurality of other metal oxide (A) particles. From the viewpoint of gas barrier properties.

The metal oxide (A) may be a hydrolysis condensate of the compound (L) containing a metal atom (M) to which a hydrolyzable characteristic group is bonded. Examples of the characteristic group include X ^{1 of} the formula (I) described later.

  In addition, the hydrolysis-condensation product of the compound (L) can be substantially regarded as a metal oxide. Therefore, in this specification, the hydrolysis condensate of the compound (L) may be referred to as “metal oxide (A)”. That is, in this specification, “metal oxide (A)” can be read as “hydrolysis condensate of compound (L)”, and “hydrolysis condensate of compound (L)” can be referred to as “metal. It can be read as “oxide (A)”.

[Metal oxide (A)]
The metal atoms constituting the metal oxide (A) (sometimes collectively referred to as “metal atoms (M)”) have a valence of 2 or more (for example, 2 to 4 or 3 to 4). Specifically, for example, metals of Group 2 of the periodic table such as magnesium and calcium; metals of Group 12 of the periodic table such as zinc; metals of Group 13 of the periodic table such as aluminum Examples include metals; metals of Group 14 of the periodic table such as silicon; transition metals such as titanium and zirconium. Silicon may be classified as a semimetal, but in this specification, silicon is included in the metal. The metal atom (M) constituting the metal oxide (A) may be one kind or two or more kinds, but it is necessary to contain at least aluminum. The metal atom (M) that can be used in combination with aluminum is selected from the group consisting of titanium and zirconium because of ease of handling for producing the metal oxide (A) and excellent gas barrier properties of the resulting multilayer structure. It is preferable that there is at least one.

  The total proportion of aluminum, titanium and zirconium in the metal atom (M) was 60 mol% or more, 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 100 mol%. May be. The proportion of aluminum in the metal atom (M) may be 60 mol% or more, 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 100 mol%.

  As the metal oxide (A), those produced by a liquid phase synthesis method, a gas phase synthesis method, a solid pulverization method or the like can be used. In view of the controllability of the thickness and production efficiency, those produced by the liquid phase synthesis method are preferred.

  In the liquid phase synthesis method, a hydrolyzable condensation product of the compound (L) is obtained by hydrolyzing and condensing the compound (L) having a hydrolyzable characteristic group bonded to the metal atom (M) as a raw material. A metal oxide (A) can be synthesized. However, the metal atom (M) included in the compound (L) needs to contain at least aluminum. Moreover, when manufacturing the hydrolysis-condensation product of a compound (L) with a liquid phase synthesis method, the compound (L) which a partly hydrolyzed compound (L) other than the method of using the compound (L) itself as a raw material ( L) partial hydrolyzate, compound (L) completely hydrolyzed product obtained by completely hydrolyzing compound (L), compound (L) partially hydrolyzed and condensed part of compound (L) Metal oxidation can also be achieved by condensing or hydrolyzing a hydrolysis condensate, a product obtained by condensing a part of a complete hydrolyzate of compound (L), or a mixture of two or more of these as raw materials. A thing (A) can be manufactured. The metal oxide (A) thus obtained is also referred to as “hydrolysis condensate of compound (L)” in the present specification. There are no particular limitations on the type of the hydrolyzable characteristic group (functional group), and examples include halogen atoms (F, Cl, Br, I, etc.), alkoxy groups, acyloxy groups, diacylmethyl groups, nitro groups, and the like. However, a halogen atom or an alkoxy group is preferable, and an alkoxy group is more preferable because of excellent controllability of the reaction.

The compound (L) preferably contains at least one compound (L ¹ ) represented by the following formula (I) because the reaction is easily controlled and the resulting multilayer structure has excellent gas barrier properties.
AlX ¹ _m R ¹ _(3-m) (I)
[In Formula (I), X ¹ is selected from F, Cl, Br, I, R ² O—, R ³ C (═O) O—, (R ⁴ C (═O)) ₂ CH— and NO _3. Selected from the group of R ¹ , R ² , R ³ and R ⁴ are each selected from the group consisting of an alkyl group, an aralkyl group, an aryl group and an alkenyl group. In Formula (I), when a plurality of X ¹ are present, these X ¹ may be the same as or different from each other. In the formula (I), when a plurality of R ¹ are present, these R ¹ may be the same or different from each other. In the formula (I), when a plurality of R ² are present, these R ² may be the same or different from each other. In the formula (I), when a plurality of R ³ are present, these R ³ may be the same or different from each other. In the formula (I), when a plurality of R ⁴ are present, these R ⁴ may be the same as or different from each other. m represents an integer of 1 to 3. ]

Examples of the alkyl group represented by R ¹ , R ² , R ³ and R ⁴ include a methyl group, an ethyl group, a normal propyl group, an isopropyl group, a normal butyl group, a s-butyl group, a t-butyl group, and 2-ethylhexyl. Groups and the like. Examples of the aralkyl group represented by R ¹ , R ² , R ³ and R ⁴ include a benzyl group, a phenethyl group and a trityl group. Examples of the aryl group represented by R ¹ , R ² , R ³ and R ⁴ include a phenyl group, a naphthyl group, a tolyl group, a xylyl group, and a mesityl group. Examples of the alkenyl group represented by R ¹ , R ² , R ³ and R ⁴ include a vinyl group and an allyl group. For example, R ¹ is preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms. X ¹ is preferably F, Cl, Br, I, or R ² O—. In a preferred example of the compound (L ¹ ), X ¹ is a halogen atom (F, Cl, Br, I) or an alkoxy group having 1 to 4 carbon atoms (R ² O—), and m is 3. In one example of the compound (L ¹ ), X ¹ is a halogen atom (F, Cl, Br, I) or an alkoxy group having 1 to 4 carbon atoms (R ² O—), and m is 3.

In addition to the compound (L ¹ ), the compound (L) may include at least one compound represented by the following formula.
M ¹ X ¹ _m R ¹ _(nm)
[Wherein M ¹ represents Ti or Zr. X ¹ is selected from the group consisting of F, Cl, Br, I, R ² O—, R ³ C (═O) O—, (R ⁴ C (═O)) ₂ CH—, and NO ₃ . R ¹ , R ² , R ³ and R ⁴ are each selected from the group consisting of an alkyl group, an aralkyl group, an aryl group and an alkenyl group. In Formula (I), when a plurality of X ¹ are present, these X ¹ may be the same as or different from each other. In the formula (I), when a plurality of R ¹ are present, these R ¹ may be the same or different from each other. In the formula (I), when a plurality of R ² are present, these R ² may be the same or different from each other. In the formula (I), when a plurality of R ³ are present, these R ³ may be the same or different from each other. In the formula (I), when a plurality of R ⁴ are present, these R ⁴ may be the same as or different from each other. n is equal to the valence of M ¹ . m represents an integer of 1 to n. ]

Specific examples of the compound (L ¹ ) include, for example, aluminum chloride, aluminum triethoxide, aluminum trinormal propoxide, aluminum triisopropoxide, aluminum trinormal butoxide, aluminum tri-s-butoxide, aluminum tri-t-butoxide, Examples thereof include aluminum compounds such as aluminum triacetate, aluminum acetylacetonate, and aluminum nitrate. Among these, as the compound (L ¹ ), at least one compound selected from aluminum triisopropoxide and aluminum tris-butoxide is preferable. As the compound (L ¹ ), one type may be used alone, or two or more types may be used in combination.

As long as the effect of the present invention is obtained, the ratio of the compound (L ¹ ) to the compound (L) is not particularly limited. The proportion of the compound other than the compound (L ¹ ) in the compound (L) is, for example, 20 mol% or less, 10 mol% or less, 5 mol% or less, or 0 mol%. In one example, the compound (L) consists only of the compound (L ¹ ).

Further, the compound (L) other than the compound (L ¹ ) is not particularly limited as long as the effects of the present invention can be obtained. However, for example, the above-mentioned water is added to metal atoms such as titanium, zirconium, magnesium, calcium, zinc, and silicon. Examples thereof include a compound having a decomposable characteristic group bonded thereto. Silicon may be classified as a semimetal, but in this specification, silicon is included in the metal. Among these, the compound (L) other than the compound (L ¹ ) is preferably a compound having titanium or zirconium as a metal atom because the resulting multilayer structure is excellent in gas barrier properties. Specific examples of the compound (L) other than the compound (L ¹ ) include, for example, titanium tetraisopropoxide, titanium tetranormal butoxide, titanium tetra (2-ethylhexoxide), titanium tetramethoxide, titanium tetraethoxide. And titanium compounds such as titanium acetylacetonate; zirconium compounds such as zirconium tetranormal propoxide, zirconium tetrabutoxide and zirconium tetraacetylacetonate.

  By hydrolyzing the compound (L), at least a part of the hydrolyzable characteristic group of the compound (L) is substituted with a hydroxyl group. Furthermore, the hydrolyzate condenses to form a compound in which the metal atom (M) is bonded through the oxygen atom (O). When this condensation is repeated, a compound that can be substantially regarded as a metal oxide is formed. In addition, a hydroxyl group usually exists on the surface of the metal oxide (A) thus formed.

  In this specification, the oxygen atom (O) bonded to only the metal atom (M), such as the oxygen atom (O) in the structure represented by MOM, with respect to the number of moles of the metal atom (M). For example, the oxygen atom (O) in the structure represented by M—O—H is excluded, and the oxygen atom bonded to the metal atom (M) and the hydrogen atom (H) is excluded) ([[ A compound in which the number of moles of oxygen atoms (O) bonded only to metal atoms (M) / [number of moles of metal atoms (M)]) is 0.8 or more is included in the metal oxide (A) And The ratio of the metal oxide (A) is preferably 0.9 or more, more preferably 1.0 or more, and further preferably 1.1 or more. Although the upper limit of the said ratio is not specifically limited, When the valence of a metal atom (M) is set to n, it will normally be represented by n / 2.

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

  A hydrolysis condensate can be manufactured from a specific raw material by the method employ | adopted by the well-known sol-gel method, for example. The raw materials include compound (L), partial hydrolyzate of compound (L), complete hydrolyzate of compound (L), partial hydrolyzed condensate of compound (L), and complete hydrolysis of compound (L). It is possible to use at least one selected from the group consisting of a part of the product condensed (hereinafter sometimes referred to as “compound (L) component”). These raw materials may be produced by a known method, or commercially available ones may be used. Although there is no particular limitation, for example, a condensate obtained by hydrolytic condensation of about 2 to 10 compounds (L) can be used as a raw material. Specifically, for example, a product obtained by hydrolyzing and condensing aluminum triisopropoxide to form a 2- to 10-mer condensate can be used as a part of the raw material.

  The number of molecules condensed in the hydrolyzed condensate of compound (L) can be controlled by the conditions at the time of condensing or hydrolyzing the compound (L) component. For example, the number of molecules to be condensed can be controlled by the amount of water, the type and concentration of the catalyst, the temperature and time for condensation or hydrolysis condensation, and the like.

  As described above, the layer (YA) of the multilayer structure of the present invention includes a reaction product (R), and the reaction product (R) includes at least an aluminum-containing metal oxide (A) and a phosphorus compound. It is a reaction product formed by reaction with (B). Such a reaction product can be formed by mixing and reacting the metal oxide (A) and the phosphorus compound (B). The metal oxide (A) used for mixing with the phosphorus compound (B) (immediately before mixing) may be the metal oxide (A) itself or a composition containing the metal oxide (A). It may be in the form of a thing. In a preferred example, the metal oxide (A) is mixed with the phosphorus compound (B) in the form of a liquid (solution or dispersion) obtained by dissolving or dispersing the metal oxide (A) in a solvent.

  A preferred method for producing a solution or dispersion of the metal oxide (A) is described below. Here, a method for producing the dispersion liquid will be described by taking as an example the case where the metal oxide (A) does not contain a metal atom other than aluminum atoms, that is, the case where the metal oxide (A) is aluminum oxide (alumina). However, a similar production method can be adopted when producing a solution or dispersion containing other metal atoms. A preferred alumina dispersion is obtained by hydrolyzing and condensing aluminum alkoxide in an aqueous solution whose pH is adjusted with an acid catalyst as necessary to obtain an alumina slurry, which is peptized in the presence of a specific amount of acid. Can do.

  The temperature of the reaction system when the aluminum alkoxide is hydrolytically condensed is not particularly limited. The temperature of the reaction system is usually in the range of 2 to 100 ° C. When water and aluminum alkoxide come into contact, the temperature of the liquid rises, but as the hydrolysis proceeds, alcohol is by-produced, and when the boiling point of the alcohol is lower than that of water, the alcohol volatilizes and the temperature of the reaction system is reduced. It may not rise above the vicinity of the boiling point of the alcohol. In such a case, since the growth of alumina may be slow, it is effective to remove the alcohol by heating to around 95 ° C. The reaction time varies depending on the reaction conditions (presence / absence of acid catalyst, amount and type). The reaction time is usually in the range of 0.01 to 60 hours, preferably in the range of 0.1 to 12 hours, and more preferably in the range of 0.5 to 6 hours. The reaction can be performed in an atmosphere of various gases such as air, carbon dioxide, nitrogen, and argon.

  The amount of water used in the hydrolytic condensation is preferably 1 to 200 mol times, more preferably 10 to 100 mol times with respect to the aluminum alkoxide. When the amount of water is less than 1 mole, hydrolysis does not proceed sufficiently, such being undesirable. On the other hand, when it exceeds 200 mol times, since manufacturing efficiency falls or a viscosity becomes high, it is not preferable. When a component containing water (for example, hydrochloric acid or nitric acid) is used, it is preferable to determine the amount of water used in consideration of the amount of water introduced by the component.

  Examples of the acid catalyst used for the hydrolysis condensation include hydrochloric acid, sulfuric acid, nitric acid, p-toluenesulfonic acid, benzoic acid, acetic acid, lactic acid, butyric acid, carbonic acid, oxalic acid, maleic acid, and the like. Among these, hydrochloric acid, sulfuric acid, nitric acid, acetic acid, lactic acid, and butyric acid are preferable, and nitric acid and acetic acid are more preferable. When an acid catalyst is used at the time of 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.

  The alumina slurry obtained by hydrolysis and condensation can be used as an alumina dispersion as it is, but the obtained alumina slurry is heated in the presence of a specific amount of acid to peptize and become transparent. An alumina dispersion having excellent viscosity stability can be obtained.

  As an acid used at the time of peptization, a monovalent inorganic acid or organic acid such as nitric acid, hydrochloric acid, perchloric acid, formic acid, acetic acid, propionic acid can be used. Among these, nitric acid, hydrochloric acid, and acetic acid are preferable, and nitric acid and acetic acid are more preferable.

  When nitric acid or hydrochloric acid is used as the acid during peptization, the amount is preferably 0.001 to 0.4 mol times, preferably 0.005 to 0.3 mol times the aluminum atom. More preferred. When the amount is less than 0.001 mole times, peptization may not sufficiently proceed or a very long time may be required. On the other hand, when it exceeds 0.4 mole times, the temporal stability of the resulting alumina dispersion tends to be lowered.

  On the other hand, when acetic acid is used as the acid during peptization, the amount thereof is preferably 0.01 to 1.0 mol times, preferably 0.05 to 0.5 mol times with respect to aluminum atoms. More preferred. When the amount is less than 0.01 mole times, peptization may not proceed sufficiently, or problems such as a very long time may occur. On the other hand, when it exceeds 1.0 mole times, the temporal stability of the resulting alumina dispersion tends to be lowered.

  The acid to be present at the time of peptization may be added at the time of hydrolysis condensation, but when acid is lost when removing alcohol by-produced by hydrolysis condensation, the amount is in the above range. It is preferable to add it again.

  By performing peptization within the range of 40 to 200 ° C., it is possible to pept in a short time with an appropriate amount of acid used to produce an alumina dispersion having a predetermined particle size and excellent viscosity stability. be able to. When the temperature during peptization is less than 40 ° C, it takes a long time for peptization, and when it exceeds 200 ° C, the increase in peptization rate by increasing the temperature is slight, while the high pressure vessel It is not preferable because it is economically disadvantageous.

  After the peptization is completed, an alumina dispersion having a predetermined concentration can be obtained by performing dilution with a solvent or concentration by heating as necessary. However, in order to suppress thickening and gelation, it is preferable to carry out the heat concentration at 60 ° C. or lower under reduced pressure.

