Laminate, laminated film, package, and method for producing laminate

Abstract

To provide a laminate having sufficient gas barrier properties.SOLUTION: A laminate includes a layer (II) including a reaction product (R) of a compound (A) containing aluminum and a phosphorus compound (B), the layer (II) disposed on at least either the front side or the back side of a base material (I), where the laminate satisfies the following condition (i) and / or (ii): (i) oxygen permeability of 0.1 cc / m2 day / atm or less as measured in accordance with JIS K7126-2 (2006); (ii) water vapor permeability of 0.1 g / m2 / day or less as measured in accordance with JIS Z0208 (1976).SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a laminate, a laminated film, a package, and a method for manufacturing a laminate, which includes a resin layer having barrier properties on a substrate.

Background Art

[0002] As laminates and films for packages for packaging food products, pharmaceutical and medical products, industrial parts, etc., laminates and laminated films that prevent corrosion and spoilage of the contained substances and enable long-term storage have become widespread. As such laminates and laminated films, laminates and laminated films in which a layer mainly composed of an inorganic substance (referred to as an "inorganic layer"), such as an inorganic oxide vapor deposition layer, is formed on the surface of a substrate containing a thermoplastic resin, are known.

[0003] Since the laminates and laminated films are excellent in barrier properties against various gases such as water vapor and oxygen, they are widely used in the fields of packaging materials for articles that require blocking of various gases, for example, packaging for preventing deterioration of foods, industrial products, pharmaceuticals, etc. In addition, the laminates and laminated films have also begun to be used in new applications in recent years, such as liquid crystal display elements, solar cells, electromagnetic wave shields, touch panels, substrates for electroluminescence (EL), color filters, etc., in addition to packaging applications.

[0004] As the laminated film, for example, Patent Document 1 discloses a barrier composite film in which at least one surface of a base film layer is sequentially coated with an anchor coat layer, an inorganic thin film layer, and a barrier resin layer containing a silane coupling agent.

[0005] In addition, as the laminate, for example, Patent Document 2 discloses a multilayer structure including a substrate made of a thermoplastic resin and a layer laminated adjacent to the substrate, wherein the water contact angle of the surface of the substrate layer in contact with the layer is less than 50.0°, and the layer contains a reaction product of a compound containing aluminum and a phosphorus compound.

Prior Art Documents

Patent Documents

[0006] [Patent Document 1] Japanese Patent Application Laid-Open No. 10-76593 [Patent Document 2] Japanese Patent Application Laid-Open No. 2016-155255 [Summary of the Invention] [Problems to be Solved by the Invention]

[0007] The barrier composite film disclosed in Patent Document 1 and the multilayer structure disclosed in Patent Document 2 do not have sufficient gas barrier properties and further improvement is required. Therefore, in the present invention, under such circumstances, an object is to provide a laminate having sufficient gas barrier properties. [Means for Solving the Problems]

[0008] However, as a result of intensive studies by the present inventors in view of such circumstances, the oxygen permeability and / or water vapor permeability of a laminate provided with a layer containing a reaction product of a compound containing aluminum and a phosphorus compound on at least one of the front and back sides of a base material is within a specific range. It has been found that the above problems can be solved, and the present invention has been completed.

[0009] That is, the present invention has the following aspects. [1] A laminate comprising a layer (II) containing a reaction product (R) of a compound (A) containing aluminum and a phosphorus compound (B) on at least one of the front and back sides of a base material (I), the laminate satisfying the following (i) and / or (ii). (i) The oxygen permeability measured in accordance with JIS K7126-2 (2006) is 0.1 cc / m 2 ·day / atm or less (ii) The water vapor permeability measured in accordance with JIS Z0208 (1976) is 0.1 g / m 2 / day or less [2] The laminate according to [1], wherein the layer (II) contains a hydrophilic resin. [3] The laminate according to [2], wherein the hydrophilic resin is contained in an amount of 0.01 to 30% by mass based on 100% by mass of the total components contained in the layer (II). [4] The laminate according to [2], wherein the hydrophilic resin is a polyvinyl alcohol-based resin. [5] The laminate according to any one of [1] to [4], wherein the reaction product (R) is a reaction product having an Al—O—P bond formed by a compound (A) containing aluminum and a phosphorus compound (B). [6] The laminate according to any one of [1] to [5], wherein the compound (A) containing aluminum is a metal oxide containing aluminum. [7] The laminate according to any one of [1] to [6], wherein the phosphorus compound (B) is an inorganic phosphorus compound. [8] The laminate according to any one of [1] to [7], wherein the layer (II) has a thickness of 0.01 to 5 μm. [9] The laminate according to any one of [1] to [8], wherein the layer (II) is a coating layer.

[10] The laminate according to any one of [1] to [9], wherein the base material (I) contains at least one thermoplastic resin selected from the group consisting of polyamide-based resins, polyolefin-based resins, polyester-based resins, and polystyrene-based resins.

[11] The laminate according to any one of [1] to

[10] , wherein the base material (I) is stretched in at least one direction.

[12] A laminated film comprising the laminate according to any one of [1] to

[11] .

[13] A package using the laminated film according to

[12] .

[14] A method for producing a laminate including a layer (II) containing a reaction product (R) of a compound (A) containing aluminum and a phosphorus compound (B) on at least one of the front and back sides of a base material (I), The method includes at least a step of forming the layer (II) by coating a coating liquid containing a compound (A) containing aluminum and a phosphorus compound (B) on the base material (I). The method for producing a laminate, wherein the coating liquid contains water and alcohol as solvents, and the ratio of the presence of water in the solvent (water / alcohol) is 5 or more.

Advantages of the Invention

[0010] Since the laminate of the present invention has a low oxygen permeability and / or water vapor permeability, it has excellent gas barrier properties.

Embodiments for Carrying Out the Invention

[0011] The present invention will be described below based on examples of embodiments for carrying out the present invention. However, the present invention is not limited to the embodiments described below.

[0012] In the present invention, "X and / or Y (X and Y are arbitrary configurations)" means at least one of X and Y, and means three cases: only X, only Y, and X and Y. When expressing "X to Y" (X and Y are arbitrary numbers), unless otherwise specified, it includes the meaning of "X or more and Y or less" and also the meaning of "preferably greater than X" or "preferably less than Y". When expressing "X or more" (X is an arbitrary number) or "Y or less" (Y is an arbitrary number), it also includes the meaning of "preferably greater than X" or "preferably less than Y". In the present invention, the "main component" means a component that has a great influence on the characteristics of the object, and the content of this component is usually 50% by mass or more in the object, preferably 55% by mass or more, more preferably 60% by mass or more, still more preferably 70% by mass or more, and may be 100% by mass. In the present invention, "film" has a meaning including from a thick sheet to a thin film.

[0013] <<Laminate>> A laminate according to an example of an embodiment of the present invention (hereinafter referred to as "this laminate") includes a layer (II) containing a reaction product (R) of a compound (A) containing aluminum and a phosphorus compound (B) on at least one of the front and back sides of a base material layer (I), and has a specific oxygen permeability and / or a specific water vapor permeability. In addition, the shape of the present laminate is not particularly limited and may be plate-like or film-like, but it is preferably film-like, that is, the present laminate is preferably a laminated film. Hereinafter, the present laminate will be described.

[0014] <Substrate (I)> The substrate (I) is not particularly limited as long as it can be formed into a plate shape or a film shape, but preferably contains a thermoplastic resin.

[0015] [Thermoplastic resin] The thermoplastic resin is preferably at least one selected from the group consisting of, for example, polyamide resins, polyolefin resins, polyester resins, and polystyrene resins, more preferably polyolefin resins, polyester resins, and polystyrene resins, and particularly preferably polyester resins.