  It is preferable that the metal oxide (A) to be mixed with the phosphorus compound (B) (a composition containing the phosphorus compound (B) when used as a composition) does not substantially contain a phosphorus atom. However, for example, due to the influence of impurities during preparation of the metal oxide (A), it is used for mixing with the phosphorus compound (B) (a composition containing the phosphorus compound (B) when used as a composition). A small amount of phosphorus atoms may be mixed in the metal oxide (A). Therefore, the metal oxide (A) used for mixing with the phosphorus compound (B) (a composition containing the phosphorus compound (B) when used as a composition) within a range in which the effects of the present invention are not impaired. May contain a small amount of phosphorus atoms. The phosphorus atom content contained in the metal oxide (A) used for mixing with the phosphorus compound (B) (a composition containing the phosphorus compound (B) when used as a composition) is more excellent in gas barrier properties. Since a multilayer structure can be obtained, it is preferably 30 mol% or less, based on the number of moles of all metal atoms (M) contained in the metal oxide (A) (100 mol%). % Or less, more preferably 5 mol% or less, further preferably 1 mol% or less, and may be 0 mol%.

  In the layer (YA) of the multilayer structure of the present invention, the metal oxide (A) particles have a specific structure bonded through phosphorus atoms derived from the phosphorus compound (B). Metal used for mixing the shape and size of the metal oxide (A) particles in the layer (YA) with the phosphorus compound (B) (a composition containing the phosphorus compound (B) when used as a composition) The shape and size of the oxide (A) particles may be the same or different from each other. That is, the shape and size of the metal oxide (A) particles used as the raw material for the layer (YA) may change during the process of forming the layer (YA). In particular, when the layer (YA) is formed using the coating liquid (U) described later, in the coating liquid (U) and the liquid (S) described later that can be used to form the layer, Or in each process after apply | coating coating liquid (U) on base material (X), a shape and size may change.

[Phosphorus Compound (B)]
The phosphorus compound (B) contains a site capable of reacting with the metal oxide (A), and typically contains a plurality of such sites. In a preferred example, the phosphorus compound (B) contains 2 to 20 such sites (atomic groups or functional groups). Examples of such a part include a part capable of reacting with a functional group (for example, a hydroxyl group) present on the surface of the metal oxide (A). For example, examples of such a site include a halogen atom directly bonded to a phosphorus atom and an oxygen atom directly bonded to a phosphorus atom. Those halogen atoms and oxygen atoms can cause a condensation reaction (hydrolysis condensation reaction) with a hydroxyl group present on the surface of the metal oxide (A). The functional group (for example, hydroxyl group) present on the surface of the metal oxide (A) is usually bonded to the metal atom (M) constituting the metal oxide (A).

  As the phosphorus compound (B), for example, a compound having a structure in which a halogen atom or an oxygen atom is directly bonded to a phosphorus atom can be used. By using such a phosphorus compound (B), a metal oxide (A) can be used. It can be combined by condensation (hydrolysis) with a hydroxyl group present on the surface. The phosphorus compound (B) may have one phosphorus atom, or may have two or more phosphorus atoms.

The phosphorus compound (B) may be at least one compound selected from the group consisting of phosphoric acid, polyphosphoric acid, phosphorous acid, phosphonic acid, and derivatives thereof. Specific examples of polyphosphoric acid include pyrophosphoric acid, triphosphoric acid, polyphosphoric acid condensed with four or more phosphoric acids, and the like. Examples of the above derivatives include salts of phosphoric acid, polyphosphoric acid, phosphorous acid, phosphonic acid, (partial) ester compounds, halides (chlorides, etc.), dehydrates (niline pentoxide, etc.) and the like. . In addition, examples of phosphonic acid derivatives include a hydrogen atom directly bonded to a phosphorus atom of phosphonic acid (HP (═O) (OH) ₂ ), which may have various functional groups. Substituted compounds (eg, nitrilotris (methylenephosphonic acid), N, N, N ′, N′-ethylenediaminetetrakis (methylenephosphonic acid), etc.), salts thereof, (partial) ester compounds, halides and dehydration Things are also included. Furthermore, organic polymers having a phosphorus atom, such as phosphorylated starch and polymer (E) described later, can also be used as the phosphorus compound (B). These phosphorus compounds (B) may be used alone or in combination of two or more. Among these phosphorus compounds (B), the stability of the coating liquid (U) in the case of forming the layer (YA) using the coating liquid (U) described later and the gas barrier property of the resulting multilayer structure are more excellent. Therefore, it is preferable to use phosphoric acid alone or to use phosphoric acid and other phosphorus compounds in combination.

  As described above, the layer (YA) of the multilayer structure of the present invention includes the reaction product (R), and the reaction product (R) includes at least the metal oxide (A) and the phosphorus compound (B). It is a reaction product formed by the reaction. Such a reaction product can be formed by mixing and reacting the metal oxide (A) and the phosphorus compound (B). The phosphorus compound (B) used for mixing with the metal oxide (A) (immediately before mixing) may be the phosphorus compound (B) itself or a form of a composition containing the phosphorus compound (B). The form of the composition containing the phosphorus compound (B) is preferable. In a preferred example, the phosphorus compound (B) is mixed with the metal oxide (A) in the form of a solution obtained by dissolving the phosphorus compound (B) in a solvent. Although any solvent can be used at that time, water or a mixed solvent containing water is a preferable solvent.

  The phosphorus compound (B) used for mixing with the metal oxide (A) or the composition containing the phosphorus compound (B) has a low metal atom content, so that a multilayer structure excellent in gas barrier properties can be obtained. To preferred. The phosphorus compound (B) or composition containing the phosphorus compound (B) to be mixed with the metal oxide (A) contains metal atoms in the phosphorus compound (B) or phosphorus compound (B). Is preferably 100 mol% or less, more preferably 30 mol% or less, and more preferably 5 mol% or less, based on the number of moles of all phosphorus atoms contained in the composition containing More preferably, it is particularly preferably 1 mol% or less, and may be 0 mol%.

[Reaction product (R)]
The reaction product (R) includes a reaction product produced by reacting only the metal oxide (A) and the phosphorus compound (B). The reaction product (R) also includes a reaction product produced by reacting the metal oxide (A), the phosphorus compound (B), and another compound. The reaction product (R) can be formed by the method described in the production method described later.

[Ratio of metal oxide (A) and phosphorus compound (B)]
In the layer (YA), the number of moles N _{M of} metal atoms constituting the metal oxide (A) and the number of moles N _{P of} phosphorus atoms derived from the phosphorus compound (B) are 1.0 ≦ (number of moles N _M ) / (Number of moles N _P ) ≦ 3.6, more preferably 1.1 ≦ (number of moles N _M ) / (number of moles N _P ) ≦ 3.0. When the value of (number of moles N _M ) / (number of moles N _P ) exceeds 3.6, the metal oxide (A) becomes excessive with respect to the phosphorus compound (B), and the particles of the metal oxide (A) Insufficient bonding occurs, and the amount of hydroxyl groups present on the surface of the metal oxide (A) increases, so that the gas barrier property and its stability tend to be lowered. On the other hand, when the value of (number of moles N _M ) / (number of moles N _P ) is less than 1.0, the phosphorus compound (B) becomes excessive with respect to the metal oxide (A), and the metal oxide (A) The excess phosphorus compound (B) that does not participate in the bond with the phosphorus compound increases, the amount of the hydroxyl group derived from the phosphorus compound (B) tends to increase, and the gas barrier property and its stability tend to decrease.

In addition, the said ratio can be adjusted with ratio of the quantity of a metal oxide (A) and the quantity of a phosphorus compound (B) in the coating liquid for forming a layer (YA). The ratio of the moles N _M and the number of moles N _P in the layer (YA) is generally constituted by a ratio in the coating solution moles of phosphorus compound of a metal atom constituting the metal oxide (A) and (B) It is the same as the ratio to the number of moles of phosphorus atoms to be made.

[Polymer (C)]
The layer (YA) included in the multilayer structure of the present invention may further contain a specific polymer (C). The polymer (C) is a polymer having at least one functional group (f) selected from the group consisting of a hydroxyl group, a carboxyl group, a carboxylic anhydride group, and a carboxyl group salt. In the layer (YA) of the multilayer structure, the polymer (C) has one or both of particles of the metal oxide (A) and a phosphorus atom derived from the phosphorus compound (B) depending on the functional group (f) it has. It may be bound directly or indirectly. Further, in the layer (YA) of the multilayer structure, the reaction product (R) is a polymer (C) portion produced by the reaction of the polymer (C) with the metal oxide (A) or the phosphorus compound (B). You may have. In the present specification, a polymer that satisfies the requirements as the phosphorus compound (B) and includes the functional group (f) is not included in the polymer (C) but is treated as the phosphorus compound (B). .

  As the polymer (C), a polymer containing a structural unit having a functional group (f) can be used. Specific examples of such structural units include 1 functional group (f) such as a vinyl alcohol unit, an acrylic acid unit, a methacrylic acid unit, a maleic acid unit, an itaconic acid unit, a maleic anhydride unit, and a phthalic anhydride unit. Examples include structural units having at least one. The polymer (C) may contain only one type of structural unit having the functional group (f), or may contain two or more types of structural units having the functional group (f).

  In order to obtain a multilayer structure having better gas barrier properties and stability, the proportion of the structural unit having the functional group (f) in the total structural units of the polymer (C) is 10 mol% or more. It is preferably 20 mol% or more, more preferably 40 mol% or more, particularly preferably 70 mol% or more, and may be 100 mol%.

  When the polymer (C) is constituted by the structural unit having the functional group (f) and other structural units other than that, the type of the other structural unit is not particularly limited. Examples of such other structural units are derived from (meth) acrylic acid esters such as methyl acrylate units, methyl methacrylate units, ethyl acrylate units, ethyl methacrylate units, butyl acrylate units, and butyl methacrylate units. Structural units derived from vinyl esters such as vinyl formate units and vinyl acetate units; structural units derived from aromatic vinyls such as styrene units and p-styrene sulfonic acid units; ethylene units, propylene units, And structural units derived from olefins such as isobutylene units. When the polymer (C) contains two or more types of structural units, the polymer (C) is any of an alternating copolymer, a random copolymer, a block copolymer, and a tapered copolymer. Also good.

  Specific examples of the polymer (C) having a hydroxyl group include polyvinyl alcohol, partially saponified products of polyvinyl acetate, polysaccharides such as polyethylene glycol, polyhydroxyethyl (meth) acrylate, starch, and polysaccharides derived from polysaccharides. Derivatives and the like. Specific examples of the polymer (C) having a carboxyl group, a carboxylic anhydride group or a carboxyl group salt include polyacrylic acid, polymethacrylic acid, poly (acrylic acid / methacrylic acid), and salts thereof. Can do. Specific examples of the polymer (C) containing a structural unit not containing the functional group (f) include an ethylene-vinyl alcohol copolymer, an ethylene-maleic anhydride copolymer, and a styrene-maleic anhydride copolymer. , Saponified products of isobutylene-maleic anhydride alternating copolymer, ethylene-acrylic acid copolymer, ethylene-ethyl acrylate copolymer, and the like. In order to obtain a multilayer structure having better gas barrier properties and its stability, the polymer (C) comprises polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polysaccharide, polyacrylic acid, polyacrylic acid salt, It is preferably at least one polymer selected from the group consisting of polymethacrylic acid and polymethacrylic acid salts.

  There is no restriction | limiting in particular in the molecular weight of a polymer (C). In order to obtain a multilayer structure having better gas barrier properties and mechanical properties (drop impact strength, etc.), the number average molecular weight of the polymer (C) is preferably 5,000 or more, and 8,000. More preferably, it is more preferably 10,000 or more. The upper limit of the number average molecular weight of the polymer (C) is not particularly limited, and is, for example, 1,500,000 or less.

  In order to further improve the gas barrier properties, the content of the polymer (C) in the layer (YA) is preferably 50% by mass or less based on the mass of the layer (YA) (100% by mass). It is more preferably at most mass%, more preferably at most 30 mass%, and may be at most 20 mass%. The polymer (C) may or may not react with other components in the layer (YA). In the present specification, the case where the polymer (C) reacts with other components is also expressed as the polymer (C). For example, when the polymer (C) is bonded to a phosphorus atom derived from the metal oxide (A) and / or the phosphorus compound (B), it is also expressed as the polymer (C). In this case, the content of the polymer (C) is calculated by dividing the mass of the polymer (C) before bonding with the metal oxide (A) and / or the phosphorus atom by the mass of the layer (YA). To do.

  The layer (YA) of the multilayer structure has a reaction product (R) (provided that the polymer (C) portion is formed by the reaction of the metal oxide (A) containing at least aluminum with the phosphorus compound (B). The reaction product (R) and the non-reacted polymer (C), but may further include other components. Also good.

  Examples of other components include inorganic acid metal salts such as carbonates, hydrochlorides, nitrates, hydrogen carbonates, sulfates, hydrogen sulfates, borates, and aluminates; oxalates, acetates, Organic acid metal salts such as tartrate and stearate; metal complexes such as acetylacetonate metal complexes (such as aluminum acetylacetonate), cyclopentadienyl metal complexes (such as titanocene), cyano metal complexes; layered clay compounds; Agents; polymer compounds other than the polymer (C); plasticizers; antioxidants; ultraviolet absorbers; flame retardants and the like.

  The content of the other components in the layer (YA) in the multilayer structure is preferably 50% by mass or less, more preferably 20% by mass or less, and further preferably 10% by mass or less. It is preferably 5% by mass or less, and may be 0% by mass (excluding other components).

[Thickness of layer (YA)]
The thickness (YA) of the multilayer structure of the present invention (when the multilayer structure has two or more layers (YA), the total thickness of each layer (YA)) is 4.0 μm or less. Preferably, it is 2.0 μm or less, more preferably 1.0 μm or less, and may be 0.9 μm or less. By thinning the layer (YA), the dimensional change of the multilayer structure during processing such as printing and laminating can be kept low, and the flexibility of the multilayer structure is further increased. It can be close to the mechanical characteristics of.

In the multilayer structure of the present invention, even when the total thickness of the layers (YA) is 1.0 μm or less (for example, 0.5 μm or less), the oxygen permeability under the conditions of 20 ° C. and 85% RH is 2 ml / ( m ² · day · atm) or less. Also, the thickness of the layer (YA) (when the multilayer structure has two or more layers (YA), the total thickness of each layer (YA)) is 0.1 μm or more (for example, 0.2 μm or more). It is preferable that The thickness per layer (YA) is preferably 0.05 μm or more (for example, 0.15 μm or more) from the viewpoint of improving the gas barrier properties of the multilayer structure of the present invention. The thickness of the layer (YA) can be controlled by the concentration of a coating liquid (U) described later used for forming the layer (YA) and the coating method.

[Layer (YB) and Layer (YC)]
The layer (Y) of the multilayer structure of the present invention may be a layer (YB) that is an aluminum deposition layer or a layer (YC) that is an aluminum oxide deposition layer. These vapor deposition layers can be manufactured by the same method as the inorganic vapor deposition layer mentioned later.

[Layer (Z)]
The layer (Z) included in the multilayer structure of the present invention includes a polymer (E) having a plurality of phosphorus atoms. By forming the layer (Z) adjacent to the layer (Y), the bending resistance of the multilayer structure of the present invention can be greatly improved.

[Polymer (E)]
The polymer (E) has a plurality of phosphorus atoms in the polymer. In one example, the phosphorus atom is contained in an acidic group or derivative thereof. Examples of the acidic group containing a phosphorus atom include a phosphoric acid group, a polyphosphoric acid group, a phosphorous acid group, and a phosphonic acid group. At least 1 phosphorus atom contains the site | part which can react with a metal oxide (A) among several phosphorus atoms which a polymer (E) has. In a preferred example, the polymer (E) contains about 10 to 1000 such phosphorus atoms. The site | part of the structure described with respect to the phosphorus compound (B) can be mentioned as an example of the site | part regarding the phosphorus atom which can react with a metal oxide (A).

  The polymer (E) is not particularly limited as long as the above conditions are satisfied, but a preferable example is a homopolymer or copolymer of (meth) acrylic acid esters containing a phosphate group at the end of the side chain. Can do. These polymers can be synthesized by synthesizing monomers of (meth) acrylic acid esters having a phosphate group at the end of the side chain and homopolymerizing them or copolymerizing with other vinyl group-containing monomers. Can be obtained at

  The (meth) acrylic acid ester containing a phosphate group at the side chain terminal used in the present invention may be at least one compound represented by the following general formula (II).

[In the formula (II), R ⁵ and R ⁶ are a hydrogen atom or an alkyl group selected from a methyl group, an ethyl group, a normal propyl group, and an isopropyl group, and some of the hydrogen atoms contained in the alkyl group are It may be substituted with other atoms or functional groups. Moreover, n is typically an integer of 1-6. ]

In a typical example, R ⁵ is a hydrogen atom or a methyl group, and R ⁶ is a hydrogen atom or a methyl group.

  Among the monomers represented by the general formula (II), examples of monomers that can be suitably used in the present invention include acid phosphooxyethyl acrylate, acid phosphooxyethyl methacrylate, and acid phosphooxypolyoxyethylene glycol acrylate. Acid phosphooxypolyoxyethylene glycol methacrylate, acid phosphooxypolyoxypropylene glycol acrylate, acid phosphooxypolyoxypropylene glycol methacrylate, 3-chloro-2-acid phosphooxypropyl acrylate and 3-chloro-2-acid phosphooxypropyl A methacrylate etc. can be mentioned. Among these, a homopolymer of acid phosphooxyethyl methacrylate is more preferable from the viewpoint of obtaining a multilayer structure excellent in bending resistance. However, monomers that can be used in the present invention are not limited to these. Some of these monomers are sold under the trade name “Phosmer” by Unichemical Co., Ltd., and can be purchased and used as appropriate.

  The polymer (E) of the present invention may be a homopolymer of a monomer represented by the general formula (II), or two or more monomers represented by the general formula (II) may be used. Or a copolymer of at least one monomer represented by the general formula (II) and another vinyl monomer.

  Other vinyl monomers that can be copolymerized with the monomer represented by the general formula (II) are particularly limited as long as they can be copolymerized with the monomer represented by the general formula (II) Instead, known ones can be used. Examples of such vinyl monomers include acrylic acid, acrylic acid esters, methacrylic acid, methacrylic acid esters, acrylonitrile, methacrylonitrile, styrene, nucleus-substituted styrenes, alkyl vinyl ethers, alkyl vinyl esters, pars. Fluoro-alkyl vinyl ethers, perfluoro-alkyl vinyl esters, maleic acid, maleic anhydride, fumaric acid, itaconic acid, maleimide, or phenylmaleimide. Among these vinyl monomers, those that can be particularly preferably used are methacrylic acid esters, acrylonitrile, styrenes, maleimide, and phenylmaleimide.

  In order to obtain a multilayer structure having better bending resistance, the proportion of the structural unit derived from the monomer represented by the general formula (II) in all the structural units of the polymer (E) is 10 It is preferably at least mol%, more preferably at least 20 mol%, further preferably at least 40 mol%, particularly preferably at least 70 mol%, and may be 100 mol%. .

  Although there is no restriction | limiting in particular in the molecular weight of a polymer (E), Typically, the number average molecular weight of a polymer (E) exists in the range of 1,000-100,000. When the number average molecular weight is in this range, the bending resistance improving effect by laminating the layer (Z) and the viscosity stability of the coating liquid (V) containing the polymer (E) described later are at a high level. Can be compatible. Further, when the molecular weight of the polymer (E) per phosphorus atom is in the range of 150 to 500, the effect of improving the bending resistance by laminating the layer (Z) may be further enhanced. is there.

  The layer (Z) included in the multilayer structure may be composed of only the polymer (E) having a plurality of phosphorus atoms, but may further include other components.

  Examples of other components include inorganic acid metal salts such as carbonates, hydrochlorides, nitrates, hydrogen carbonates, sulfates, hydrogen sulfates, borates, and aluminates; oxalates, acetates, Organic acid metal salts such as tartrate and stearate; metal complexes such as acetylacetonate metal complexes (such as aluminum acetylacetonate), cyclopentadienyl metal complexes (such as titanocene), cyano metal complexes; layered clay compounds; Agents; polymer compounds other than the polymer (E); plasticizers; antioxidants; ultraviolet absorbers; flame retardants and the like.

  The content of the other components in the layer (Z) in the multilayer structure is preferably 50% by mass or less, more preferably 20% by mass or less, and further preferably 10% by mass or less. It is preferably 5% by mass or less, and may be 0% by mass (excluding other components).

  The polymerization reaction for forming the polymer (E) can be performed using a polymerization initiator in a solvent in which both the monomer component as a raw material and the polymer to be produced are dissolved. Examples of polymerization initiators include 2,2-azobisisobutyronitrile, 2,2-azobis (2,4-dimethylvaleronitrile), dimethyl 2,2-azobis (2-methylpropionate), dimethyl Examples include azo initiators such as 2,2-azobisisobutyrate, peroxide initiators such as lauryl peroxide, benzoyl peroxide, and tert-butyl peroctoate. When copolymerizing with other vinyl monomers, a solvent is appropriately selected depending on the combination of comonomers. You may use 2 or more types of mixed solvents as needed.

  The polymerization reaction of an example is performed at a polymerization temperature of 50 to 100 ° C. while dropping a mixed solution consisting of a monomer, a polymerization initiator and a solvent into the solvent, and after the completion of the addition, the polymerization temperature is about 1 to 24 hours. The temperature is maintained and stirring is continued to complete the polymerization.

  When the monomer component is 1, the solvent is preferably used in a weight ratio of about 1.0 to 3.0, and the polymerization initiator is preferably used in a weight ratio of about 0.005 to 0.05. A more preferred weight ratio is 1.5 to 2.5 for the solvent and about 0.01 for the polymerization initiator. If the amount of the solvent and polymerization initiator used is not within the above ranges, the polymer may gel and become insoluble in various solvents, and problems such as inability to apply using the solution may occur.

  The layer (Z) included in the multilayer structure of the present invention can be formed by applying a solution of the polymer (E). Although any solvent can be used at that time, water, alcohols or a mixed solvent thereof can be mentioned as a preferred solvent.

[Thickness of layer (Z)]
The thickness per layer of the layer (Z) is preferably 0.05 μm or more (for example, 0.15 μm or more) from the viewpoint of better bending resistance of the multilayer structure of the present invention. The upper limit of the thickness of the layer (Z) is not particularly limited, but the effect of improving the bending resistance reaches saturation when the thickness is 1.0 μm or more. Therefore, it is economical that the upper limit of the thickness of the layer (Z) is 1.0 μm. Is preferable. The thickness of the layer (Z) can be controlled by the concentration of a coating liquid (V) described later used for forming the layer (Z) and the coating method.

[Substrate (X)]
There is no restriction | limiting in particular in the material of the base material (X) which the multilayer structure of this invention has, The base material which consists of various materials can be used. Examples of the material of the substrate (X) include resins such as thermoplastic resins and thermosetting resins; fiber aggregates such as fabrics and papers; wood; glass; metals; metal oxides and the like. The base material may have a composite structure or a multilayer structure made of a plurality of materials.

  There is no restriction | limiting in particular in the form of base material (X), Layered base materials, such as a film and a sheet | seat, may be sufficient as various molded objects which have solid shapes, such as a sphere, a polyhedron, and a pipe. Among these, the layered base material is particularly useful when a multilayer structure (laminated structure) is used for a packaging material for packaging food or the like, a solar cell member, or the like.

  Examples of the layered substrate include a thermoplastic resin film layer, a thermosetting resin film layer, a fiber polymer sheet (fabric, paper, etc.) layer, a wood sheet layer, a glass layer, an inorganic vapor deposition layer, and a metal foil layer. Examples thereof include a single-layer or multi-layer substrate including at least one layer selected from the group. Among these, a substrate including at least one layer selected from the group consisting of a thermoplastic resin film layer, a paper layer, and an inorganic vapor deposition layer is preferable. In this case, the substrate may be a single layer or a plurality of layers. It may be a layer. A multilayer structure (laminated structure) using such a substrate is excellent in processability to a packaging material and various properties required for use as a packaging material.

  Examples of the thermoplastic resin film forming the thermoplastic resin film layer include polyolefin resins such as polyethylene and polypropylene; polyester resins such as polyethylene terephthalate, polyethylene-2,6-naphthalate, polybutylene terephthalate, and copolymers thereof. Resin; Polyamide resin such as nylon-6, nylon-66, nylon-12, etc .; hydroxyl group-containing polymer such as polyvinyl alcohol and ethylene-vinyl alcohol copolymer; polystyrene; poly (meth) acrylate; polyacrylonitrile; polyacetic acid Polyvinylate; Polyarylate; Regenerated cellulose; Polyimide; Polyetherimide; Polysulfone; Polyethersulfone; Polyetheretherketone; Thermoplastic such as ionomer resin Film obtained by molding a resin can be exemplified. As a base material of a laminate used for a packaging material for packaging food or the like, a film made of polyethylene, polypropylene, polyethylene terephthalate, nylon-6, or nylon-66 is preferable.

  The thermoplastic resin film may be a stretched film or an unstretched film. A stretched film, particularly a biaxially stretched film is preferred because the processability (printing, laminating, etc.) of the resulting multilayer structure is excellent. The biaxially stretched film may be a biaxially stretched film produced by any one of a simultaneous biaxial stretching method, a sequential biaxial stretching method, and a tubular stretching method.

  Examples of the paper used for the paper layer include kraft paper, fine paper, imitation paper, glassine paper, parchment paper, synthetic paper, white board paper, Manila ball, milk carton base paper, cup base paper, ivory paper, and the like. By using a base material including a paper layer, a multilayer structure for a paper container can be obtained.

  It is preferable that the inorganic vapor deposition layer has a barrier property against oxygen gas or water vapor. As the inorganic vapor deposition layer, a light shielding property such as a metal vapor deposition layer such as aluminum or a material having transparency can be appropriately used. The inorganic vapor-deposited layer can be formed by vapor-depositing an inorganic substance on the substrate, and the entire laminate in which the inorganic vapor-deposited layer is formed on the substrate can be used as the base material (X) having a multilayer structure. . Examples of the inorganic deposited layer having transparency include a layer formed from an inorganic oxide such as aluminum oxide, silicon oxide, silicon oxynitride, magnesium oxide, tin oxide, or a mixture thereof; silicon nitride, silicon carbonitride, etc. A layer formed from an inorganic nitride of the above; a layer formed from an inorganic carbide such as silicon carbide. Among these, a layer formed from aluminum oxide, silicon oxide, magnesium oxide, and silicon nitride is preferable from the viewpoint of excellent barrier properties against oxygen gas and water vapor.

  Although the preferable thickness of an inorganic vapor deposition layer changes with kinds of component which comprises an inorganic vapor deposition layer, it is in the range of 2-500 nm normally. Within this range, a thickness that improves the barrier properties and mechanical properties of the multilayer structure may be selected. If the thickness of the inorganic vapor deposition layer is less than 2 nm, the reproducibility of the barrier property development of the inorganic vapor deposition layer with respect to oxygen gas or water vapor tends to decrease, and the inorganic vapor deposition layer may not exhibit sufficient barrier properties. is there. On the other hand, when the thickness of the inorganic vapor deposition layer exceeds 500 nm, the barrier property of the inorganic vapor deposition layer tends to be lowered when the multilayer structure is pulled or bent. The thickness of the inorganic vapor deposition layer is more preferably in the range of 5 to 200 nm, and still more preferably in the range of 10 to 100 nm.

  Examples of the method for forming the inorganic vapor deposition layer include vacuum vapor deposition, sputtering, ion plating, and chemical vapor deposition (CVD). Among these, the vacuum evaporation method is preferable from the viewpoint of productivity. As a heating method in performing vacuum vapor deposition, any of an electron beam heating method, a resistance heating method, and an induction heating method is preferable. Moreover, in order to improve the adhesiveness with the base | substrate with which an inorganic vapor deposition layer is formed, and the denseness of an inorganic vapor deposition layer, you may vapor-deposit using a plasma assist method or an ion beam assist method. Moreover, in order to raise the transparency of an inorganic vapor deposition layer, you may employ | adopt the reactive vapor deposition method which blows in oxygen gas etc. and produces a reaction in the case of vapor deposition.

  When the substrate (X) is layered, the thickness thereof is preferably in the range of 1 to 1000 μm, preferably 5 to 500 μm from the viewpoint of improving the mechanical strength and workability of the resulting multilayer structure. More preferably, it is in the range of 9 to 200 μm.

[Adhesive layer (H)]
In the multilayer structure of the present invention, the layer (Y) and / or the layer (Z) may be laminated so as to be in direct contact with the substrate (X), but the substrate (X) and the layer (Y) And / or the layer (Y) and / or the layer (Z) may be laminated | stacked on the base material (X) through the contact bonding layer (H) arrange | positioned between the layers (Z). According to this configuration, the adhesion between the substrate (X) and the layer (Y) and / or the layer (Z) may be improved. The adhesive layer (H) may be formed of an adhesive resin. The adhesive layer (H) made of an adhesive resin can be formed by treating the surface of the substrate (X) with a known anchor coating agent or applying a known adhesive to the surface of the substrate (X). As the adhesive, a two-component reactive polyurethane adhesive in which a polyisocyanate component and a polyol component are mixed and reacted is preferable. Moreover, adhesiveness may be further improved by adding a small amount of additives such as a known silane coupling agent to the anchor coating agent or adhesive. Preferable examples of the silane coupling agent include silane coupling agents having a reactive group such as an isocyanate group, an epoxy group, an amino group, a ureido group, and a mercapto group. By subjecting the base material (X) and the layer (Y) and / or the layer (Z) to strong bonding via the adhesive layer (H), the multilayer structure of the present invention is subjected to processing such as printing and laminating. In this case, the deterioration of gas barrier properties and appearance can be more effectively suppressed.

  By increasing the thickness of the adhesive layer (H), the strength of the multilayer structure of the present invention can be increased. However, when the adhesive layer (H) is too thick, the appearance tends to deteriorate. The thickness of the adhesive layer (H) is preferably in the range of 0.03 to 0.18 μm. According to this configuration, when the multilayer structure of the present invention is subjected to processing such as printing or laminating, it is possible to more effectively suppress deterioration of gas barrier properties and appearance, and further, the multilayer structure of the present invention. The drop strength of the packaging material using the body can be increased. The thickness of the adhesive layer (H) is more preferably in the range of 0.04 to 0.14 μm, and still more preferably in the range of 0.05 to 0.10 μm.

[Configuration of multilayer structure]
The multilayer structure (laminate) of the present invention may be constituted only by the base material (X), the layer (Y) and the layer (Z), or the base material (X), the layer (Y), and the layer (Z ) And the adhesive layer (H) alone. The multilayer structure of the present invention may include a plurality of layers (Y) and / or a plurality of layers (Z). In addition, the multilayer structure of the present invention includes a member other than the substrate (X), the layer (Y), the layer (Z) and the adhesive layer (H) (for example, a thermoplastic resin film layer, a paper layer, an inorganic vapor deposition layer) Etc.) may be further included. The multilayer structure of the present invention having such other members (such as other layers) can be formed by, for example, attaching the layer (Y) and the layer (Z) directly to the substrate (X) or via the adhesive layer (H). After laminating, it can be produced by further bonding or forming other members (other layers, etc.) directly or via an adhesive layer. By including such other members (such as other layers) in the multilayer structure, the characteristics of the multilayer structure can be improved or new characteristics can be imparted. For example, heat-sealability can be imparted to the multilayer structure of the present invention, and barrier properties and mechanical properties can be further improved.

  In particular, when the outermost surface layer of the multilayer structure of the present invention is a polyolefin layer, heat sealability can be imparted to the multilayer structure or the mechanical properties of the multilayer structure can be improved. 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, 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 is laminated as another layer. It is preferable. From the viewpoint of improving mechanical properties, the polyester is preferably polyethylene terephthalate (PET), the polyamide is preferably nylon-6, and the hydroxyl group-containing polymer is preferably an ethylene-vinyl alcohol copolymer. In addition, you may provide the layer which consists of an anchor coat layer and an adhesive agent between each layer as needed.