[0016] [Polyamide resin] Examples of the polyamide resin include polyamide resins obtained by polycondensation of aliphatic, alicyclic, or aromatic diamines such as hexamethylenediamine, decamethylenediamine, dodecamethylenediamine, trimethylhexamethylenediamine, 1,3- or 1,4-bis(aminomethyl)cyclohexane, bis(p-aminocyclohexylmethane), m- or p-xylylenediamine, and aliphatic, alicyclic, or aromatic dicarboxylic acids such as adipic acid, suberic acid, sebacic acid, cyclohexanedicarboxylic acid, terephthalic acid, and isophthalic acid, polyamide resins obtained by condensation of aminocarboxylic acids such as ε-aminocaproic acid and 11-aminoundecanoic acid, polyamide resins obtained from lactams such as ε-caprolactam and ε-laurolactam, or copolymer polyamide resins thereof.

[0017] Specific examples of the polyamide resin include, for example, polyamide-6, polyamide-6,6, polyamide-6,10, polyamide-9, polyamide-11, polyamide-12, polyamide-6 / 6,6, polyamide-6 / 6,10, polyamide-6 / 11, etc.

[0018] [Polyolefin resin] Examples of the polyolefin resin include homopolymers obtained by polymerizing α-olefins such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, and 1-decene, or copolymers having α-olefins as the main monomer components. Among them, from the viewpoint of transparency and the like, polyethylene resins having ethylene as the main monomer component and polypropylene resins having propylene as the main monomer component are preferable. Here, the main monomer component refers to a monomer component that occupies 50 to 100% by mass of the resin.

[0019] The polyethylene resin is not particularly limited as long as it is a resin having ethylene as the main monomer component, and examples thereof include low-density polyethylene, linear low-density polyethylene, linear ultra-low-density polyethylene, medium-density polyethylene, and high-density polyethylene. Further, the polyethylene resin may be a homopolymer of ethylene, or may be a copolymer having ethylene as the main monomer component and another copolymerizable monomer component.

[0020] Examples of the other copolymerizable monomer components (comonomers) include α-olefins having 3 to 10 carbon atoms such as propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, and 1-octene, vinyl esters such as vinyl acetate and vinyl propionate, unsaturated carboxylic acid esters such as methyl (meth)acrylate and ethyl (meth)acrylate and their ionomers, and unsaturated compounds such as conjugated dienes and non-conjugated dienes.

[0021] Examples of the polypropylene resin include a homopolymer of propylene, or a random copolymer or block copolymer having propylene as the main monomer and another copolymerizable monomer.

[0022] Examples of the other copolymerizable monomers include α-olefins having 2 to 20 carbon atoms such as ethylene, 1-butene, 1-hexene, 4-methylpentene-1, 1-octene, etc., dienes such as divinylbenzene, 1,4-cyclohexadiene, dicyclopentadiene, cyclooctadiene, ethylidene norbornene, etc. These may be used alone or copolymerized in two or more kinds.

[0023] Specific examples of the polypropylene-based copolymer include propylene-ethylene copolymer, propylene-α-olefin copolymer, propylene-ethylene-butene-1 copolymer, propylene-ethylene-α-olefin copolymer, block polypropylene, random polypropylene, homopolypropylene, etc.

[0024] [Polyester resin] Examples of the polyester resin include resins obtained by copolymerizing a diol component and a dicarboxylic acid component.

[0025] Examples of the diol component include ethylene glycol, 1,2-propanediol, 1,3-propanediol, neopentyl glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, cyclohexanedimethanol, diethylene glycol, triethylene glycol, polyalkylene glycol, tetramethylcyclobutanediol, 2,2-bis(4-hydroxyethoxyphenyl)propane, 4,4'-thiodiphenol, bisphenol A, 4,4'-methylenediphenyl, 4,4'-hydroxybiphenyl, and dihydroxybenzene, etc. These diol components may be used alone or in combination of two or more kinds.

[0026] Examples of the dicarboxylic acid component include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, diphenylcarboxylic acid, diphenylsulfonedicarboxylic acid, diphenoxyethanedicarboxylic acid, 5-sodium sulfoisophthalic acid, and phthalic acid; aliphatic dicarboxylic acids such as oxalic acid, succinic acid, eicosanoic acid, adipic acid, sebacic acid, dimer acid, dodecanedioic acid, maleic acid, and fumaric acid; alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid; and polyfunctional acids such as trimellitic acid and pyromellitic acid. These dicarboxylic acid components may be used alone or in combination of two or more.

[0027] Specific examples of the polyester resin include polyethylene terephthalate, polyethylene naphthalate, glycol-modified polyethylene terephthalate, etc., and polyethylene terephthalate is preferred.

[0028] [Polystyrene resin] The polystyrene resin is a resin having a styrene structure as part or all of the repeating unit. Examples thereof include copolymers of styrene monomers such as styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, p-chlorostyrene, p-nitrostyrene, p-aminostyrene, p-carboxystyrene, and p-phenylstyrene, and other monomers such as ethylene, propylene, butadiene, isoprene, acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, acrylic acid, methacrylic acid, maleic anhydride, and vinyl acetate. In addition, examples of the polystyrene resin include those obtained by mixing a small amount of butadiene rubber particles with polystyrene, so-called high impact polystyrene (HIPS), etc.

[0029] The thermoplastic resin is preferably the main component of the substrate (I). The "main component" means the component that occupies the largest mass percentage among the components contained in the base material (I). When the total mass of the components contained in the base material (I) is 100% by mass, the proportion occupied by this component is usually 50% by mass or more, preferably 60% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, particularly preferably 90% by mass or more, and may be 100% by mass.

[0030] 〔Other resins〕 The base material (I) may contain resins other than the above-mentioned thermoplastic resins, such as thermosetting resins such as epoxy resins, polyphenylene ether resins, polyimide resins, phenolic resins, orthodivinylbenzene resins, etc., silicone resins, fluorine resins, etc. These can be used alone or in combination of two or more.

[0031] When the base material (I) contains other resins, the content thereof is usually 30% by mass or less, preferably 20% by mass or less, more preferably 10% by mass or less, still more preferably 5% by mass or less, particularly preferably 1% by mass or less, based on 100% by mass of the total components contained in the base material (I) in terms of mechanical properties and heat resistance.

[0032] 〔Other components〕 The base material (I) may contain particles for the purpose of roughening the surface of the base material (I) to impart slipperiness and mainly for preventing the occurrence of scratches in each manufacturing process described below.

[0033] The particles are not particularly limited as long as they can impart slipperiness. For example, inorganic particles such as silica, calcium carbonate, magnesium carbonate, barium carbonate, calcium sulfate, calcium phosphate, magnesium phosphate, kaolin, aluminum oxide, titanium oxide, etc., and organic particles such as acrylic resins, styrene resins, urea resins, phenolic resins, epoxy resins, benzoguanamine resins, etc. can be mentioned. These can be used alone or in combination of two or more.

[0034] The shape of the particles is not particularly limited, and may be, for example, spherical, massive, rod-shaped, flat-shaped, or the like. Also, the hardness, specific gravity, color, etc. of the particles are not particularly limited as long as they do not affect the effects of the present invention.

[0035] The average particle diameter of the particles is usually 5 μm or less, preferably 0.01 to 3.0 μm, more preferably 0.5 to 2.5 μm. If the average particle diameter of the particles is within the above range, the surface roughness of the base material (I) does not become too rough, and there is a tendency to reduce problems when forming the layer (II) on the base material (I).