  The multilayer structure of the present invention can be formed by laminating at least one layer (Y) and layer (Z) and at least one other layer (including a base material). Examples of other layers include polyester layers, polyamide layers, polyolefin layers (which may be pigment-containing polyolefin layers, heat-resistant polyolefin layers, or biaxially stretched heat-resistant polyolefin layers), hydroxyl group-containing polymer layers (for example, ethylene- Vinyl alcohol copolymer layer), paper layer, inorganic vapor deposition film layer, thermoplastic elastomer layer, and adhesive layer. As long as the multilayer structure includes a base material, a layer (Y) and a layer (Z), and at least one pair of the layer (Y) and the layer (Z) is laminated adjacently, these other layers and layers (Y), the number of layers (Z) and the order of lamination are not particularly limited. As a preferred example, at least one set of the base material (X), the layer (Y), and the layer (Z) is laminated in the order of the base material (X) / layer (Y) / layer (Z). A multilayer structure having a structure may be mentioned. In addition, these other layers can also be replaced with a molded body (molded body having a three-dimensional shape) made of the material.

Specific examples of the configuration of the multilayer structure of the present invention are shown below. In the following specific examples, each layer may be replaced with a molded body (molded body having a three-dimensional shape) made of the material. The multilayer structure may have an adhesive layer such as an adhesive layer (H), but the description of the adhesive layer is omitted in the following specific examples. In the following specification, the layer (YZ) means a structure in which the layer (Y) and the layer (Z) are adjacently stacked, and the order is layer (Y) / layer (Z) or layer. Either (Z) / layer (Y) may be used.
(1) Layer (YZ) / Polyester layer,
(2) layer (YZ) / polyester layer / layer (YZ),
(3) layer (YZ) / polyamide layer,
(4) layer (YZ) / polyamide layer / layer (YZ),
(5) Layer (YZ) / Polyolefin layer,
(6) Layer (YZ) / Polyolefin layer / Layer (YZ),
(7) Layer (YZ) / Hydroxyl-containing polymer layer,
(8) Layer (YZ) / Hydroxyl-containing polymer layer / Layer (YZ),
(9) Layer (YZ) / paper layer,
(10) layer (YZ) / paper layer / layer (YZ),
(11) layer (YZ) / inorganic vapor deposition layer / polyester layer,
(12) Layer (YZ) / Inorganic vapor deposition layer / Polyamide layer,
(13) Layer (YZ) / Inorganic vapor deposition layer / Polyolefin layer,
(14) Layer (YZ) / Inorganic vapor deposition layer / Hydroxyl-containing polymer layer,
(15) Layer (YZ) / Polyester layer / Polyamide layer / Polyolefin layer,
(16) Layer (YZ) / Polyester layer / Layer (YZ) / Polyamide layer / Polyolefin layer,
(17) Polyester layer / layer (YZ) / polyamide layer / polyolefin layer,
(18) layer (YZ) / polyamide layer / polyester layer / polyolefin layer,
(19) layer (YZ) / polyamide layer / layer (YZ) / polyester layer / polyolefin layer,
(20) Polyamide layer / layer (YZ) / polyester layer / polyolefin layer,
(21) Layer (YZ) / Polyolefin layer / Polyamide layer / Polyolefin layer,
(22) layer (YZ) / polyolefin layer / layer (YZ) / polyamide layer / polyolefin layer,
(23) Polyolefin layer / layer (YZ) / polyamide layer / polyolefin layer,
(24) Layer (YZ) / Polyolefin layer / Polyolefin layer,
(25) layer (YZ) / polyolefin layer / layer (YZ) / polyolefin layer,
(26) Polyolefin layer / layer (YZ) / polyolefin layer,
(27) Layer (YZ) / Polyester layer / Polyolefin layer,
(28) Layer (YZ) / Polyester layer / Layer (YZ) / Polyolefin layer,
(29) Polyester layer / layer (YZ) / polyolefin layer,
(30) layer (YZ) / polyamide layer / polyolefin layer,
(31) layer (YZ) / polyamide layer / layer (YZ) / polyolefin layer,
(32) Polyamide layer / layer (YZ) / polyolefin layer,
(33) layer (YZ) / polyester layer / paper layer,
(34) layer (YZ) / polyamide layer / paper layer,
(35) layer (YZ) / polyolefin layer / paper layer,
(36) Polyolefin layer / paper layer / polyolefin layer / layer (YZ) / polyester layer / polyolefin layer,
(37) Polyolefin layer / paper layer / polyolefin layer / layer (YZ) / polyamide layer / polyolefin layer,
(38) Polyolefin layer / paper layer / polyolefin layer / layer (YZ) / polyolefin layer,
(39) Paper layer / Polyolefin layer / Layer (YZ) / Polyester layer / Polyolefin layer,
(40) Polyolefin layer / paper layer / layer (YZ) / polyolefin layer,
(41) Paper layer / layer (YZ) / polyester layer / polyolefin layer,
(42) Paper layer / layer (YZ) / polyolefin layer,
(43) layer (YZ) / paper layer / polyolefin layer,
(44) layer (YZ) / polyester layer / paper layer / polyolefin layer,
(45) Polyolefin layer / paper layer / polyolefin layer / layer (YZ) / polyolefin layer / hydroxyl group-containing polymer layer,
(46) Polyolefin layer / paper layer / polyolefin layer / layer (YZ) / polyolefin layer / polyamide layer,
(47) Polyolefin layer / paper layer / polyolefin layer / layer (YZ) / polyolefin layer / polyester layer.

According to the present invention, a multilayer structure satisfying one or both of the following performances can be obtained. In a preferred example, the thickness of the layer (Y) (when the multilayer structure has two or more layers (Y), the total thickness of each layer (Y)) is 1.0 μm or less (for example, 0.5 μm or more). The multilayer structure having a thickness of 1.0 μm or less satisfies the following performance. The details of the measurement conditions for oxygen permeability will be described in Examples.
(Performance 1) The oxygen permeability under the conditions of 20 ° C. and 85% RH is 2 ml / (m ² · day · atm) or less.
(Performance 2) The oxygen permeability under the conditions of 20 ° C. and 85% RH after holding for 5 minutes in the stretched state of 5% under the conditions of 23 ° C. and 50% RH is 4 ml / (m ² · day · atm) or less.

[Usage]
The multilayer structure of the present invention is excellent in gas barrier properties, and can maintain gas barrier properties at a high level even when subjected to physical stress such as deformation or impact. Moreover, according to the present invention, a multilayer structure having an excellent appearance can be obtained. Therefore, the multilayer structure of the present invention can be applied to various uses. For example, the product of the present invention may be a product including the multilayer structure of the present invention, and the multilayer structure may be a product used for a packaging material, a solar cell member, or a display member. In addition to the gas barrier property, the multilayer structure of the present invention can also have a barrier property against water vapor. In that case, the water vapor barrier property even when subjected to physical stress such as deformation or impact. Can be maintained at a high level. In particular, when used for products such as solar cell members and display members, this characteristic may greatly contribute to the durability of the product.

  The multilayer structure of the present invention is particularly preferably used as a packaging material. Examples of uses other than packaging materials include LCD substrate films, organic EL substrate films, electronic paper substrate films, electronic device sealing films, PDP films, LED films, IC tag films, and solar cell applications. Electronic device-related films such as back sheets and solar cell protective films, optical communication members, flexible films for electronic devices, fuel cell membranes, fuel cell sealing films, and various functional film substrate films are included.

  This packaging material can be applied to various applications, and is preferably used for applications that require a barrier property against oxygen and for applications in which the inside of the packaging material is replaced with various functional gases. For example, the packaging material of the present invention is preferably used as a food packaging material. When used as a packaging material for food, it is particularly preferably used in a form having a fold, such as a stand-up pouch. In addition to food packaging materials, the packaging material of the present invention is preferably used as a packaging material for packaging chemicals such as agricultural chemicals and pharmaceuticals; medical equipment; industrial materials such as machine parts and precision materials; and clothing. Can do.

  In addition, the packaging material of the present invention can be used after being processed into various molded products. Such a molded article may be a vertical bag-filled sealing bag, a vacuum packaging bag, a pouch with a spout, a laminated tube container, an infusion bag, a container lid, a paper container, or a vacuum insulator.

  Heat sealing is performed on the molded product (for example, a vertical bag-filled seal bag). When heat sealing is performed, it is usually necessary to dispose a heat-sealable layer on the inner side of the molded product or on both the inner side and the outer side of the molded product. When the heat-sealable layer is only on the inner side of the molded product (bag), the seal of the body portion is usually a palm-sealed seal. When the heat-sealable layer is on both the inner side and the outer side of the molded product, the seal of the body part is usually an envelope sticker. As the heat-sealable layer, a polyolefin layer (hereinafter sometimes referred to as “PO layer”) is preferable.

  The molded article including the multilayer structure of the present invention is, for example, a vertical bag filling and sealing bag for packaging a liquid, a viscous body, a powder, a solid rose, or a food or beverage combining these. Also good. The vertical bag-filling-seal bag including the multilayer structure of the present invention has excellent gas barrier properties, and the gas barrier property is maintained even when subjected to physical stress such as deformation or impact. According to the bag, the quality deterioration of the contents can be suppressed over a long period of time.

  Hereinafter, the multilayer film including the base material (X) and the layer (YZ) laminated on the base material (X) may be referred to as a barrier multilayer film. This barrier multilayer film is also a kind of multilayer structure of the present invention. Layers for imparting various characteristics (for example, heat sealability) may be laminated on the barrier multilayer film. For example, the multilayer structure of the present invention may have a configuration of barrier multilayer film / adhesive layer / polyolefin layer or polyolefin layer / adhesive layer / barrier multilayer film / adhesive layer / polyolefin layer. That is, the multilayer structure of the present invention may include a polyolefin layer disposed on one outermost surface. Moreover, the multilayer structure of the present invention may include a first polyolefin layer disposed on one outermost surface and a second polyolefin layer disposed on the other outermost surface. The first polyolefin layer and the second polyolefin layer may be the same or different.

  The vertical bag-filling-seal bag may be formed by laminating at least one barrier multilayer film and at least one other layer. Examples of other layers include a polyester layer, a polyamide layer, a polyolefin layer, a paper layer, an inorganic vapor deposition film layer, an EVOH layer, and an adhesive layer. The number of these layers and the order of lamination are not particularly limited, but when heat sealing is performed, a configuration for that is adopted.

  The structure of the multilayer structure particularly preferable as the vertical bag-filling-seal bag is a structure of barrier multilayer film / polyamide layer / PO layer, barrier multilayer film / PO layer, PO layer / barrier multilayer film / PO layer. It is done. In these configurations, for example, a polyamide film can be used as the base material of the barrier multilayer film. The vertical bag-filling-sealed seal bag maintains its gas barrier property even when subjected to physical stress such as deformation or impact. An adhesive layer may be provided between the layers constituting the vertical bag-filling seal bag. Moreover, when the layer (YZ) of the multilayer structure of the present invention is on one side of the base material, the layer (YZ) may face either the outside or the inside of the vertical bag-filling sealing bag.

  The molded product including the multilayer structure of the present invention may be a vacuum packaging bag for packaging food containing solid content. The vacuum packaging bag has excellent gas barrier properties, and the gas barrier properties are maintained even when subjected to physical stress such as deformation or impact. Therefore, the vacuum packaging bag has almost no deterioration in gas barrier properties over a long period of time. Since the vacuum packaging bag is flexible and easily adheres to foods containing solids, it can be easily deaerated during vacuum packaging. Therefore, the vacuum packaging bag can reduce the residual oxygen in the vacuum packaging body, and is excellent in food long-term storage. In addition, after vacuum packaging, a squared or bent portion is less likely to occur, so that defects such as pinholes and cracks are less likely to occur. Moreover, according to this vacuum packaging bag, it can suppress that pinhole generate | occur | produces by friction between vacuum packaging bags or a vacuum packaging bag and a corrugated cardboard. In addition, the vacuum packaging bag has excellent gas barrier properties, and even when subjected to physical stress such as deformation or impact, the gas barrier properties are maintained, so that deterioration of the quality of the contents (for example, food) can be suppressed over a long period of time. it can.

  The vacuum packaging bag may be formed by laminating at least one barrier multilayer film and at least one other layer. Examples of other layers include a polyester layer, a polyamide layer, a polyolefin layer, an inorganic vapor deposition film layer, an EVOH layer, and an adhesive layer. The number of these layers and the order of lamination are not particularly limited, but when heat sealing is performed, a configuration for that is adopted.

  Examples of the structure of the multilayer structure particularly preferable as the vacuum packaging bag include a structure of barrier multilayer film / polyamide layer / PO layer and polyamide layer / barrier multilayer film / PO layer. In these configurations, for example, a polyamide film can be used as the base material of the barrier multilayer film. A vacuum packaging bag using such a multilayer structure is particularly excellent in gas barrier properties after vacuum packaging or after vacuum packaging and heat sterilization. An adhesive layer may be provided between the layers. Moreover, when the layer (YZ) is laminated | stacked only on the single side | surface of a base material, a layer (YZ) may be in the outer side of a vacuum packaging bag with respect to a base material, and may exist inside.

  The molded product including the multilayer structure of the present invention may be a pouch with a spout for packaging various liquid substances. The pouch with a spout can be used as a container for liquid beverages (for example, soft drinks), jelly beverages, yogurt, fruit sauce, seasonings, functional water, and liquid foods. The pouch with spout can also be preferably used as a container for liquid pharmaceuticals such as amino acid infusions, electrolyte infusions, saccharide infusions, and fat emulsions for infusion. The pouch with a spout is excellent in gas barrier properties, and the gas barrier properties are maintained even when subjected to physical stress such as deformation or impact. Therefore, by using the pouch with a spout, it is possible to prevent the contents from being altered even after transportation and after long-term storage. Moreover, since this pouch with a spout is excellent in transparency, it is easy to check the contents and the quality of the contents due to deterioration.

  The pouch with a spout may be formed by laminating at least one barrier multilayer film and at least one other layer. Examples of other layers include a polyester layer, a polyamide layer, a polyolefin layer, an inorganic vapor deposition film layer, an EVOH layer, and an adhesive layer. The number of these layers and the order of lamination are not particularly limited, but when heat sealing is performed, a configuration for that is adopted.

  Examples of the structure of the multilayer structure particularly preferable as the pouch with a spout include a structure of barrier multilayer film / polyamide layer / PO layer and polyamide layer / barrier multilayer film / PO layer. An adhesive layer may be provided between the layers. Moreover, when the layer (YZ) is laminated | stacked only on the single side | surface of a base material, a layer (YZ) may be in the outer side of a pouch with a spout with respect to a base material, and may exist inside.

  The molded article including the multilayer structure of the present invention may be a laminated tube container for packaging cosmetics, medicines, pharmaceuticals, foods, dentifrices and the like. The laminated tube container has excellent gas barrier properties, and the gas barrier properties are maintained even when subjected to physical stress such as deformation or impact. In addition, since the laminated tube container has good transparency, it is easy to confirm the contents and the deterioration of the contents due to deterioration.

  The laminate tube container may be formed by laminating at least one barrier multilayer film and at least one other layer. Examples of other layers include a polyamide layer, a polyolefin layer (which may be a pigment-containing polyolefin layer), an inorganic vapor deposition film layer, an EVOH layer, and an adhesive layer. The number of these layers and the order of lamination are not particularly limited, but when heat sealing is performed, a configuration for that is adopted.

  Particularly preferred configurations for the laminate tube container include PO layer / barrier multilayer film / PO layer, and PO layer / pigment-containing PO layer / PO layer / barrier multilayer film / PO layer. An adhesive layer may be disposed between the layers. Moreover, when the layer (YZ) is laminated | stacked only on the single side | surface of a base material, a layer (YZ) may be in the outer side of a slamination tube container with respect to a base material, and may exist inside.

  The molded article containing the multilayer structure of the present invention may be an infusion bag. For example, an infusion bag filled with a liquid medicine such as an amino acid infusion, an electrolyte infusion, a saccharide infusion, or a fat emulsion for infusion. It may be. The infusion bag has excellent gas barrier properties, and the gas barrier properties are maintained even when subjected to physical stress such as deformation or impact. Therefore, according to the infusion bag, it is possible to prevent the filled liquid medicine from being deteriorated before the heat sterilization treatment, during the heat sterilization treatment, after the heat sterilization treatment, after transportation, and after storage.

  The infusion bag may be formed by laminating at least one barrier multilayer film and at least one other layer. Examples of other layers include polyamide layers, polyolefin layers, inorganic vapor deposition film layers, EVOH layers, thermoplastic elastomer layers, and adhesive layers. The number of these layers and the order of lamination are not particularly limited, but when heat sealing is performed, a configuration for that is adopted.

  Examples of the structure of the multilayer structure particularly preferable as an infusion bag include the structures of barrier multilayer film / polyamide layer / PO layer, and polyamide layer / barrier multilayer film / PO layer. An adhesive layer may be disposed between the layers. Moreover, when the layer (YZ) is laminated | stacked only on one surface of a base material, a layer (YZ) may exist in the outer side of an infusion bag with respect to a base material, and may exist inside.

  The molded product including the multilayer structure of the present invention may be a lid material for containers filled with food products such as processed meat products, processed vegetable products, processed fishery products, and fruits. The container lid material is excellent in gas barrier properties, and the gas barrier properties are maintained even when subjected to physical stress such as deformation or impact, so that deterioration of the quality of food as a content can be suppressed over a long period of time. And this container lid | cover material is preferably used as a lid | cover material of the container used for the preservation | save of contents, such as foodstuff.

  The container lid may be formed by laminating at least one barrier multilayer film and at least one other layer. Examples of other layers include a polyamide layer, a polyolefin layer, an inorganic vapor deposition film layer, an EVOH layer, a polyester layer, a paper layer, and an adhesive layer. The number of these layers and the order of lamination are not particularly limited, but when heat sealing is performed, a configuration for that is adopted.

  Examples of the structure of the multilayer structure particularly preferable as the container lid material include the structures of barrier multilayer film / polyamide layer / PO layer and barrier multilayer film / PO layer. In these configurations, for example, a polyamide film can be used as the base material of the barrier multilayer film. An adhesive layer may be provided between the layers. When the layer (YZ) of the multilayer structure is on one side of the base material, the layer (YZ) may be on the inner side (container side) than the base material, or on the outer side of the base material. Good.

  The molded article including the multilayer structure of the present invention may be a paper container. Even when the paper container is bent, the gas barrier property is hardly lowered. Moreover, since the transparency of a layer (YZ) is favorable, this paper container is preferably used for a container with a window. Furthermore, the paper container is suitable for heating by a microwave oven.

  The paper container may be formed by laminating at least one barrier multilayer film and at least one other layer. Examples of other layers include polyester layers, polyamide layers, polyolefin layers (which may be heat resistant polyolefin layers or biaxially stretched heat resistant polyolefin layers), inorganic vapor deposited film layers, hydroxyl group-containing polymer layers, paper layers, and Includes an adhesive layer. The number of these layers and the order of lamination are not particularly limited, but when heat sealing is performed, a configuration for that is adopted.

  As a configuration of the multilayer structure particularly preferable as a paper container, a configuration of heat resistant polyolefin layer / paper layer / heat resistant polyolefin layer / barrier multilayer film / heat resistant polyolefin layer may be mentioned. An adhesive layer may be disposed between the layers. In the above example, the heat resistant polyolefin layer is composed of, for example, either a biaxially stretched heat resistant polyolefin film or an unstretched heat resistant polyolefin film. From the viewpoint of ease of molding, the heat-resistant polyolefin layer disposed in the outermost layer of the multilayer structure is preferably an unstretched polypropylene film. Similarly, the heat-resistant polyolefin layer disposed inside the outermost layer of the multilayer structure is preferably an unstretched polypropylene film. In a preferred example, all heat-resistant polyolefin layers constituting the multilayer structure are unstretched polypropylene films.

  The molded article including the multilayer structure of the present invention may be a vacuum heat insulator that can be used for various applications that require cold insulation and heat insulation. Since the vacuum heat insulator can maintain a heat insulation effect over a long period of time, heat insulation for homes used for household appliances such as refrigerators, hot water supply facilities and rice cookers, wall portions, ceiling portions, attic portions, floor portions, etc. It can be used for heat insulation panels such as wood, vehicle roofing and vending machines.

  The vacuum heat insulator may be formed by laminating at least one barrier multilayer film and at least one other layer. Examples of other layers include a polyester layer, a polyamide layer, a polyolefin layer, and an adhesive layer. The number of these layers and the order of lamination are not particularly limited, but when heat sealing is performed, a configuration for that is adopted.

  Examples of the structure of the multilayer structure particularly preferable as the vacuum heat insulator include the structures of barrier multilayer film / polyamide layer / PO layer and polyamide layer / barrier multilayer film / PO layer. An adhesive layer may be provided between the layers. Moreover, when the layer (YZ) is laminated | stacked only on one surface of a base material, a layer (YZ) may exist in the outer side of a vacuum heat insulating body with respect to a base material, and may exist inside.

[Method for producing multilayer structure]
Hereinafter, the manufacturing method of the multilayer structure of this invention is demonstrated. According to this method, the multilayer structure of the present invention can be easily produced. The materials used in the method for producing a multilayer structure of the present invention, the configuration of the multilayer structure, and the like are the same as those described above, and therefore, description of overlapping portions may be omitted. For example, the multilayer of the present invention is applied to the substrate (X), the layer (Y), the layer (Z), the metal oxide (A), the phosphorus compound (B), the polymer (C) and the polymer (E). The description in the description of the structure can be applied. In addition, the matter which demonstrated this manufacturing method is applicable to the multilayer structure of this invention. The matters described for the multilayer structure of the present invention can be applied to the production method of the present invention.

  The production method of the present invention is a production method of a multilayer structure having one or more base materials (X), layers (Y) and layers (Z). Layer (Y) contains aluminum atoms. The layer (Z) contains a polymer (E) having a plurality of phosphorus atoms. At least one set of layer (Y) and layer (Z) are laminated adjacent to each other. The production method of the present invention includes a step (IV) of forming a layer (Z) by applying a coating liquid (V) containing a polymer (E) having a plurality of phosphorus atoms.

  When the layer (Y) included in the multilayer structure of the present invention is a layer (YB) that is an aluminum deposition layer or a layer (YC) that is an aluminum oxide deposition layer, the layer (YB) and the layer Since (YC) can be formed by the general vapor deposition method described above, detailed description thereof is omitted. In the following, the layer (Y) of the multilayer structure of the present invention is a layer (YA) containing a reaction product (R) formed by reacting a metal oxide (A) containing at least aluminum with a phosphorus compound (B). ) Will be described in detail. In addition, about the formation method (process (IV) mentioned later) of a layer (Z), when the layer (Y) is any of a layer (YA), a layer (YB), and a layer (YC), the same formation method Can be adopted.

  The layer (Y) of the multilayer structure of the present invention is a layer (YA) containing a reaction product (R) formed by a reaction between a metal oxide (A) containing at least aluminum and a phosphorus compound (B). In some cases, the method for producing a multilayer structure of the present invention includes steps (I), (II), (III) and (IV). In the step (I), a metal oxide (A) containing at least aluminum, at least one compound containing a site capable of reacting with the metal oxide (A), and a solvent are mixed with each other to obtain a metal oxide. (A) A coating liquid (U) containing the at least one compound and the solvent is prepared. In the step (II), a precursor layer of the layer (YA) is formed on the substrate (X) by applying the coating liquid (U) on the substrate (X). In step (III), the precursor layer is heat-treated at a temperature of 140 ° C. or higher to form a layer (YA) on the substrate (X). In step (IV), the layer (Z) is formed by applying a coating liquid (V) containing a polymer (E) having a plurality of phosphorus atoms. The above steps are typically performed in the order of (I), (II), (III), and (IV), but the layer (Z) is placed between the substrate (X) and the layer (YA). In the case of forming in (4), step (IV) may be carried out before step (II). Further, as will be described later, the step (III) can be performed after the step (IV).

[Step (I)]
Hereinafter, the at least one compound containing a site capable of reacting with the metal oxide (A) used in the step (I) may be referred to as “at least one compound (Z)”. In step (I), at least the metal oxide (A), at least one compound (Z), and a solvent are mixed. In one aspect, in the step (I), a raw material containing the metal oxide (A) and at least one compound (Z) is reacted in a solvent. The raw material may contain other compounds in addition to the metal oxide (A) and at least one compound (Z). Typically, the metal oxide (A) is mixed in the form of particles.

In the coating liquid (U), the number of moles N _M of metal atoms (M) constituting the metal oxide (A) and the number of moles N _{P of} phosphorus atoms contained in the phosphorus compound (B) are 1.0 ≦ The relationship of (number of moles N _M ) / (number of moles N _P ) ≦ 3.6 is satisfied. Since the preferable range of the value of (number of moles N _M ) / (number of moles N _P ) has been described above, redundant description is omitted.

  At least one compound (Z) includes a phosphorus compound (B). The number of moles of metal atoms contained in at least one compound (Z) is preferably in the range of 0 to 1 times the number of moles of phosphorus atoms contained in the phosphorus compound (B). Typically, the at least one compound (Z) is a compound containing a plurality of sites capable of reacting with the metal oxide (A), and the number of moles of metal atoms contained in the at least one compound (Z). Is in the range of 0 to 1 times the number of moles of phosphorus atoms contained in the phosphorus compound (B).

  The ratio of (number of moles of metal atoms contained in at least one compound (Z)) / (number of moles of phosphorus atoms contained in phosphorus compound (B)) ranges from 0 to 1 (for example, from 0 to 0.9). By setting the range, a multilayer structure having more excellent gas barrier properties can be obtained. This ratio is preferably 0.3 or less, more preferably 0.05 or less, further preferably 0.01 or less, in order to further improve the gas barrier properties of the multilayer structure. It may be. Typically, at least one compound (Z) consists only of the phosphorus compound (B). In step (I), the ratio can be easily reduced.

Step (I) preferably includes the following steps (a) to (c).
Step (a): A step of preparing a liquid (S) containing the metal oxide (A).
Step (b): A step of preparing a solution (T) containing the phosphorus compound (B).
Step (c): A step of mixing the liquid (S) obtained in the steps (a) and (b) and the solution (T).

  Step (b) may be performed prior to step (a), may be performed simultaneously with step (a), or may be performed after step (a). Hereinafter, each step will be described more specifically.

  In the step (a), a liquid (S) containing the metal oxide (A) is prepared. The liquid (S) is a solution or a dispersion. The liquid (S) can be prepared, for example, by a technique adopted in a known sol-gel method. For example, the above-mentioned compound (L) component, water, and an acid catalyst or an organic solvent as necessary are mixed, and the compound (L) component is condensed or hydrolyzed by a method employed in a known sol-gel method. Can be prepared. The dispersion of the metal oxide (A) obtained by condensing or hydrolyzing the compound (L) component can be used as it is as the liquid (S) containing the metal oxide (A). However, if necessary, a specific treatment (such as peptization as described above, addition or subtraction of a solvent for concentration control) may be performed on the dispersion.

  Step (a) may include a step of condensing (for example, hydrolytic condensation) at least one selected from the group consisting of compound (L) and a hydrolyzate of compound (L). Specifically, the step (a) includes compound (L), partial hydrolyzate of compound (L), complete hydrolyzate of compound (L), partial hydrolyzed condensate of compound (L), and compound (L A step of condensing or hydrolyzing at least one selected from the group consisting of a part of the complete hydrolyzate of L) condensed may be included.

  Another example of the method for preparing the liquid (S) includes a method including the following steps. First, metal is vaporized as a metal atom by thermal energy, and the metal atom is brought into contact with a reactive gas (oxygen) to generate metal oxide molecules and clusters. Then, the metal oxide (A) particle | grains with a small particle size are manufactured by cooling them instantaneously. Next, the liquid (S) (dispersion containing a metal oxide (A)) is obtained by dispersing the particles in water or an organic solvent. In order to improve the dispersibility in water or an organic solvent, the metal oxide (A) particles may be subjected to a surface treatment or a stabilizer such as a surfactant may be added. Moreover, you may improve the dispersibility of a metal oxide (A) by controlling pH.

  As another example of the method for preparing the liquid (S), the bulk metal oxide (A) is pulverized using a pulverizer such as a ball mill or a jet mill, and dispersed in water or an organic solvent. By making it, the method of setting it as liquid (S) (dispersion containing a metal oxide (A)) can be mentioned. However, in this case, it may be difficult to control the shape and size distribution of the metal oxide (A) particles.

  There is no restriction | limiting in particular in the kind of organic solvent which can be used in a process (a), For example, alcohol, such as methanol, ethanol, isopropanol, and normal propanol, is used suitably.

  The content of the metal oxide (A) in the liquid (S) is preferably in the range of 0.1 to 40% by mass, more preferably in the range of 1 to 30% by mass, More preferably, it is in the range of 20 mass%.

  In step (b), a solution (T) containing the phosphorus compound (B) is prepared. The solution (T) can be prepared by dissolving the phosphorus compound (B) in a solvent. When the solubility of the phosphorus compound (B) is low, dissolution may be promoted by heat treatment or ultrasonic treatment.

  The solvent used for preparing the solution (T) may be appropriately selected depending on the type of the phosphorus compound (B), but preferably contains water. As long as the dissolution of the phosphorus compound (B) is not hindered, the solvent is alcohol such as methanol and ethanol; ether such as tetrahydrofuran, dioxane, trioxane and dimethoxyethane; ketone such as acetone and methyl ethyl ketone; glycol such as ethylene glycol and propylene glycol Glycol derivatives such as methyl cellosolve, ethyl cellosolve, n-butyl cellosolve; glycerin; acetonitrile; amides such as dimethylformamide; dimethyl sulfoxide;

  The content of the phosphorus compound (B) in the solution (T) is preferably in the range of 0.1 to 99% by mass, more preferably in the range of 0.1 to 95% by mass, More preferably, it is in the range of 1 to 90% by mass. The content of the phosphorus compound (B) in the solution (T) may be in the range of 0.1 to 50% by mass, in the range of 1 to 40% by mass, It may be in the range of 30% by mass.

  In the step (c), the liquid (S) and the solution (T) are mixed. At the time of mixing the liquid (S) and the solution (T), in order to suppress a local reaction, it is preferable to mix while suppressing the addition rate and vigorously stirring. At this time, the solution (T) may be added to the stirring liquid (S), or the liquid (S) may be added to the stirring solution (T). When mixed in the step (c), the temperature of the liquid (S) and the temperature of the solution (T) are both preferably 50 ° C. or less, more preferably 30 ° C. or less, and both 20 ° C. More preferably, it is as follows. By setting the temperature at the time of mixing to 50 ° C. or less, the metal oxide (A) and the phosphorus compound (B) are uniformly mixed, and the gas barrier properties of the resulting multilayer structure can be improved. Furthermore, the coating liquid (U) excellent in storage stability may be obtained by continuing stirring for about 30 minutes after the completion of mixing.

  Moreover, the coating liquid (U) may contain a polymer (C). The method for including the polymer (C) in the coating liquid (U) is not particularly limited. For example, the polymer (C) may be dissolved in the liquid (S), the solution (T), or the liquid mixture of the liquid (S) and the solution (T) after being added in the form of powder or pellets. Further, the polymer (C) solution may be added to and mixed with the liquid (S), the solution (T), or the liquid mixture of the liquid (S) and the solution (T). Moreover, you may add and mix the liquid (S), the solution (T), or the liquid mixture of a liquid (S) and a solution (T) to the solution of a polymer (C). Before the step (c), the liquid (S) and the solution (T) are mixed in the step (c) by containing the polymer (C) in either the liquid (S) or the solution (T). In this case, the reaction rate between the metal oxide (A) and the phosphorus compound (B) is relaxed, and as a result, a coating liquid (U) having excellent temporal stability may be obtained.

  When the coating liquid (U) contains the polymer (C), a multilayer structure including the layer (YA) containing the polymer (C) can be easily produced.