[0036] When the base material (I) contains particles, the content is usually 5% by mass or less, preferably 0.0003 to 3% by mass, more preferably 0.01 to 2% by mass, based on 100% by mass of the total components contained in the base material (I). By setting the content of the particles within the above range, there is a tendency to achieve both the slipperiness and transparency of the base material (I).

[0037] Also, the base material (I) can contain, if necessary, conventionally known additives such as antioxidants, antistatic agents, heat stabilizers, lubricants, dyes, pigments, ultraviolet absorbers, etc. These may be used alone or in combination of two or more.

[0038] 〔Method for producing the base material (I)〕 The base material (I) can be obtained, for example, by melt-extruding components containing the above-mentioned thermoplastic resin into a plate shape or a film shape by a general molding method such as melt extrusion molding or hot pressing. However, the production method of the base material (I) is not limited to this method.

[0039] When the shape of the base material (I) is film-shaped, the base material (I) may be unstretched or stretched, but from the viewpoint of mechanical strength, it is preferably stretched in at least one direction, and more preferably biaxially stretched. The stretching may be uniaxial or biaxial stretching according to known methods. Further, when the base material (I) is a biaxially stretched film, the biaxial stretching may be simultaneous biaxial stretching or sequential biaxial stretching.

[0040] 〔Constitution of the base material (I)〕 The base material (I) may be a single layer or a multilayer. When the base material (I) is a multilayer, layers containing the same type of thermoplastic resin may be laminated, or layers containing different types of thermoplastic resin may be laminated. When the base material (I) is a multilayer, the layers can be laminated to each other by common molding methods such as coextrusion and dry lamination.

[0041] 〔Surface of the base material (I)〕 As described above, this laminate needs to be provided with a layer (II) containing a reaction product (R) of a compound (A) containing aluminum and a phosphorus compound (B) on at least one of the front and back sides of the base material (I). Therefore, at least one of the front and back surfaces of the base material (I) is preferably surface-treated from the viewpoints of adhesion and uniformity between the base material (I) and the layer (II).

[0042] The method of the surface treatment is not particularly limited. For example, it includes corona treatment, plasma treatment, antistatic treatment, coating treatment with a primer, physical vapor deposition, chemical vapor deposition, acid or alkali treatment, chromic acid treatment, ozone exposure, flame exposure, high-voltage electric shock exposure, ionization radiation treatment, ultraviolet irradiation treatment, flame treatment, photochromism treatment, etc. These may be used alone or in combination of two or more. Among them, corona treatment, plasma treatment, antistatic treatment, and coating treatment with a primer are preferable, and corona treatment is particularly preferable.

[0043] Further, an adhesive layer may be formed on the surface of the base material (I) by applying a known adhesive or the like.

[0044] 〔Thickness of the base material〕 The thickness of the base material (I) can be appropriately selected according to the intended use. For example, when the film is wound into a roll, from the perspective of proper processing and the like, the thickness is usually 5 to 1000 μm, preferably 10 to 200 μm.

[0045] 〔Physical properties of the base material (I)〕 The base material (I) preferably has the following physical properties.

[0046] From the perspective of gas barrier properties, the peak temperature of the loss tangent (tanδ) in the dynamic viscoelasticity measurement of the base material (I) is usually 50 to 150 °C, preferably 60 to 140 °C, more preferably 70 to 130 °C.

[0047] Further, when the base material (I) contains a polyester resin as a thermoplastic resin, from the perspective of gas barrier properties, the storage modulus (E’) at 130 °C in the dynamic viscoelasticity measurement is usually 10 to 1000 MPa, preferably 30 to 700 MPa, more preferably 50 to 500 MPa.

[0048] The loss tangent (tanδ) can be determined by measuring the dynamic viscoelasticity in accordance with JIS K7244-4 (1999) using a dynamic viscoelasticity measuring device under the conditions of a measurement temperature range of -100 to 200 °C, a heating rate of 3 °C / min, a frequency of 10 Hz, a strain of 0.1%, and a tensile mode. Also, the storage modulus (E’) can be determined from the value at 130 °C in the measurement of the dynamic viscoelasticity.

[0049] <Layer (II)> The layer (II) contains a reaction product (R) of a compound (A) containing aluminum and a phosphorus compound (B). In this laminate, the layer (II) is a layer useful for improving the gas barrier properties of the laminate and is preferably a coating layer. Also, from the perspective of gas barrier properties, it is preferable that the layer (II) is adjacent to the base material (I).

[0050] 〔Compound (A) containing aluminum〕 Examples of the aluminum-containing compound (A) include aluminum oxide, aluminum chloride, aluminum triethoxide, aluminum trinormalpropoxide, aluminum triisopropoxide, aluminum trinormalbutoxide, aluminum tris-butoxide, aluminum trit-butoxide, aluminum triacetate, aluminum acetylacetonate, aluminum nitrate, etc. These may be used alone or in combination of two or more.

[0051] The aluminum-containing compound (A) is preferably a metal oxide containing aluminum from the viewpoint of reactivity with the phosphorus compound (B), more preferably aluminum oxide, particularly preferably boehmite and pseudo-boehmite, and especially preferably pseudo-boehmite.

[0052] [Phosphorus Compound (B)] The phosphorus compound (B) has a site capable of reacting with the aluminum-containing compound (A) (hereinafter referred to as the "reaction site"), and the number of reaction sites in the phosphorus compound (B) is usually 2 to 20. Also, the phosphorus compound (B) may have one phosphorus atom or may have two or more phosphorus atoms.

[0053] Examples of the reaction site include a halogen atom directly bonded to a phosphorus atom and an oxygen atom directly bonded to a phosphorus atom. These halogen atoms and oxygen atoms directly bonded to the phosphorus atom can react with a functional group present on the surface of the aluminum-containing compound (A) [for example, in the case where the functional group is a hydroxyl group, a condensation reaction (hydrolysis condensation reaction)].

[0054] Specific examples of the phosphorus compound (B) include phosphoric acid, phosphorous acid, phosphonic acid, polyphosphoric acid, and their derivatives, and organic polymers having a phosphorus atom such as phosphorylated starch. These may be used alone or in combination of two or more.

[0055] Examples of the polyphosphoric acid include pyrophosphoric acid, triphosphoric acid, and polyphosphoric acid condensed from four or more phosphoric acids.

[0056] Examples of the derivative include salts, (partial) ester compounds, halides (such as chlorides), and anhydrides of phosphoric acid, phosphorous acid, phosphonic acid, and polyphosphoric acid. In addition, the derivatives of the phosphonic acid include compounds in which a hydrogen atom directly bonded to the phosphorus atom of phosphonic acid (H-P(=O)(OH)2) is substituted with an alkyl group (the alkyl group may have various functional groups), [for example, nitrilotris(methylenephosphonic acid), N,N,N,N'-ethylenediaminetetrakis(methylenephosphonic acid), etc.], and their salts, (partial) ester compounds, halides, and anhydrides.

[0057] Among these phosphorus compounds (B), inorganic phosphorus compounds are preferred, and phosphoric acid is particularly preferred, from the viewpoints of excellent storage stability of the coating liquid described later and excellent gas barrier properties of the present laminate.

[0058] [Ratio of the compound (A) containing aluminum and the phosphorus compound (B)] In the layer (II), the ratio of the compound (A) containing aluminum and the phosphorus compound (B) is preferably such that the molar number (NM) of aluminum atoms of the compound (A) containing aluminum and the molar number (NP) of phosphorus atoms of the phosphorus compound (B) satisfy the relationship of 0.8 ≦ NM / NP ≦ 4.5, more preferably satisfy the relationship of 1.0 ≦ NM / NP ≦ 3.6, and even more preferably satisfy the relationship of 1.1 ≦ NM / NP ≦ 3.0. When the value of NM / NP is within the above range, the abundance ratio of the compound (A) containing aluminum and the phosphorus compound (B) becomes appropriate, and the bonding between the particles of the compound (A) containing aluminum becomes sufficient, so that the barrier properties and reliability tend to be improved. On the one hand, when the value of NM / NP exceeds 4.5, the compound (A) containing aluminum becomes excessive with respect to the phosphorus compound (B), the bonding between the particles of the compound (A) containing aluminum becomes insufficient, and the amount of functional groups present on the surface of the compound (A) containing aluminum increases. As a result, the barrier property and reliability tend to decrease. On the other hand, when the value of NM / NP is less than 0.8, the phosphorus compound (B) becomes excessive with respect to the compound (A) containing aluminum, and the amount of excess phosphorus compound (B) that does not participate in the bonding with the compound (A) containing aluminum increases. Also, the amount of reaction sites of the phosphorus compound (B) tends to increase, and the barrier property and reliability tend to decrease.

[0059] The ratio can be adjusted by the content of the compound (A) containing aluminum and the content of the phosphorus compound (B) in the coating liquid for forming the layer (II) described later. Also, the ratio of the number of moles (NM) of aluminum atoms to the number of moles (NP) of phosphorus atoms in the layer (II) is usually the same as the ratio in the coating liquid.

[0060] 〔Reaction product (R)〕 The reaction product (R) is a reaction product of the compound (A) containing aluminum and the phosphorus compound (B), and is obtained by dehydration condensation of the compound (A) containing aluminum and the phosphorus compound (B) by the sol-gel method.

[0061] Among them, it is preferable from the viewpoint of gas barrier property that the reaction product (R) is a reaction product having an Al-O-P bond formed by the compound (A) containing aluminum and the phosphorus compound (B). The Al-O-P bond is usually formed by a dehydration condensation reaction between the compound (A) containing aluminum and the phosphorus compound (B).

[0062] 〔Hydrophilic resin〕 The layer (II) preferably contains a hydrophilic resin. When the layer (II) contains a hydrophilic resin, the hydrophilic resin serves as a binder for the reaction product (R), preventing the reaction product (R) from falling off, and also tends to prevent the layer (II) from cracking and the coating film strength from decreasing when the laminate is bent.

[0063] The hydrophilic resin preferably has the following characteristics when formed into a film, for example. That is, when a film with a thickness of 30 μm is prepared using the hydrophilic resin and immersed in water at 25°C for 2 hours while standing, the area change rate is preferably 105% or more. The area change rate can be obtained by the following formula. Area change rate (%) = Film area after immersion / Film area before immersion × 100

[0064] Examples of the hydrophilic resin include water-soluble resins such as vinyl alcohol-based resins, polysaccharides, acrylic resins, and polyether-based resins. The above hydrophilic resins may be used alone or in combination of two or more. Among them, vinyl alcohol-based resins are preferred in terms of excellent barrier properties. Hereinafter, specific hydrophilic resins will be described in detail.

[0065] [Vinyl alcohol-based resin] The vinyl alcohol-based resin generally excludes resins known as ethylene-vinyl alcohol copolymer resins (ethylene content 20 to 60 mol%), and examples include polyvinyl alcohol (hereinafter referred to as "PVA")-based resins.

[0066] The PVA-based resin is preferably an unmodified PVA resin, but a modified PVA-based resin may also be used.

[0067] The unmodified PVA resin can usually be produced by polymerizing a vinyl ester-based monomer and then saponifying it. The modified PVA-based resin can be produced by saponifying a polymer of a vinyl ester-based monomer and another unsaturated monomer, or by post-modifying an unmodified PVA resin.

[0068] Examples of the vinyl ester-based monomer include aliphatic vinyl esters such as vinyl formate, vinyl acetate, vinyl propionate, vinyl valerate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl caprate, vinyl laurate, vinyl stearate, vinyl versatate, vinyl trifluoroacetate, and aromatic vinyl esters such as vinyl benzoate. Among them, aliphatic vinyl esters having 3 to 20 carbon atoms, more preferably 4 to 10 carbon atoms, and particularly preferably 4 to 7 carbon atoms are preferable, and vinyl acetate is particularly preferable. These are usually used alone, but a plurality of them may be used simultaneously if necessary.

[0069] Examples of the other unsaturated monomers include olefins such as ethylene, propylene, isobutylene, α-octene, α-dodecene, and α-octadecene; unsaturated acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, maleic anhydride, and itaconic acid, or salts thereof, or mono- or dialkyl esters thereof; nitriles such as acrylonitrile and methacrylonitrile; amides such as acrylamide and methacrylamide; olefin sulfonic acids such as ethylene sulfonic acid, allyl sulfonic acid, and methallyl sulfonic acid, or salts thereof; alkyl vinyl ethers; N-acrylamidomethyltrimethylammonium chloride, allyltrimethylammonium chloride, dimethylallyl vinyl ketone, N-vinylpyrrolidone, vinyl chloride, vinylidene chloride, polyoxyalkylene (meth)allyl ether such as polyoxyethylene (meth)allyl ether and polyoxypropylene (meth)allyl ether, polyoxyalkylene (meth)acrylate such as polyoxyethylene (meth)acrylate and polyoxypropylene (meth)acrylate, polyoxyalkylene (meth)acrylamide such as polyoxyethylene (meth)acrylamide and polyoxypropylene (meth)acrylamide, polyoxyethylene (1-(meth)acrylamide-1,1-dimethylpropyl) ester, polyoxyethylene vinyl ether, polyoxypropylene vinyl ether, polyoxyethylene allylamine, polyoxypropylene allylamine, polyoxyethylene vinylamine, polyoxypropylene vinylamine, and the like. These can be used alone or in combination of two or more. Note that the "(meth)allyl" means allyl or methallyl, the "(meth)acrylate" means acrylate or methacrylate, and the "(meth)acrylic" means acrylic or methacrylic, respectively.

[0070] The PVA-based resin can be obtained by any known polymerization method, saponification method, and post-modification method.

[0071] The introduction amount of the other unsaturated monomer and the modification amount by post-modification are appropriately set depending on the type of monomer, but are usually 15 mol% or less, particularly 10 mol% or less. If the introduction amount and the modification amount are too large, the crystallinity of the PVA-based resin tends to decrease, and the gas barrier property tends to decrease.

[0072] The average saponification degree of the PVA-based resin is usually 70 to 100 mol%, preferably 80 to 100 mol%, particularly preferably 85 to 100 mol%, and more preferably 90 to 99.99 mol%. If the average saponification degree is less than 70 mol%, the oxygen permeability under high humidity tends to increase. The average saponification degree is measured in accordance with JIS K6726 (1994).

[0073] The average degree of polymerization of the PVA-based resin is usually 100 to 4000, preferably 200 to 3000, and particularly preferably 250 to 2500. If such an average degree of polymerization is too low, mechanical properties such as film strength tend to decrease, and if it is too high, it tends to be difficult to handle, such as difficulty in forming an aqueous solution. The average degree of polymerization is measured in accordance with JIS K6726 (1994).

[0074] In addition, as the PVA-based resin, two or more kinds having different modification types, modification amounts, average saponification degrees, average degrees of polymerization, etc. may be used in combination.