  The coating liquid (U) may contain at least one acid compound (D) selected from acetic acid, hydrochloric acid, nitric acid, trifluoroacetic acid, and trichloroacetic acid, if necessary. Hereinafter, the at least one acid compound (D) may be simply referred to as “acid compound (D)”. The method for including the acid compound (D) in the coating liquid (U) is not particularly limited. For example, the acid compound (D) may be added as it is to the liquid (S), the solution (T), or the liquid mixture of the liquid (S) and the solution (T) and mixed. Alternatively, the acid compound (D) solution may be added to and mixed with the liquid (S), the solution (T), or the liquid mixture of the liquid (S) and the solution (T). Moreover, you may add and mix the liquid (S), the solution (T), or the liquid mixture of a liquid (S) and a solution (T) to the solution of an acid compound (D). Prior to the step (c), either the liquid (S) or the solution (T) contains the acid compound (D), whereby the liquid (S) and the solution (T) are mixed in the step (c). In some cases, the reaction rate between the metal oxide (A) and the phosphorus compound (B) is relaxed, and as a result, a coating liquid (U) having excellent temporal stability may be obtained.

  In the coating liquid (U) containing the acid compound (D), the reaction between the metal oxide (A) and the phosphorus compound (B) is suppressed, and the precipitation and aggregation of the reaction product in the coating liquid (U) are suppressed. can do. Therefore, the appearance of the obtained multilayer structure may be improved by using the coating liquid (U) containing the acid compound (D). Moreover, since the boiling point of the acid compound (D) is 200 ° C. or less, the acid compound (D) can be easily removed from the layer (YA) by volatilizing the acid compound (D) in the production process of the multilayer structure. Can be removed.

  The content of the acid compound (D) in the coating liquid (U) is preferably in the range of 0.1 to 5.0% by mass, and is preferably in the range of 0.5 to 2.0% by mass. More preferred. Within these ranges, the effect of adding the acid compound (D) can be obtained, and the acid compound (D) can be easily removed. When the acid component remains in the liquid (S), the addition amount of the acid compound (D) may be determined in consideration of the residual amount.

  The liquid obtained by mixing in the step (c) can be used as it is as the coating liquid (U). In this case, the solvent contained in the liquid (S) or solution (T) is usually the solvent for the coating liquid (U). Further, the coating liquid (U) may be prepared by treating the liquid obtained by mixing in the step (c). For example, treatments such as addition of an organic solvent, pH adjustment, viscosity adjustment, and additive addition may be performed.

  You may add an organic solvent to the liquid obtained by mixing of a process (c) in the range which does not inhibit stability of the coating liquid (U) obtained. The addition of the organic solvent may facilitate the application of the coating liquid (U) to the substrate (X) in the step (II). As an organic solvent, what is mixed uniformly in the coating liquid (U) obtained is preferable. Examples of preferred organic solvents include, for example, alcohols such as methanol, ethanol, n-propanol and isopropanol; ethers such as tetrahydrofuran, dioxane, trioxane and dimethoxyethane; ketones such as acetone, methyl ethyl ketone, methyl vinyl ketone and methyl isopropyl ketone; Examples include glycols such as ethylene glycol and propylene glycol; glycol derivatives such as methyl cellosolve, ethyl cellosolve, and n-butyl cellosolve; glycerin; acetonitrile; amides such as dimethylformamide and dimethylacetamide; dimethyl sulfoxide;

  From the viewpoint of the storage stability of the coating liquid (U) and the coating property of the coating liquid (U) on the substrate, the solid content concentration of the coating liquid (U) is preferably in the range of 1 to 20% by mass. More preferably, it is 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 (U) is determined by, for example, adding a predetermined amount of the coating liquid (U) to the petri dish, removing volatiles such as a solvent at 100 ° C. together with the petri dish, and calculating the mass of the remaining solid content. It can be calculated by dividing by the mass of the coating liquid (U) added first. At that time, measure the mass of the remaining solid every time it dries for a certain period of time, and the solid content concentration is defined as the mass of the remaining solids when the mass difference between the two consecutive masses reaches a negligible level. It is preferable to calculate.

  From the viewpoint of the storage stability of the coating liquid (U) and the gas barrier property of the multilayer structure, the pH of the coating liquid (U) is preferably in the range of 0.1 to 6.0, and is preferably 0.2 to 5.0. More preferably, it is in the range of 0.5 to 4.0.

  The pH of the coating liquid (U) can be adjusted by a known method, for example, by adding an acidic compound or a basic compound. Examples of acidic compounds include hydrochloric acid, nitric acid, sulfuric acid, acetic acid, butyric acid, and ammonium sulfate. Examples of basic compounds include sodium hydroxide, potassium hydroxide, ammonia, trimethylamine, pyridine, sodium carbonate, and sodium acetate.

  The state of the coating liquid (U) changes with the passage of time, and eventually tends to become a gel-like composition or precipitate. The time until the state changes as such depends on the composition of the coating liquid (U). In order to stably apply the coating liquid (U) on the substrate (X), it is preferable that the viscosity of the coating liquid (U) is stable over a long period of time. The solution (U) had a viscosity measured with a Brookfield viscometer (B-type viscometer: 60 rpm) even after standing at 25 ° C. for 2 days, with the viscosity at the completion of step (I) as the reference viscosity. It is preferable to prepare so that it may become within 5 times the viscosity. When the viscosity of the coating liquid (U) is within the above range, a multilayer structure having excellent storage stability and more excellent gas barrier properties is often obtained.

  As a method of adjusting the viscosity of the coating liquid (U) to be within the above range, for example, a method of adjusting the concentration of solid content, adjusting pH, or adding a viscosity modifier can be employed. . Examples of viscosity modifiers include carboxymethylcellulose, starch, bentonite, tragacanth gum, stearate, alginate, methanol, ethanol, n-propanol, and isopropanol.

  As long as the effects of the present invention can be obtained, the coating liquid (U) may contain other substances than the substances described above. For example, the coating liquid (U) is an inorganic metal salt such as carbonate, hydrochloride, nitrate, hydrogen carbonate, sulfate, hydrogen sulfate, borate, aluminate; oxalate, acetate, tartrate Organic acid metal salts such as stearates; metal complexes such as acetylacetonate metal complexes (such as aluminum acetylacetonate), cyclopentadienyl metal complexes (such as titanocene), cyano metal complexes; layered clay compounds; It may contain a polymer compound other than the polymer (C); a plasticizer; an antioxidant; an ultraviolet absorber;

[Step (II)]
In the step (II), a precursor layer of the layer (YA) is formed on the substrate (X) by applying the coating liquid (U) on the substrate (X). The coating liquid (U) may be applied directly on at least one surface of the substrate (X). Also, before applying the coating liquid (U), the surface of the substrate (X) is treated with a known anchor coating agent, or a known adhesive is applied to the surface of the substrate (X). Then, the adhesive layer (H) may be formed on the surface of the substrate (X). Moreover, the precursor of the layer (YA) is formed on the layer (Z) by applying the coating liquid (U) on the layer (Z) previously formed on the substrate (X) by the step (IV) described later. A body layer can also be formed.

  In addition, the coating liquid (U) may be degassed and / or defoamed as necessary. As a method of deaeration and / or defoaming treatment, for example, there are methods by evacuation, heating, centrifugation, ultrasonic waves, etc., but a method including evacuation can be preferably used.

  The viscosity of the coating liquid (U) applied in the step (II) and measured with a Brookfield rotational viscometer (SB type viscometer: rotor No. 3, rotational speed 60 rpm) The temperature is preferably 3000 mPa · s or less, and more preferably 2000 mPa · s or less. When the viscosity is 3000 mPa · s or less, the leveling property of the coating liquid (U) is improved, and a multilayer structure having a better appearance can be obtained. The viscosity of the coating liquid (U) when applied in the step (II) can be adjusted by the concentration, temperature, stirring time after mixing in the step (c) and stirring strength. For example, in some cases, the viscosity can be lowered by lengthening the stirring after mixing in the step (c).

  The method for applying the coating liquid (U) on the substrate (X) is not particularly limited, and a known method can be employed. Preferred methods include, for example, a casting method, a dipping method, a roll coating method, a gravure coating method, a screen printing method, a reverse coating method, a spray coating method, a kiss coating method, a die coating method, a metalling bar coating method, and a chamber doctor combined coating method. And curtain coating method.

  Usually, in the step (II), the precursor layer of the layer (YA) is formed by removing the solvent in the coating liquid (U). There is no restriction | limiting in particular in the removal method of a solvent, A well-known drying method is applicable. Specifically, drying methods such as a hot air drying method, a hot roll contact method, an infrared heating method, and a microwave heating method can be applied alone or in combination. The drying temperature is preferably 0 to 15 ° C. or lower than the flow start temperature of the substrate (X). When the coating liquid (U) contains the polymer (C), the drying temperature is preferably 15 to 20 ° C. lower than the thermal decomposition start temperature of the polymer (C). The drying temperature is preferably in the range of 70 to 200 ° C, more preferably in the range of 80 to 180 ° C, and further 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 a heat treatment in step (III) described later.

  When laminating the layer (YA) on both surfaces of the layered substrate (X), the coating liquid (U) is applied to one surface of the substrate (X), and then the first layer ( First layer (YA) precursor layer) and then applying the coating liquid (U) to the other surface of the substrate (X), and then removing the solvent to remove the second layer (first layer). 2 layers (YA) precursor layers) may be formed. The composition of the coating liquid (U) applied to each surface may be the same or different.

  When a layer (YA) is laminated on a plurality of surfaces of the substrate (X) having a three-dimensional shape, a layer (a precursor layer of the layer (YA)) may be formed for each surface by the above method. Or you may form a several layer (precursor layer of a layer (YA)) simultaneously by apply | coating a coating liquid (U) to several surfaces of a base material (X), and drying it simultaneously.

[Step (III)]
In step (III), the layer (YA) is formed by heat-treating the precursor layer (precursor layer of layer (YA)) formed in step (II) at a temperature of 140 ° C. or higher.

  In step (III), a reaction in which the metal oxide (A) particles are bonded via phosphorus atoms (phosphorus atoms derived from the phosphorus compound (B)) proceeds. In another aspect, in the step (III), a reaction for generating the reaction product (R) proceeds. In order to allow the reaction to proceed sufficiently, the temperature of the heat treatment is 140 ° C. or higher, more preferably 170 ° C. or higher, and even more preferably 190 ° C. or higher. If the heat treatment temperature is low, it takes a long time to obtain a sufficient degree of reactivity, which causes a decrease in productivity. The preferable upper limit of the temperature of heat processing changes with kinds etc. of base material (X). For example, when a thermoplastic resin film made of polyamide resin is used as the base material (X), the heat treatment temperature is preferably 190 ° C. or lower. Moreover, when using the thermoplastic resin film which consists of polyester resins as a base material (X), it is preferable that the temperature of heat processing is 220 degrees C or less. The heat treatment can be performed in air, a nitrogen atmosphere, an argon atmosphere, or the like.

  The heat treatment time is preferably in the range of 0.1 second to 1 hour, more preferably in the range of 1 second to 15 minutes, and still more preferably in the range of 5 to 300 seconds. An example of the heat treatment is performed in the range of 140 to 220 ° C. for 0.1 second to 1 hour. In another example of the heat treatment, the heat treatment is performed in the range of 170 to 200 ° C. for 5 to 300 seconds (for example, 10 to 300 seconds).

  The method of the present invention for producing a multilayer structure may include irradiating the precursor layer of layer (YA) or layer (YA) with ultraviolet light. The ultraviolet irradiation may be performed at any stage after the step (II) (for example, after the removal of the solvent of the applied coating liquid (U) is almost completed). The method is not particularly limited, and a known method can be applied. The wavelength of the irradiated ultraviolet light is preferably in the range of 170 to 250 nm, more preferably in the range of 170 to 190 nm and / or in the range of 230 to 250 nm. Further, instead of ultraviolet irradiation, irradiation with radiation such as an electron beam or γ-ray may be performed. By performing ultraviolet irradiation, the gas barrier performance of the multilayer structure may be expressed more highly.

  In order to dispose the adhesive layer (H) between the substrate (X) and the layer (YA), the surface of the substrate (X) is coated with a known anchor coating agent before applying the coating liquid (U). When the treatment is performed or a known adhesive is applied to the surface of the substrate (X), an aging treatment is preferably performed. Specifically, after the coating liquid (U) is applied and before the heat treatment step of step (III), the base material (X) to which the coating liquid (U) is applied is kept at a relatively low temperature for a long time. It is preferable to leave. The temperature of the aging treatment is preferably less than 110 ° C, more preferably 100 ° C or less, and further preferably 90 ° C or less. The temperature of the aging treatment is preferably 10 ° C or higher, more preferably 20 ° C or higher, and further preferably 30 ° C or higher. The aging time is preferably in the range of 0.5 to 10 days, more preferably in the range of 1 to 7 days, and still more preferably in the range of 1 to 5 days. By performing such an aging treatment, the adhesive force between the substrate (X) and the layer (YA) becomes stronger.

[Step (IV)]
In step (IV), layer (Z) is formed on substrate (X) (or layer (Y)) by applying coating liquid (V) containing polymer (E) having a plurality of phosphorus atoms. To do. Usually, the coating liquid (V) is a solution in which the polymer (E) is dissolved in a solvent.

  The coating liquid (V) may be prepared by dissolving the polymer (E) in a solvent, or the solution obtained when the polymer (E) is produced may be used as it is. When the solubility of the polymer (E) is low, dissolution may be promoted by heat treatment or ultrasonic treatment.

  The solvent used in the coating liquid (V) may be appropriately selected according to the type of the polymer (E), but is preferably water, alcohols or a mixed solvent thereof. As long as the dissolution of the polymer (E) is not hindered, the solvent is an ether such as tetrahydrofuran, dioxane, trioxane or dimethoxyethane; a ketone such as acetone or methyl ethyl ketone; a glycol such as ethylene glycol or propylene glycol; a methyl cellosolve, ethyl cellosolve, It may contain glycol derivatives such as n-butyl cellosolve; glycerin; acetonitrile; amides such as dimethylformamide; dimethyl sulfoxide; sulfolane and the like.

  The solid content concentration of the polymer (E) in the coating liquid (V) is preferably in the range of 0.1 to 60% by mass from the viewpoint of storage stability and coating property of the solution, More preferably within the range of 50% by weight, even more preferably within the range of 1.0 to 40% by weight. The solid content concentration can be determined by the same method as described for the coating liquid (U).

  From the viewpoint of the storage stability of the coating liquid (V) and the gas barrier properties of the multilayer structure, the pH of the solution of the polymer (E) is preferably in the range of 0.1 to 6.0, 0.2 to 5 More preferably, it is in the range of 0.0, and more preferably in the range of 0.5 to 4.0.

  The pH of the coating liquid (V) can be adjusted by a known method, for example, by adding an acidic compound or a basic compound. Examples of acidic compounds include hydrochloric acid, nitric acid, sulfuric acid, acetic acid, butyric acid, and ammonium sulfate. Examples of basic compounds include sodium hydroxide, potassium hydroxide, ammonia, trimethylamine, pyridine, sodium carbonate, and sodium acetate.

  Moreover, when it is necessary to control the viscosity of the coating liquid (V), for example, methods such as adjusting the solid content concentration, adjusting the pH, and adding a viscosity modifier can be employed. Examples of viscosity modifiers include carboxymethylcellulose, starch, bentonite, tragacanth gum, stearate, alginate, methanol, ethanol, n-propanol, and isopropanol.

  As long as the effects of the present invention can be obtained, the coating liquid (V) may contain other substances other than the substances described above. For example, the solution of the polymer (E) includes carbonates, hydrochlorides, nitrates, hydrogencarbonates, sulfates, hydrogensulfates, borates, aluminates, etc .; oxalates, acetates, Organic acid metal salts such as tartrate and stearate; Metal complexes such as acetylacetonate metal complexes (such as aluminum acetylacetonate), cyclopentadienyl metal complexes (such as titanocene), cyano metal complexes; layered clay compounds; An agent; a polymer compound other than the polymer (E); a plasticizer; an antioxidant; an ultraviolet absorber;

  In addition, the coating liquid (V) may be degassed and / or defoamed as necessary. As a method of deaeration and / or defoaming treatment, for example, there are methods by evacuation, heating, centrifugation, ultrasonic waves, etc., but a method including evacuation can be preferably used.