[0075] [Polysaccharide] Examples of the polysaccharide include starch, cellulose, and the like. Examples of the starch include natural starches such as corn starch and potato starch, and modified starches such as etherified starch, esterified starch, crosslinked starch, grafted starch, roasted dextrin, enzyme-modified dextrin, alpha-starch, and oxidized starch. Examples of the cellulose include carboxymethyl cellulose, methyl cellulose, ethyl cellulose, hydroxymethyl cellulose, hydroxypropyl methyl cellulose, hydroxyethyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl cellulose, nitrocellulose, cationized cellulose, etc., and metal salts such as sodium salts thereof.

[0076] [Acrylic resin] Examples of the acrylic resin include polyacrylamide, polyacrylic acid, and metal salts such as sodium salts thereof.

[0077] [Polyether resin] Examples of the polyether resin include polyethylene glycol, polypropylene glycol, etc.

[0078] Among the hydrophilic resins, vinyl alcohol-based resins and polysaccharides are preferable, more preferably PVA-based resins, modified starches (particularly soluble starches), and hydroxypropyl methyl cellulose, and most preferably unmodified PVA resins, from the viewpoint of excellent barrier properties.

[0079] When the layer (II) contains a hydrophilic resin, its content is usually 0.01 to 30% by mass, preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass, based on 100% by mass of the total components contained in the layer (II), from the viewpoint of excellent barrier properties.

[0080] Further, the hydrophilic resin may or may not react with other components in the layer (II).

[0081] [Other components] As long as the effects of the present invention can be obtained, the layer (II) may contain other components in addition to the components described above. Examples of other components include, for example, layered clay compounds, crosslinking agents, polymer compounds other than hydrophilic resins, plasticizers, antioxidants, ultraviolet absorbers, flame retardants, and the like. These may be used alone or in combination of two or more. Further, the layer (II) may contain an acid catalyst, an acid compound, etc. contained in the coating liquid described later.

[0082] 〔Thickness of layer (II)〕 From the viewpoint of gas barrier properties, the thickness of the layer (II) is usually 0.01 to 5 μm, preferably 0.05 to 4 μm, and particularly preferably 0.1 to 3 μm.

[0083] Also, from the viewpoints of gas barrier properties and optical properties, the thickness of the layer (II) is usually 0.03 to 50% of the thickness of the base material (I), preferably 0.15 to 40%, and particularly preferably 0.3 to 30%.

[0084] <Surface protection layer (III)> This laminate includes the layer (II) on at least one of the front and back sides of the base material (I), and may include a surface protection layer (III) as another layer other than these layers. The surface protection layer (III) is preferably provided on the surface of the layer (II) for the purpose of protecting the layer (II) and improving the gas barrier properties.

[0085] The surface protection layer (III) preferably consists of a resin that is difficult to be scratched. Also, when this laminate is used for a device that may be used outdoors like a solar cell, the surface protection layer (III) preferably consists of a resin having high weather resistance (for example, light resistance). Furthermore, when it is necessary to transmit light through this laminate, the surface protection layer (III) preferably consists of a resin having high light transmittance.

[0086] Examples of the resin that can be used for the surface protective layer (III) include acrylic resins, polycarbonate, polyethylene terephthalate, polyethylene naphthalate, ethylene-tetrafluoroethylene copolymer, polytetrafluoroethylene, ethylene-chlorotrifluoroethylene copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, ethylene-tetrafluoroethylene copolymer, polyvinylidene fluoride, and polyvinyl fluoride. These may be used alone or in combination of two or more. Among them, acrylic resins are preferred.

[0087] In addition, the surface protective layer (III) may contain various additives (such as ultraviolet absorbers, stabilizers, light stabilizers, antioxidants, etc.) to enhance durability.

[0088] As the ultraviolet absorber, known ultraviolet absorbers can be used, such as benzotriazole-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, salicylate-based ultraviolet absorbers, cyanoacrylate-based ultraviolet absorbers, nickel-based ultraviolet absorbers, triazine-based ultraviolet absorbers, etc. These may be used alone or in combination of two or more.

[0089] When high weather resistance is required for this laminate, the surface protective layer (III) preferably consists of an acrylic resin added with an ultraviolet absorber.

[0090] 〔Thickness of layer (III)〕 The thickness of layer (III) is usually 0.01 - 5 μm, preferably 0.05 - 4 μm, and particularly preferably 0.1 - 3 μm.

[0091] Also, the thickness of layer (III) is usually 0.03 - 50% of the thickness of the base material (I), preferably 0.15 - 40%, and particularly preferably 0.3 - 30%.

[0092] <Manufacturing method of this laminate> This laminate is obtained by a production method that includes at least a step of forming a layer (II) by coating at least one of the front and back sides of the base material (I) with a coating liquid containing a compound (A) containing aluminum and a phosphorus compound (B), wherein the coating liquid contains water and alcohol as solvents, and the ratio of the amount of water to the amount of alcohol (water / alcohol) in the solvent is 5 or more.

[0093] Specifically, the layer (II) is formed through the following steps: (i) preparing a coating liquid by mixing a compound (A) containing aluminum, a phosphorus compound (B), and a solvent; (ii) forming a precursor layer of the layer (II) by applying the coating liquid onto the base material (I); and (iii) forming the layer (II) on the base material (I) by treating the precursor layer. The following steps will be described.

[0094] [Step (i)] The coating liquid can be prepared, for example, by a method employed in a known sol-gel method, and preferably includes the following steps (ia) to (ic). Step (ia): A step of mixing a compound (A) containing aluminum and a solvent to prepare a liquid. Step (ib): A step of preparing a solution containing a phosphorus compound (B). Step (ic): A step of mixing the liquid obtained in step (ia) and the solution obtained in step (ib) to prepare a coating liquid.

[0095] Step (ib) may be performed before step (ia), simultaneously with step (ia), or after step (ia). Hereinafter, each step will be described in more detail.

[0096] [Step (ia)] In step (ia), a compound (A) containing aluminum and a solvent are mixed to prepare a liquid. Note that the liquid is a solution or a dispersion.

[0097] The solvent is not particularly limited as long as it is a solvent in which the compound (A) containing aluminum can be dissolved or dispersed, and examples thereof include water, alcohol, etc. Usually, a mixed solvent of water and alcohol is used.

[0098] Examples of the alcohol include lower alcohols having 1 to 5 carbon atoms such as methanol, ethanol, propanol, n-butanol, isopropanol, etc., and ethanol is preferred.

[0099] When the solvent contains water and alcohol, the presence ratio of water in the solvent (water / alcohol) is preferably 5 or more, more preferably 6 or more, still more preferably 7 or more, and particularly preferably 8 or more. Also, the upper limit is usually 25, and preferably 20. When the presence ratio of water is within the above range, the storage stability of the liquid tends to improve. The presence ratio of water in the solvent is the value obtained by dividing the mass of water in the solvent by the mass of alcohol in the solvent.

[0100] Also, from the viewpoint of reactivity, the liquid may contain an acid catalyst. Examples of the acid catalyst include inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, boric acid, etc., and organic acids such as acetic acid, phthalic acid, fumaric acid, maleic acid, malic acid, acrylic acid, methacrylic acid, trifluoromethylsulfonic acid, ethylsulfonic acid, etc. These can be used alone or in combination of two or more.

[0101] The liquid can be prepared, for example, by mixing the compound (A) containing aluminum, a solvent, and, if necessary, an acid catalyst, and condensing or hydrolytically condensing the compound (A) containing aluminum by a method employed in the known sol-gel method.

[0102] If necessary, specific treatment (such as peptization or adjustment of the solvent for concentration control) may be performed on the dispersion.

[0103] The content of the aluminum-containing compound (A) in the liquid is usually 0.1 to 30% by mass, preferably 1 to 20% by mass, more preferably 2 to 15% by mass.

[0104] Also, from the viewpoint of storage stability, the pH of the liquid is preferably 1.5 to 6.5.

[0105] [Step (ib)] In step (ib), a solution containing a phosphorus compound (B) is prepared. The solution can be prepared by dissolving the phosphorus compound (B) in a solvent.

[0106] As the solvent, the solvents described in step (ia) can be used, and preferably water.

[0107] Also, when the solubility of the phosphorus compound (B) in the solvent is low, heat treatment or ultrasonic treatment may be performed to promote dissolution.

[0108] The content of the phosphorus compound (B) in the solution is usually 0.1 to 50% by mass, preferably 0.5 to 40% by mass, more preferably 1 to 30% by mass, and particularly preferably 2 to 10% by mass.

[0109] [Step (ic)] In step (ic), the liquid obtained in step (ia) and the solution obtained in step (ib) are mixed to prepare a coating liquid.

[0110] When mixing the liquid obtained in step (ia) and the solution obtained in step (ib), in order to suppress local reactions, it is preferable to suppress the addition rate and mix while strongly stirring. At this time, the solution may be added to the stirring liquid, or the liquid may be added to the stirring solution.

[0111] Also, it is preferable to maintain the temperature during mixing at 30°C or lower (preferably 20°C or lower) from the viewpoint of obtaining a coating liquid with excellent storage stability. Furthermore, by continuing stirring for about 30 minutes from the time when mixing is completed, there is a tendency that a coating liquid with more excellent storage stability can be obtained.

[0112] The coating liquid may contain at least one acid compound selected from acetic acid, hydrochloric acid, nitric acid, trifluoroacetic acid, and trichloroacetic acid, if necessary. When the coating liquid contains the above acid compound, when mixing the above liquid and the above solution in step (ic), the reaction rate between the compound (A) containing aluminum and the phosphorus compound (B) is alleviated, and as a result, there is a tendency that a coating liquid with excellent storage stability can be obtained.

[0113] When the coating liquid contains the acid compound, its content is usually 0.1 to 5.0% by mass, preferably 0.5 to 2.0% by mass. When the content of the acid compound is within the above range, the effect of adding the acid compound can be sufficiently obtained, and there is a tendency that the removal of the acid compound is easy. Further, when an acid component such as an acid catalyst remains in the liquid, the addition amount of the acid compound may be determined in consideration of the remaining amount.

[0114] The coating liquid thus obtained can be used as it is, but further, addition of a solvent, adjustment of pH, adjustment of viscosity may be performed, and a hydrophilic resin or other components described in the above layer (II) may be added.

[0115] When the coating liquid contains the hydrophilic resin and other components, these may be added in any of the above steps (ia) to (ic). Among them, it is preferable to add the hydrophilic resin in step (ia).

[0116] The content of the compound (A) containing aluminum in the coating liquid is usually 0.1 to 10% by mass, preferably 0.5 to 8% by mass, more preferably 1 to 5% by mass, and particularly preferably 1.5 to 3% by mass.

[0117] The content of the phosphorus compound (B) in the coating liquid is usually 0.1 to 10% by mass, preferably 0.5 to 8% by mass, more preferably 1 to 6% by mass, and particularly preferably 1.5 to 4% by mass.

[0118] In addition, in the coating liquid, the compound (A) containing aluminum and the phosphorus compound (B) preferably have a ratio such that the number of moles (NM) of aluminum atoms in the compound (A) containing aluminum and the number of moles (NP) of phosphorus atoms in the phosphorus compound (B) are as described above.

[0119] When the coating liquid contains a hydrophilic resin, its content is usually 0.001 to 5% by mass of the coating liquid, preferably 0.005 to 3% by mass, and more preferably 0.01 to 1% by mass.

[0120] The coating liquid contains water and alcohol as solvents, and the presence ratio of water in the solvent (water / alcohol) is 5 or more, preferably 6 or more, more preferably 7 or more, and particularly preferably 8 or more. Also, the upper limit is usually 25 or less, preferably 20 or less. When the presence ratio of water is within the above range, a laminate excellent in barrier properties can be obtained when layer (II) is formed. Note that the presence ratio of water in the solvent is the value obtained by dividing the mass of water in the solvent contained in the coating liquid by the mass of alcohol in the solvent.

[0121] 〔Step (ii)〕 In the step (ii), a precursor layer of layer (II) is formed on the substrate (I) by applying a coating liquid on the substrate (I).

[0122] The coating liquid may be directly applied to at least one of the front and back sides of the substrate (I).

[0123] The method of applying the coating liquid onto the substrate (I) is not particularly limited, and known methods can be adopted. For example, casting method, dipping method, roll coating method, gravure coating method, screen printing method, reverse coating method, spray coating method, kiss coating method, die coating method, metering bar coating method, combined chamber doctor coating method, curtain coating method, etc. can be mentioned.

[0124] After applying the coating liquid onto the substrate (I), the precursor layer of layer (II) is formed by removing the solvent in the coating liquid.

[0125] When forming layer (II) on both sides of the substrate (I), after applying the coating liquid onto one side of the substrate (I) and then removing the solvent to form the first layer (precursor layer of the first layer (II)), and then, after applying the coating liquid onto the other side of the substrate (I) and removing the solvent, the second layer (precursor layer of the second layer (II)) can be formed. The composition of the coating liquid applied to each side may be the same or different.

[0126] The method for removing the solvent is not particularly limited, and known drying methods can be applied. Specific drying methods include, for example, hot air drying method, hot roll contact method, infrared heating method, microwave heating method, etc. These can be used alone or in combination of two or more.

[0127] The drying temperature is preferably 0 to 15 °C or more lower than the flow start temperature of the substrate (I). Also, when the coating liquid contains a hydrophilic resin, the drying temperature is preferably 15 to 20 °C or more lower than the thermal decomposition start temperature of the hydrophilic resin. The specific drying temperature is usually 70 to 200 °C, preferably 80 to 180 °C, and particularly preferably 90 to 160 °C. Furthermore, the removal of the solvent may be carried out either under normal pressure or under reduced pressure.

[0128] Alternatively, the solvent may be removed by the heat treatment in step (iii) described below.

[0129] 〔Step (iii)〕 In step (iii), the precursor layer of layer (II) formed in step (ii) is processed to form layer (II). By the above treatment, a reaction in which particles of compound (A) containing aluminum are bonded via phosphorus atoms (phosphorus atoms derived from phosphorus compound (B)) proceeds, and reaction product (R) is generated.

[0130] Examples of the treatment method include heat treatment, electromagnetic wave irradiation treatment such as ultraviolet rays, etc. Among them, heat treatment is preferred.

[0131] The temperature of the heat treatment is usually 110°C or higher, preferably 120°C or higher, more preferably 140°C or higher, and particularly preferably 170°C or higher. If the temperature of the heat treatment is within the above range, the time required to obtain a sufficient amount of reaction product (R) is shortened, and the productivity tends to improve. The upper limit of the heat treatment temperature varies depending on the type of substrate (I) etc., but is usually equal to or lower than the flow start temperature of substrate (I). For example, when a polyamide-based resin is used as substrate (I), the upper limit of the heat treatment temperature is usually 190°C or lower. Also, when a polyester-based resin is used as substrate (I), the upper limit of the heat treatment temperature is usually 220°C or lower. The heat treatment can be carried out in air, under a nitrogen atmosphere, or under an argon atmosphere, etc.

[0132] The heat treatment time is usually 0.1 seconds to 1 hour, preferably 1 second to 15 minutes, more preferably 5 to 300 seconds.