  The viscosity of the coating liquid (V) applied in step (IV) and measured with a Brookfield type rotational viscometer (SB type viscometer: rotor No. 3, rotation speed 60 rpm) The temperature is preferably 1000 mPa · s or less, more preferably 500 mPa · s or less. When the viscosity is 1000 mPa · s or less, the leveling property of the coating liquid (V) is improved, and a multilayer structure having a better appearance can be obtained. The viscosity of the coating liquid (V) when applied in the step (IV) can be adjusted by the concentration, temperature and the like.

  The method for applying the solution of the coating liquid (V) on the substrate (X) or the layer (Y) is not particularly limited, and a known method can be adopted. Preferred methods include, for example, a casting method, a dipping method, a roll coating method, a gravure coating method, a screen printing method, a reverse coating method, a spray coating method, a kiss coating method, a die coating method, a metalling bar coating method, and a chamber doctor combined coating method. And curtain coating method.

  Usually, in the step (IV), the layer (Z) is formed by removing the solvent in the coating liquid (V). There is no restriction | limiting in particular in the removal method of a solvent, A well-known drying method is applicable. Specifically, drying methods such as a hot air drying method, a hot roll contact method, an infrared heating method, and a microwave heating method can be applied alone or in combination. The drying temperature is preferably 0 to 15 ° C. or lower than the flow start temperature of the substrate (X). The drying temperature is preferably in the range of 70 to 200 ° C, more preferably in the range of 80 to 180 ° C, and further preferably in the range of 90 to 160 ° C. The removal of the solvent may be carried out under normal pressure or reduced pressure. When step (IV) is performed after step (II), the solvent may be removed by the heat treatment in step (III) described above.

  When laminating the layer (Z) on both sides of the layered substrate (X) with or without the layer (Y), the solvent is removed after applying the coating liquid (V) on one side. The first layer (Z) may be formed by applying the coating liquid (V) to the other surface, and then the solvent may be removed to form the second layer (Z). The composition of the coating liquid (V) applied to each surface may be the same or different.

  When a layer (Z) is laminated on a plurality of surfaces of a substrate (X) having a three-dimensional shape with or without a layer (Y), the layer (Z) is formed for each surface by the above method. May be. Or you may form a some layer (Z) simultaneously by apply | coating a coating liquid (V) to a some surface simultaneously, and making it dry.

  As described above, the steps are typically carried out in the order of (I), (II), (III), and (IV), but the layer (Z) is divided into the substrate (X) and the layer (Y). In the case where it is formed between the steps, step (IV) may be performed before step (II), and step (III) may be performed after step (IV). From the viewpoint of obtaining a multilayer structure having an excellent appearance, it is preferable to carry out step (IV) after step (III).

  The multilayer structure thus obtained can be used as it is as the multilayer structure of the present invention. However, another member (such as another layer) may be further bonded or formed on the multilayer structure as described above to form the multilayer structure of the present invention. The member can be bonded by a known method.

  In one aspect, the production method of the present invention includes a step (W) of forming a layer (Y) containing aluminum atoms and a coating liquid (V) containing a polymer (E) having a plurality of phosphorus atoms. Step (IV) of forming the layer (Z). As described above, when the layer (Y) is the layer (YA), the step (W) may include steps (I), (II), and (III). Further, when the layer (Y) is the layer (YB) or the layer (YC), the step (W) may include a step of forming those layers by a vapor deposition method.

  Hereinafter, the present invention will be described more specifically by way of examples. However, the present invention is not limited to the following examples. In addition, each measurement and evaluation in an Example and a comparative example were implemented with the method of the following (1)-(4).

(1) Infrared absorption spectrum of layer (Y) The infrared absorption spectrum of the layer (YA) formed in the examples was measured by the following method.

First, an infrared absorption spectrum of the layer (YA) laminated on the base material (X) was measured using a Fourier transform infrared spectrophotometer (manufactured by Perkin Elmer, “Spectrum One”). The infrared absorption spectrum was measured in the range of 700 to 4000 cm ⁻¹ in ATR (total reflection measurement) mode. When the thickness of the layer (YA) is 1 μm or less, an absorption peak derived from the base material (X) is detected in the infrared absorption spectrum by the ATR method, and the absorption intensity derived only from the layer (YA) is accurately obtained. It may not be possible. In such a case, the infrared absorption spectrum of only the substrate (X) was separately measured, and only the peak derived from the layer (X) was extracted by subtracting it. A similar method can also be adopted when the layer (YA) is laminated on the layer (Z). In addition, when the layer (YA) is formed inside the multilayer structure (for example, in the case of having a stacking order of base material (X) / layer (YA) / layer (Z)), the layer (YA) The infrared absorption spectrum is measured before forming the layer (Z), or after the layer (Z) is formed, it is peeled off at the interface of the layer (YA), and the infrared absorption spectrum of the exposed layer (YA) is measured. Can be obtained.

Based on the infrared absorption spectrum of the thus obtained layer (YA), the maximum absorption wave numbers (n ¹⁾ in the range of 800～1400Cm ^-1, and the absorbance at the maximum absorption wave (n ¹⁾ (A ¹⁾ Asked. The maximum absorption wave numbers (n ²⁾ based on the stretching vibration of the hydroxyl group in the range of 2500～4000Cm ^-1, and were determined absorbance at the maximum absorption wave (n ²⁾ to (A ^2). Further, the half width of the absorption peak of the maximum absorption wave number (n ¹ ) is obtained by calculating the wave number of two points having an absorbance (absorbance (A ¹ ) / 2) half of the absorbance (A ¹ ) at the absorption peak. Obtained by calculating the difference in wave numbers. When the absorption peak with the maximum absorption wave number (n ¹ ) overlaps with the absorption peak derived from other components, it is separated into absorption peaks derived from the respective components by the least square method using a Gaussian function. After that, the half width of the absorption peak of the maximum absorption wave number (n ¹ ) was obtained in the same manner as described above.

(2) Appearance of multilayer structure The appearance of the obtained multilayer structure was evaluated visually as follows.
A: It was colorless and transparent and uniform and had a very good appearance.
B: Slight cloudiness or unevenness was observed, but the appearance was good.

(3) Oxygen permeability (Os) under conditions of 20 ° C. and 85% RH
The oxygen transmission rate was measured using an oxygen transmission amount measuring device ("MOCON OX-TRAN 2/20" manufactured by Modern Control). Specifically, the multilayer structure is set so that the layer (YZ) (or layer (YZ)) faces the oxygen supply side and the base material (X) faces the carrier gas side, the temperature is 20 ° C., and the oxygen supply Oxygen permeability (unit: ml / (m ² · day · atm) under conditions of 85% RH on the side, 85% RH on the carrier gas side, oxygen pressure of 1 atm, and carrier gas pressure of 1 atm ) Was measured. Nitrogen gas containing 2% by volume of hydrogen gas was used as the carrier gas.

(4) Oxygen permeability (Of) under conditions of 20 ° C. and 85% RH after holding for 5 minutes in a stretched state of 5% under the conditions of 23 ° C. and 50% RH
A multilayer structure having a size of 21 cm × 30 cm was produced. And after leaving the multilayer structure to stand for 24 hours or more under the conditions of 23 ° C. and 50% RH, it is stretched 5% in the major axis direction under the same conditions, and the stretched state is maintained for 5 minutes. A multilayer structure was obtained. The oxygen transmission rate was measured using an oxygen transmission amount measuring device ("MOCON OX-TRAN 2/20" manufactured by Modern Control). Specifically, the multilayer structure is set so that the layer (YZ) faces the oxygen supply side and the base material (X) faces the carrier gas side, the temperature is 20 ° C., and the humidity on the oxygen supply side is 85% RH. The oxygen permeability (unit: ml / (m ² · day · atm)) was measured under conditions where the humidity on the carrier gas side was 85% RH, the oxygen pressure was 1 atm, and the carrier gas pressure was 1 atm. Nitrogen gas containing 2% by volume of hydrogen gas was used as the carrier gas.

[Example of production of coating liquid (U)]
The manufacture example of the coating liquid (U) used in order to manufacture a layer (YA) is shown.
The temperature was raised to 70 ° C. while stirring 230 parts by mass of distilled water. In the distilled water, 88 parts by mass of aluminum isopropoxide was added dropwise over 1 hour, the liquid temperature was gradually raised to 95 ° C., and the generated isopropanol was distilled off to carry out hydrolysis and condensation. After adding 4.0 parts by mass of a 60% by mass nitric acid aqueous solution to the obtained liquid and stirring the mixture at 95 ° C. for 3 hours, the aggregates of the hydrolyzed condensate particles were peptized, and then the solid content concentration was It concentrated so that it might become 10 mass% in conversion of an alumina. To 18.66 parts by mass of the dispersion thus obtained, 58.19 parts by mass of distilled water, 19.00 parts by mass of methanol, and 0.50 parts by mass of a 5% by mass aqueous polyvinyl alcohol solution are added so as to be uniform. To obtain a dispersion liquid (S1). Moreover, 3.66 mass parts of 85 mass% phosphoric acid aqueous solution was used as a solution (T1). Subsequently, both the dispersion (S1) and the solution (T1) were adjusted to 15 ° C. Next, while maintaining the liquid temperature of 15 ° C., the solution (T1) was dropped while stirring the dispersion (S1) to obtain a coating liquid (U1). While maintaining the obtained coating liquid (U1) at 15 ° C., stirring was continued until the viscosity reached 1500 mPa · s. In the coating liquid (U1), the number of moles of metal atoms (N _M ) constituting the metal oxide (A) (alumina) and the number of moles of phosphorus atoms constituting the phosphorus compound (B) (phosphoric acid) ( N _p ) (number of moles (N _M ) / number of moles (N _p )) was 1.15.

The coating solution (U2), the coating solution (U3) and the coating solution (U4) were respectively changed in the same manner except that the ratio of N _M / N _P was changed to 4.48, 1.92 and 0.82, respectively. Obtained.

[Production Example of Coating Liquid (V)]
First, a round bottom flask (internal volume: 50 ml) equipped with a stirrer, reflux condenser, dropping funnel and thermometer was purged with nitrogen, and 12 g of methyl ethyl ketone (hereinafter sometimes abbreviated as “MEK”) as a solvent was charged. It was immersed in an oil bath and heated to 80 ° C. to start refluxing. From this time, a small amount of nitrogen gas was allowed to flow throughout the entire polymerization process. Next, a mixed solution of 8.5 g of acid phosphooxyethyl methacrylate (hereinafter sometimes abbreviated as “PHM”), 5 g of MEK, and 100 mg of azobisisobutyronitrile was prepared, and the same speed was obtained from the dropping funnel over 10 minutes. It was dripped at. After completion of the dropping, the temperature was maintained at 80 ° C., and stirring was continued for about 12 hours to obtain a yellowish viscous liquid polymer solution.

  The polymer solution was poured into about 10 times the amount of 1,2-dichloroethane, the supernatant was removed by decantation, the precipitate was recovered, and the polymer was isolated. The recovered polymer is dissolved in tetrahydrofuran (hereinafter sometimes abbreviated as “THF”), which is a good solvent for the polymer, and reprecipitated in about 10 times the amount of 1,2-dichloroethane by repeating the operation three times. And purified. When the molecular weight of the purified polymer was measured by gel permeation chromatography using THF as a solvent at a polymer concentration of 1 wt%, the molecular weight was about 10,000 in terms of polystyrene.

  The purified polymer was dissolved in a mixed solvent of water and isopropanol at a concentration of 10 wt% to obtain a coating liquid (V1).

  By a method similar to the preparation of the coating liquid (V1), a coating liquid (V2) comprising a homopolymer of acid phosphooxypolyoxypropylene glycol methacrylate (hereinafter sometimes abbreviated as “PHP”) was obtained. Further, similarly, a coating liquid (V3) and a coating liquid obtained by copolymerizing PHM and acrylonitrile (hereinafter sometimes abbreviated as “AN”) at a molar ratio of 2/1 and 1/1, respectively. (V4) was obtained respectively.

[Example 1]
As a base material, a stretched polyethylene terephthalate film (manufactured by Toray Industries, Inc., “Lumirror P60” (trade name), thickness 12 μm, hereinafter sometimes abbreviated as “PET”) was prepared. On the substrate (PET), the coating liquid (U1) was applied by a bar coater so that the thickness after drying was 0.5 μm, and dried at 110 ° C. for 5 minutes. Next, heat treatment was performed at 180 ° C. for 1 minute to obtain a structure (A1) having a structure of layer (Y1) (0.5 μm) / PET (12 μm). Next, the coating liquid (V1) is applied on the layer (Y1) of the structure (A1) by a bar coater so that the thickness after drying is 0.3 μm, and dried at 110 ° C. for 5 minutes, A multilayer structure (B1) of the present invention having a structure of (Z1) (0.3 μm) / layer (Y1) (0.5 μm) / PET (12 μm) was obtained.

The moisture permeability (water vapor transmission rate: WVTR) of the obtained multilayer structure (B1) was measured using a water vapor transmission amount measuring device ("MOCON PERMATRAN 3/33" manufactured by Modern Control). Specifically, the composite structure is set so that the layer (Z1) faces the water vapor supply side and the PET layer faces the carrier gas side, the temperature is 40 ° C., the water vapor supply side humidity is 90% RH, the carrier gas side The moisture permeability (unit: g / (m ² · day)) was measured under the condition of 0% RH. The moisture permeability of the multilayer structure (B1) was 0.2 g / (m ² · day).

[Examples 2-3]
A multilayer structure was obtained by the same method as in Example 1 except that the thickness of the layer (Z) was changed according to Table 1.

[Examples 4 to 6]
A multilayer structure was obtained in the same manner as in Example 1 except that the coating liquid (V) used was changed according to Table 1.

[Examples 7 to 9]
A multilayer structure was obtained in the same manner as in Example 1 except that the heat treatment conditions were changed according to Table 1.

[Examples 10 to 12]
A multilayer structure was obtained in the same manner as in Example 1 except that the coating liquid (U) used was changed according to Table 1.

[Example 13]
A multilayer structure was obtained by the same method as in Example 1 except that the heat treatment step was performed after the formation of the layer (Z).

[Example 14]
A multilayer structure was obtained by the same method as in Example 1 except that the layer (Y) and the layer (Z) were laminated on both surfaces of the substrate. When the moisture permeability of the obtained multilayer structure was measured in the same manner as in Example 1, it was 0.1 g / (m ² · day) or less.

[Example 15]
A multilayer structure is obtained by the same method as in Example 1 except that the base material is a stretched nylon film (“Emblem ONBC” (trade name), unit thickness 15 μm, sometimes abbreviated as “ONY”) manufactured by Unitika Ltd. Got the body.

[Example 16]
A multilayer structure was obtained by the same method as in Example 1 except that the layer (Y) was formed after the formation of the layer (Z).

[Example 17]
A multilayer structure was obtained by the same method as in Example 1 except that the layer (Y) was an aluminum deposited layer having a thickness of 0.03 μm. The aluminum layer was formed by a vacuum evaporation method.

[Example 18]
A multilayer structure was obtained in the same manner as in Example 1 except that the layer (Y) was an aluminum oxide vapor deposition layer having a thickness of 0.03 μm. The aluminum oxide layer was formed by a vacuum evaporation method.

[Comparative Examples 1 to 18]
In Examples 1 to 18, those in which the layer (Z) was not formed were referred to as Comparative Examples 1 to 18.

[Comparative Example 19]
A multilayer structure was obtained by the same method as in Example 1 except that the layer (Y) was a layer (Y) ′ which was a deposited layer of silicon oxide having a thickness of 0.03 μm. The silicon oxide layer was formed by a vacuum evaporation method.

[Comparative Example 20]
A multilayer structure was obtained in the same manner as in Example 1 except that the layer (Y) was not formed.

[Comparative Example 21]
A multilayer structure was obtained in the same manner as in Example 1 except that the layer (Z) was formed on PET. That is, in Comparative Example 20, a multilayer structure of Comparative Example 20 having a structure of layer (Y1) (0.5 μm) / PET (12 μm) / layer (Z1) (0.3 μm) was produced.

[Comparative Example 22]
In Comparative Example 19, the layer (Z) was not formed as Comparative Example 22.

[Comparative Example 23]
Only PET as a substrate was used as Comparative Example 23.