[0133] As an example of a specific heat treatment, it is 110 to 220°C for 0.1 seconds to 1 hour. Also, as another example of the heat treatment, it is carried out at 120 to 200°C for 5 to 300 seconds (preferably 60 to 300 seconds).

[0134] Whether layer (II) is formed by treating the precursor layer can be confirmed by determining the ratio [absorbance (A2') / absorbance (A1')], which is the ratio of the maximum absorbance (A1') based on the Al-O-P bond in the range of 800 to 1400 cm -1 to the maximum absorbance (A2') based on the stretching vibration of the hydroxyl group in the range of 2500 to 4000 cm -1 in the infrared absorption spectrum. Since the Al-O-P bond is not sufficiently formed in the precursor layer, the relationship of [absorbance (A2') / absorbance (A1')]≧0.2 is usually satisfied. On the other hand, in layer (II), since the Al-O-P bond is sufficiently formed, the relationship of [absorbance (A2') / absorbance (A1')]<0.2 is satisfied. Therefore, by checking the value of [absorbance (A2') / absorbance (A1')], it is possible to confirm whether the Al-O-P bond is formed. It is more preferable that [absorbance (A2') / absorbance (A1')]<0.1. Setting it within the above range is preferable from the viewpoint that the Al-O-P bond in layer (II) is sufficiently formed and the gas barrier property of the obtained laminate is highly expressed.

[0135] When the above-mentioned adhesive layer is formed on the surface of the base material (I), it is preferable to perform an aging treatment before performing the above treatment. By performing such an aging treatment, the adhesive strength between the base material (I) and layer (II) tends to be stronger.

[0136] Specifically, before the treatment, it is preferable to leave the base material (I) on which the precursor layer of layer (II) is formed at a relatively low temperature for a long time.

[0137] The temperature of the aging treatment is usually less than 110°C, preferably 100°C or less, more preferably 90°C or less. The lower limit is usually 10°C or more, preferably 20°C or more, more preferably 30°C or more.

[0138] The aging treatment time is usually 0.5 to 10 days, preferably 1 to 7 days, more preferably 1 to 5 days.

[0139] By the step (iii), a layer (II) containing a reaction product (R) of a compound (A) containing aluminum and a phosphorus compound (B) is formed on at least one of the front and back sides of the substrate (I).

[0140] When the laminate has a surface protective layer (III), the surface protective layer (III) may be formed by a known method, such as gravure coating, gravure reverse coating, kiss reverse gravure coating, spin coating, bar coating, die coating, etc.

[0141] The thickness of the laminate thus obtained is usually 5 to 1500 μm, preferably 10 to 200 μm.

[0142] [Physical properties of the laminate] The laminate can have the following physical properties.

[0143] [Oxygen permeability] The laminate has an oxygen transmission rate (OTR) of 0.1 cc / m 2 / day / atm or less, preferably 0.09 cc / m 2 / day / atm or less, more preferably 0.08 cc / m 2 / day / atm or less under the conditions of 23 °C and 80% relative humidity measured according to JIS K7126-2 (2006).

[0144] [Water vapor transmission rate] The laminate has a water vapor transmission rate (WVTR) of 0.1 g / m 2 / day or less, preferably 0.09 g / m 2 / day, more preferably 0.08 g / m 2 / day under the conditions of 40 °C and 90% relative humidity measured according to JIS Z0208 (1976).

[0145] This laminate has an oxygen transmission rate (OTR) and / or a water vapor transmission rate (WVTR) that satisfy the above-described ranges, and it is more preferable that both the oxygen transmission rate (OTR) and the water vapor transmission rate (WVTR) satisfy the above-described ranges.

[0146] To obtain a laminate having the above oxygen transmission rate and water vapor transmission rate, for example, a method of setting the abundance ratio of water to alcohol (water / alcohol) in the solvent contained in the coating liquid for forming layer (II) to 5 or more can be mentioned. That is, by setting the abundance ratio of water to alcohol in the solvent to 5 or more, the ratio of water increases, the interaction between the compound (A) containing aluminum and the phosphorus compound (B) becomes stronger, and by appropriately containing alcohol, gelation due to the interaction between the compound (A) containing aluminum and the phosphorus compound (B) can be suppressed. Therefore, it is presumed that the resulting laminate has excellent gas barrier properties when layer (II) is formed.

[0147] 〔Uses of This Laminate〕 This laminate can be used for packages, liquid crystal display elements, solar cells, electromagnetic wave shields, touch panels, EL substrates, color filters, etc. Among them, this laminate can be preferably used for packages.

[0148] <<Package>> The above package may be produced using this laminate (laminated film) as it is, or may be produced using a film obtained by laminating this laminate (laminated film) with another film.

[0149] Examples of the other film include polyolefin-based films, polyamide-based films, polyester-based films, acrylic-based films, etc. These may be used alone or in combination of two or more.

[0150] When laminating this laminate with another film, known methods such as laminating using an adhesive layer or laminating by a thermal lamination method may be used.

[0151] The form of the packaging body is not particularly limited, and examples include a bag body, a tube, a lid material, a bottom material, etc. It can be used for packaging that houses foods, pharmaceuticals and medical products, electronic components, industrial components, etc. Since it can suppress the permeation of water vapor, oxygen gas, etc., it can prevent the corrosion and spoilage of the contents and enable long-term storage.

Examples

[0152] Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the following examples as long as it does not exceed the gist thereof. In the examples, "parts" and "%" mean mass basis.

[0153] Prior to the examples, coating liquids (c1) to (c12) were prepared according to the following preparation methods. The compositions of the coating liquids (c1) to (c12) are shown in Table 1 below.

[0154] [Preparation of Coating Liquid (c1)] To 20 parts of aluminosol 10A (manufactured by Kawaken Fine Chemical Co., Ltd., a dispersion of a compound having a pseudo-boehmite structure, Al2O3 equivalent concentration 10%, average primary major axis 50 nm, average primary minor axis 10 nm, average primary aspect ratio 5), 55.2 parts of distilled water, 0.5 part of a 4% aqueous solution of unmodified PVA (degree of polymerization 1700, saponification degree 99 mol%), and 5.2 parts of ethanol were added. While stirring at room temperature, 27.0 parts of an 8.5% phosphoric acid aqueous solution was added dropwise and mixed. After the addition was completed, stirring was continued for 30 minutes to obtain a coating liquid (c1) with a total solid content concentration of 4%.

[0155] [Preparation of Coating Liquid (c2)] It was prepared in the same manner as the coating liquid (c1) except that the distilled water to be added was changed to 50.1 parts and the ethanol was changed to 10.4 parts.

[0156] [Preparation of Coating Liquid (c3)] It was prepared in the same manner as the coating liquid (c1) except that the distilled water to be added was changed to 55.0 parts, the 4% aqueous solution of unmodified PVA was changed to 5.0 parts, and the ethanol was changed to 5.4 parts.

[0157] [Preparation of Coating Liquid (c4)] The coating solution (c2) was prepared in the same manner as the coating solution (c1), except that the amount of distilled water added was changed to 49.6 parts, the 4% aqueous solution of unmodified PVA was changed to 5.0 parts, and ethanol was changed to 10.8 parts.

[0158] [Preparation of Coating Solution (c5)] The coating solution (c5) was prepared in the same manner as the coating solution (c1), except that the amount of distilled water added was changed to 45.9 parts and ethanol was changed to 14.5 parts.

[0159] [Preparation of Coating Solution (c6)] The coating solution (c6) was prepared in the same manner as the coating solution (c1), except that the amount of distilled water added was changed to 29.3 parts and ethanol was changed to 31.1 parts.