  The production conditions and evaluation results of the above Examples and Comparative Examples are shown in Tables 1 to 3 below. In the table, “-” means “not used”, “cannot be calculated”, “not implemented”, “cannot be measured”, and the like.

  As is clear from the table, the multilayer structures of the examples were able to maintain the gas barrier properties at a high level even when subjected to strong stretching stress. In addition, the multilayer structure of the example showed a good appearance.

[Example 19]
In Example 19, a vertical bag-filled sealing bag was produced using the multilayer structure of the present invention. First, a multilayer structure (B1) was produced by the same method as in Example 1. Next, a two-component adhesive (manufactured by Mitsui Takeda Chemical Co., Ltd., A-520 (trade name) and A-50 (trade name)) is coated on the multilayer structure (B1) and dried. Then, this and a stretched nylon film (ONY described above) were laminated to obtain a laminate. Subsequently, the stretched nylon film of the laminate was coated with a two-component adhesive (Mitsui Takeda Chemical Co., Ltd., A-520 (trade name) and A-50 (trade name)) and dried. This was laminated with an unstretched polypropylene film (manufactured by Tosero Co., Ltd., RXC-21 (trade name), thickness 70 μm, hereinafter abbreviated as “CPP70”). Thus, a multilayer structure (C19) having a structure of PET / layer (Y1) / layer (Z1) / adhesive / ONY / adhesive / CPP70 was obtained.

  Next, the multilayer structure (C19) is cut into a width of 400 mm and supplied to a vertical bag making and filling packaging machine (manufactured by ORIHIRO Co., Ltd.). 470 mm). Next, 2 kg of water was filled into a vertical bag-filling sealing bag made of a multilayer structure (C19) using a bag-filling and packaging machine. The processability of the multilayer structure (C19) in the bag making and filling machine was good, and no defects such as wrinkles and streaks were found in the appearance of the obtained vertical bag filling and sealing bag.

[Example 20]
In Example 20, a vacuum packaging bag was produced using the multilayer structure of the present invention. First, a multilayer structure (B1) was produced by the same method as in Example 1. Next, a two-component adhesive (manufactured by Mitsui Takeda Chemical Co., Ltd., A-520 (trade name) and A-50 (trade name)) is coated on a stretched nylon film (ONY described above) and dried. Was prepared and laminated with the multilayer structure (B1). Next, the laminated multilayer structure (B1) is coated with a two-component adhesive (A-520 (trade name) and A-50 (trade name) manufactured by Mitsui Takeda Chemical Co., Ltd.) and dried. Was prepared and laminated with an unstretched polypropylene film (CPP70 described above). In this way, a multilayer structure (C20) having a configuration of ONY / adhesive / layer (Z1) / layer (Y1) / PET / adhesive / CPP70 was obtained.

  Next, two 22 cm × 30 cm rectangular laminates were cut from the multilayer structure (C20). Then, two multilayer structures (C20) were overlaid so that CPP 70 was inside, and a bag was formed by heat-sealing the three sides of the rectangle. The bag was filled with wooden spheres (diameter 30 mm) as a solid food model in a state where they were spread in one layer so that the spheres were in contact with each other. Thereafter, the air inside the bag was evacuated and the last side was heat-sealed to produce a vacuum package. In the obtained vacuum package, the multilayer structure (C20) was in close contact along the irregularities of the sphere.

[Example 21]
In Example 21, a pouch with a spout was produced using the multilayer structure of the present invention. First, a multilayer structure (C21) having a structure of PET / layer (Y1) / layer (Z1) / adhesive / ONY / adhesive / CPP70 was obtained in the same manner as in Example 19. Next, after cutting out two multilayer structures (C21) into a predetermined shape, the two multilayer structures (C21) are overlaid so that the CPP 70 is on the inside, the periphery is heat-sealed, and further, made of polypropylene. A spout was attached by heat sealing. In this way, a flat pouch-type pouch with a spout could be produced without problems.

[Example 22]
In Example 22, a laminated tube container was produced using the multilayer structure of the present invention. First, a multilayer structure (B1) was produced by the same method as in Example 1. Next, each of two unstretched polypropylene films (manufactured by Tosero Co., Ltd., RXC-21 (trade name), thickness 100 μm, hereinafter sometimes abbreviated as “CPP100”) is a two-component adhesive ( A product prepared by coating A-520 (trade name) and A-50 (trade name) manufactured by Mitsui Takeda Chemical Co., Ltd. and dried was prepared and laminated with the multilayer structure (B1). Thus, a multilayer structure (C22) having a structure of CPP100 / adhesive / layer (Z1) / layer (Y1) / PET / adhesive / CPP100 was obtained.

  Next, after cutting out the multilayer structure (C22) into a predetermined shape, a cylindrical body was manufactured by heat-sealing the overlapped portions in a cylindrical shape. Next, the cylindrical body was attached to a mandrel for forming a tube container, and a frustoconical shoulder portion and a leading end portion thereof were produced at one end of the cylindrical body. The shoulder and the tip were formed by compression molding polypropylene resin. Next, a polypropylene resin cap was attached to the tip. Next, the other open end of the cylindrical body was heat sealed. Thus, the laminated tube container was able to be produced without a problem.

[Example 23]
In Example 23, an infusion bag was produced using the multilayer structure of the present invention. First, a multilayer structure (C23) having a structure of PET / layer (Y1) / layer (Z1) / adhesive / ONY / adhesive / CPP70 was obtained in the same manner as in Example 19. Next, after cutting out two multilayer structures (C23) into a predetermined shape, the two multilayer structures (C23) are overlaid so that the CPP 70 is on the inside, the periphery is heat-sealed, and further made of polypropylene. A spout was attached by heat sealing. In this way, an infusion bag could be produced without problems.

[Example 24]
In Example 24, a container lid was produced using the multilayer structure of the present invention. First, a multilayer structure (C24) having a structure of PET / layer (Y1) / layer (Z1) / adhesive / ONY / adhesive / CPP70 was obtained by the same method as in Example 19. Next, the multilayer structure (C24) was cut into a circle having a diameter of 88 mm as a container lid. In addition, a cylindrical container (high reflex HR 78-84 manufactured by Toyo Seikan Co., Ltd.) having a diameter of 78 mm, a flange width of 6.5 mm, and a height of 30 mm and comprising three layers of polyolefin layer / steel layer / polyolefin layer Got ready. The container was almost completely filled with water, and a container lid made of a multilayer structure (C24) was heat sealed to the flange portion. In this way, a lidded container using the container lid material could be produced without problems.

[Example 25]
In Example 25, a paper container was produced using the multilayer structure of the present invention. First, a multilayer structure (B1) was produced by the same method as in Example 1. Next, an adhesive is applied to both sides of a 400 g / m ² paperboard, and a polypropylene resin (hereinafter sometimes abbreviated as “PP”) is extrusion laminated on both sides, thereby forming a PP layer on both sides of the paperboard. (Thickness 20 μm each) was formed. Thereafter, an adhesive is applied to the surface of one PP layer, the multilayer structure (B1) is laminated thereon, an adhesive is further applied to the surface of the multilayer structure (B1), and an unstretched polypropylene film (described above) CPP70). In this way, a multilayer structure (C25) having a configuration of PP / paperboard / PP / adhesive / layer (Z1) / layer (Y1) / PET / adhesive / CPP70 was produced. In the production of the multilayer structure (C25), an anchor coating agent was used as necessary. Using the multilayer structure (C25) thus obtained, a brick-type paper container could be produced without problems.

[Example 26]
In Example 26, a vacuum thermal insulator was produced using the multilayer structure of the present invention. First, a multilayer structure (C26) having a configuration of ONY / adhesive / layer (Z1) / layer (Y1) / PET / adhesive / CPP70 was obtained in the same manner as in Example 20. Next, after cutting out two multilayer structures (C26) into a predetermined shape, the two multilayer structures (C26) are overlaid so that the CPP 70 is inside, and the three sides of the rectangle are heat sealed. A bag was formed. Next, a heat insulating core material was filled from the opening of the bag, and the bag was sealed using a vacuum packaging machine (VAC-STAR 2500 model manufactured by Frimark GmbH) at a temperature of 20 ° C. and an internal pressure of 10 Pa. Thus, the vacuum heat insulating body was able to be produced without a problem. In addition, the silica fine powder dried for 4 hours in 120 degreeC atmosphere was used for the heat insulating core material.

[Example 27]
In Example 27, a solar cell module was produced using the multilayer structure of the present invention. First, a multilayer structure (B1) was produced by the same method as in Example 1. Next, an amorphous silicon solar battery cell placed on a 10 cm square tempered glass is sandwiched with an ethylene-vinyl acetate copolymer having a thickness of 450 μm, and a layer (Z1) of the multilayer structure (B1) is formed thereon. A solar cell module was fabricated by bonding so as to face each other. The bonding was performed by performing vacuum drawing at 150 ° C. for 3 minutes and then performing pressure bonding for 9 minutes. The solar cell module produced in this way operated well and showed good electrical output characteristics over a long period of time.

  The multilayer structure of the present invention has excellent gas barrier properties and a good appearance. Further, even when subjected to physical stress such as deformation and impact, the gas barrier property can be maintained at a high level. Therefore, the multilayer structure of the present invention can be preferably used as a packaging material for foods, medicines, medical equipment, industrial materials, clothing and the like.

  In addition to packaging materials, LCD substrate film, organic EL substrate film, electronic paper substrate film, electronic device sealing film, PDP film, LED film, IC tag film, solar cell use Examples include electronic device-related films such as backsheets, solar cell protective films, optical communication members, flexible films for electronic devices, fuel cell membranes, fuel cell sealing films, and substrate films for various functional films. Can do.

Claims (20)

A multilayer structure having at least one base (X), layer (Y) and layer (Z),
The layer (Y) contains an aluminum atom, the layer (Z) contains a polymer (E) having a plurality of phosphorus atoms, and at least one set of the layer (Y) and the layer (Z) are adjacent to each other. A laminated, multi-layer structure ,
The polymer (E) is a homopolymer of (meth) acrylic acid esters containing a phosphoric acid group, and contains a side chain whose terminal is a phosphoric acid group .   At least one set of the base material (X), the layer (Y), and the layer (Z) are laminated in the order of the base material (X) / the layer (Y) / the layer (Z). The multilayer structure according to claim 1, comprising: The multilayer structure according to claim 1 or 2 , wherein the polymer (E) is a homopolymer of acid phosphooxyethyl methacrylate. The layer (Y) is a layer (YA) containing the reaction product (R),
The reaction product (R) is a reaction product obtained by reacting a metal oxide (A) containing aluminum with a phosphorus compound (B),
Wave number infrared absorption is maximized in the region of 800～1400Cm ^-1 in the infrared absorption spectrum of the layer (YA) (n ¹⁾ is in the range of 1080~1130cm ^-1, any one of claims 1 to 3 A multilayer structure as described in 1. In the infrared absorption spectrum of the layer (YA), the absorbance at the wave number (n ¹⁾ and (A ^1), the wave number absorbance at (n ²⁾ (A ²⁾ and, but the absorbance (A ²⁾ / absorbance (A ¹⁾ Satisfies the relation of ≦ 0.2,
5. The multilayer according to claim 4 , wherein the wave number (n ² ) is a wave number at which infrared absorption based on a stretching vibration of a hydroxyl group in a range of 2500 to 4000 cm ⁻¹ is maximized in the infrared absorption spectrum of the layer (YA). Structure. The multilayer structure according to claim 4 or 5 , wherein the half-value width of the absorption peak of the wave number (n ¹ ) is 200 cm ^-1 or less. The metal oxide (A) is a hydrolysis condensate of a compound (L) containing a metal atom (M) to which a hydrolyzable characteristic group is bonded,
The compound (L) is at least one compound containing (L ^1), a multilayer structure according to any one of claims 4-6 represented by the following formula (I).
AlX ¹ _m R ¹ _(3-m) (I)
[In Formula (I), X ¹ is selected from F, Cl, Br, I, R ² O—, R ³ C (═O) O—, (R ⁴ C (═O)) ₂ CH— and NO _3. Selected from the group of R ¹ , R ² , R ³ and R ⁴ are each selected from the group consisting of an alkyl group, an aralkyl group, an aryl group and an alkenyl group. In Formula (I), when a plurality of X ¹ are present, these X ¹ may be the same as or different from each other. In the formula (I), when a plurality of R ¹ are present, these R ¹ may be the same or different from each other. In the formula (I), when a plurality of R ² are present, these R ² may be the same or different from each other. In the formula (I), when a plurality of R ³ are present, these R ³ may be the same or different from each other. In the formula (I), when a plurality of R ⁴ are present, these R ⁴ may be the same as or different from each other. m represents an integer of 1 to 3. ] The multilayer structure according to claim 7 , wherein the compound (L ¹ ) is at least one compound selected from aluminum triisopropoxide and aluminum tris-butoxide. The phosphorus compound (B) is phosphoric acid, polyphosphoric acid, phosphorous acid, is at least one compound selected from phosphonic acids and derivatives thereof, according to any one of claims 4-8 Multilayer structure. In the layer (YA), the number of moles N _M of metal atoms (M) constituting the metal oxide (A) and the number of moles N _{P of} phosphorus atoms derived from the phosphorus compound (B) are: The multilayer structure according to any one of claims 4 to 9 , satisfying a relationship of 0 ≦ (the number of moles N _M ) / (the number of moles N _P ) ≦ 3.6. The layer (Y) is a vapor-deposited layer of the deposition layer or aluminum oxide of the aluminum, the multilayer structure according to any one of claims 1-3. The multilayer structure according to any one of claims 1 to 11 , wherein the substrate (X) comprises at least one layer selected from the group consisting of a thermoplastic resin film layer, a paper layer, and an inorganic vapor deposition layer. The multilayer structure according to any one of claims 1 to 12 , wherein an oxygen permeability under conditions of 20 ° C and 85% RH is 2 ml / (m ² · day · atm) or less. The oxygen permeability under the condition of 20 ° C. and 85% RH after holding for 5 minutes in the state of 5% stretching under the condition of 23 ° C. and 50% RH is 4 ml / (m ² · day · atm) or less. The multilayer structure according to any one of claims 1 to 13 . A product comprising the multilayer structure according to any one of claims 1 to 14 ,
A product in which the multilayer structure is used for a packaging material, a solar cell member or a display member. A method for producing a multilayer structure having at least one substrate (X), layer (Y) and layer (Z),
The layer (Y) contains aluminum atoms, the layer (Z) contains a polymer (E) having a plurality of phosphorus atoms, and at least one layer (Y) and layer (Z) are laminated adjacent to each other. ,
A production method comprising the step (IV) of forming the layer (Z) by applying a coating liquid (V) containing a polymer (E) having a plurality of phosphorus atoms ,
The said polymer (E) is a homopolymer of (meth) acrylic acid ester containing a phosphoric acid group, and contains the side chain whose terminal is a phosphoric acid group . The production method according to claim 16 , wherein the polymer (E) is a homopolymer of acid phosphooxyethyl methacrylate. The layer (Y) is a layer (YA) containing the reaction product (R),
The reaction product (R) is a reaction product obtained by reacting a metal oxide (A) containing aluminum with a phosphorus compound (B),
By mixing the metal oxide (A), at least one compound containing a site capable of reacting with the metal oxide (A), and a solvent, the metal oxide (A) and the at least one compound are mixed. A step (I) of preparing a coating liquid (U) containing a seed compound and the solvent;
(II) forming a precursor layer of the layer (YA) on the substrate (X) by applying the coating liquid (U) on the substrate (X);
And (III) forming the layer (YA) by heat-treating the precursor layer of the layer (YA) at a temperature of 140 ° C. or higher,
The at least one compound comprises the phosphorus compound (B);
In the coating liquid (U), the number of moles N _M of metal atoms (M) constituting the metal oxide (A) and the number of moles N _{P of} phosphorus atoms contained in the phosphorus compound (B) are 1 .0 ≦ satisfy the relationship of (the number of moles N _M) / (the number of moles N _P) ≦ 3.6, a process according to claim 16 or 17. The manufacturing method of Claim 18 which implements the said process (IV) after the said process (III). The manufacturing method according to claim 16 or 17 , wherein the layer (Y) is an aluminum deposition layer or an aluminum oxide deposition layer.