[0160] [Preparation of Coating Solution (c7)] The coating solution (c7) was prepared in the same manner as the coating solution (c1), except that the amount of distilled water added was changed to 60.4 parts and ethanol was changed to 0 parts.

[0161] [Preparation of Coating Solution (c8)] The coating solution (c8) was prepared in the same manner as the coating solution (c1), except that the amount of distilled water added was changed to 47.7 parts, ethanol was changed to 53.2 parts, and the 8.5% phosphoric acid aqueous solution to be dropped was changed to 63.0 parts.

[0162] [Preparation of Coating Solution (c9)] The coating solution (c9) was prepared in the same manner as the coating solution (c1), except that the amount of distilled water added was changed to 34.8 parts, ethanol was changed to 37.7 parts, and the 8.5% phosphoric acid aqueous solution to be dropped was changed to 37.8 parts.

[0163] [Preparation of Coating Solution (c10)] The coating solution (c10) was prepared in the same manner as the coating solution (c1), except that the amount of distilled water added was changed to 31.6 parts, ethanol was changed to 33.9 parts, and the 8.5% phosphoric acid aqueous solution to be dropped was changed to 31.5 parts.

[0164] [Preparation of Coating Solution (c11)] It was prepared in the same manner as coating liquid (c1), except that the distilled water to be added was changed to 27.5 parts, ethanol to 29.0 parts, and the 8.5% phosphoric acid aqueous solution to be added dropwise to 23.6 parts.

[0165] [Preparation of Coating Liquid (c12)] It was prepared in the same manner as coating liquid (c1), except that the distilled water to be added was changed to 25.1 parts, ethanol to 26.2 parts, and the 8.5% phosphoric acid aqueous solution to be added dropwise to 18.9 parts.

[0166] [Table 1]

[0167] <Fabrication of Laminates (Examples 1 - 5, Comparative Examples 1 - 7)> Coating liquids (c1) - (c12) were coated on the corona - treated surface of a 38 - μm - thick polyethylene terephthalate (PET) film [biaxially stretched film, "FE2001" manufactured by Futamura Chemical Co., Ltd.] that had been corona - treated on one side using a bar coater, and dried at 110°C for 5 minutes to form a precursor layer of layer (II). Thereafter, heat treatment was carried out at 200°C for 1 minute to form layer (II), and laminates (with a thickness of 1 μm after drying) of Examples 1 - 5, Comparative Example 1, and Comparative Examples 3 - 7 were obtained. In Comparative Example 2, coating liquid (c7) gelled and could not be coated on the PET film. This is presumably because the solvent of coating liquid (c7) is only water, so the interaction between Al2O3 and phosphoric acid in the solvent became strong and gelling occurred. Also, as a result of measuring the infrared absorption spectrum of layer (II) of the laminates of Examples 1 - 5, Comparative Example 1, and Comparative Examples 3 - 7, the maximum absorbance (A1') based on the Al - O - P bond in the range of 800 - 1400 cm -1 and the maximum absorbance (A2') based on the stretching vibration of the hydroxyl group in the range of 2500 - 4000 cm -1 satisfied the relationship of [absorbance (A2') / absorbance (A1')]<0.2, and it was confirmed that the Al - O - P bond was formed in layer (II).

[0168] Using the obtained laminates of Examples 1 to 5 and Comparative Examples 1, 3 to 7, the oxygen permeability and water vapor permeability were evaluated, and a comprehensive evaluation was performed based on the results of the oxygen permeability and water vapor permeability. The results are shown in Table 2 below.

[0169] [Oxygen Permeability] The oxygen transmission rate (OTR) of the laminates of Examples 1 to 5 and Comparative Examples 1, 3 to 7 was measured under the conditions of 23°C and 80% relative humidity in accordance with JIS K7126-2 (2006).

[0170] [Water Vapor Permeability] The water vapor transmission rate (WVTR) of the laminates of Examples 1 to 5 and Comparative Examples 1, 3 to 7 was measured under the conditions of 40°C and 90% relative humidity in accordance with JIS Z0208 (1976).

[0171] [Comprehensive Evaluation] Based on the measured oxygen transmission rate (OTR) and water vapor transmission rate (WVTR), the evaluation was carried out according to the following evaluation criteria. [Evaluation Criteria] ◎: Oxygen permeability is 0.1 cc / m 2 ·day / atm or less, and water vapor permeability is 0.1 g / m 2 / day or less 〇: Oxygen permeability is 0.1 cc / m 2 ·day / atm or less, or water vapor permeability is 0.1 g / m 2 / day or less ×: Oxygen permeability exceeds 0.1 cc / m 2 ·day / atm, and water vapor permeability exceeds 0.1 g / m 2 / day

[0172]

Table 2

[0173] From the results in Table 2 above, the laminates of Examples 1 to 5 were excellent in gas barrier properties because of their low oxygen permeability and water vapor permeability. On the other hand, the laminates of Comparative Examples 1 and 3 to 7 had high oxygen permeability and water vapor permeability and were inferior in gas barrier properties. Further, in Comparative Example 2, the coating liquid gelled and layer (II) could not be formed.

Industrial Applicability

[0174] Since this laminate has excellent gas barrier properties, it can be suitably used for packages, liquid crystal display elements, solar cells, electromagnetic wave shields, touch panels, EL substrates, color filters, and the like.

Claims

1. A laminate comprising a layer (II) containing a reaction product (R) of a compound (A) containing aluminum and a phosphorus compound (B) on at least one of the front and back sides of a base material (I), the laminate satisfying the following (i) and / or (ii). (i) The oxygen permeability measured in accordance with JIS K7126-2 (2006) is 0.1 cc / m 2 ·day / atm or less (ii) The water vapor permeability measured in accordance with JIS Z0208 (1976) is 0.1 g / m 2 / day or less

2. The laminate according to claim 1, wherein the layer (II) contains a hydrophilic resin.

3. The laminate according to claim 2, wherein the hydrophilic resin is contained in an amount of 0.01 to 30% by mass based on 100% by mass of the total components contained in the layer (II).

4. The laminate according to claim 2, wherein the hydrophilic resin is a polyvinyl alcohol-based resin.

5. The laminate according to claim 1, wherein the reaction product (R) is a reaction product having an Al—O—P bond formed by a compound (A) containing aluminum and a phosphorus compound (B).

6. The laminate according to claim 1, wherein the compound (A) containing aluminum is a metal oxide containing aluminum.

7. The laminate according to claim 1, wherein the phosphorus compound (B) is an inorganic phosphorus compound.

8. The laminate according to claim 1, wherein the thickness of the layer (II) is 0.01 to 5 μm.

9. The laminate according to claim 1, wherein the layer (II) is a coating layer.

10. The laminate according to claim 1, wherein the base material (I) contains at least one thermoplastic resin selected from the group consisting of polyamide resins, polyolefin resins, polyester resins, and polystyrene resins.

11. The laminate according to claim 1, wherein the base material (I) is stretched in at least one direction.

12. A laminated film comprising the laminate according to any one of claims 1 to 11.

13. A package using the laminated film according to claim 12.

14. A method for producing a laminate comprising a layer (II) containing a reaction product (R) of a compound (A) containing aluminum and a phosphorus compound (B) on at least one of the front and back sides of a base material (I), comprising at least a step of forming the layer (II) by coating a coating liquid containing a compound (A) containing aluminum and a phosphorus compound (B) on the base material (I), The method for producing a laminate, wherein the coating liquid contains water and alcohol as solvents, and the ratio of the presence of water in the solvent (water / alcohol) is 5 or more.

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