WO2016103717A1 - Structure multicouche, matériau d'emballage ainsi que marchandise mettant en œuvre celle-ci, et feuille protectrice pour dispositif électronique - Google Patents

Structure multicouche, matériau d'emballage ainsi que marchandise mettant en œuvre celle-ci, et feuille protectrice pour dispositif électronique Download PDF

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Publication number
WO2016103717A1
WO2016103717A1 PCT/JP2015/006456 JP2015006456W WO2016103717A1 WO 2016103717 A1 WO2016103717 A1 WO 2016103717A1 JP 2015006456 W JP2015006456 W JP 2015006456W WO 2016103717 A1 WO2016103717 A1 WO 2016103717A1
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layer
group
multilayer structure
compound
phosphoric acid
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PCT/JP2015/006456
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English (en)
Japanese (ja)
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佐々木　良一
康貴 犬伏
清水　裕司
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株式会社クラレ
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Priority to JP2016565932A priority Critical patent/JP6564788B2/ja
Publication of WO2016103717A1 publication Critical patent/WO2016103717A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38—Packaging materials of special type or form
    • B65D65/40—Applications of laminates for particular packaging purposes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D81/00—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents
    • B65D81/24—Adaptations for preventing deterioration or decay of contents; Applications to the container or packaging material of food preservatives, fungicides, pesticides or animal repellants
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D85/00—Containers, packaging elements or packages, specially adapted for particular articles or materials
    • B65D85/50—Containers, packaging elements or packages, specially adapted for particular articles or materials for living organisms, articles or materials sensitive to changes of environment or atmospheric conditions, e.g. land animals, birds, fish, water plants, non-aquatic plants, flower bulbs, cut flowers or foliage

Definitions

  • the present invention relates to a multilayer structure, a packaging material and a product using the same, and a protective sheet for an electronic device.
  • a multilayer structure in which a gas barrier layer containing aluminum or aluminum oxide as a constituent component is formed on a plastic film is well known.
  • Such a multilayer structure is used as a packaging material for protecting an article (for example, food) that is easily deteriorated by oxygen.
  • Many of these gas barrier layers are formed on a plastic film by a dry process such as physical vapor deposition (PVD) or chemical vapor deposition (CVD).
  • PVD physical vapor deposition
  • CVD chemical vapor deposition
  • such a multilayer structure is also used as a constituent member of a protective sheet of an electronic device that requires gas barrier properties and water vapor barrier properties for the purpose of protecting the features of the electronic device.
  • aluminum vapor deposition film has light shielding properties in addition to gas barrier properties, and is mainly used as a packaging material for dry foods.
  • the aluminum oxide vapor-deposited film having transparency has a feature that the contents can be visually recognized, and foreign matter inspection and microwave heating can be performed by a metal detector. Therefore, the film is used as a packaging material in a wide range of applications including retort food packaging.
  • Patent Document 1 discloses a multilayer structure having a transparent gas barrier layer constituted by a reaction product of aluminum oxide particles and a phosphorus compound.
  • Patent Document 1 discloses a method in which a coating liquid containing aluminum oxide particles and a phosphorus compound is applied on a plastic film, followed by drying and heat treatment.
  • the conventional multilayer structure having a gas barrier layer is excellent in initial gas barrier properties, but when subjected to physical stress such as deformation or impact, the gas barrier layer has defects such as cracks or pinholes, resulting in gas barrier properties. May be reduced.
  • Patent Document 2 has proposed a multilayer structure that not only has excellent gas barrier properties but also can maintain the gas barrier properties at a high level even when subjected to physical stress such as deformation and impact.
  • An object of the present invention is to provide a novel multilayer structure excellent in gas barrier property and water vapor barrier property and excellent in retort resistance, and a packaging material using the same.
  • Another object of the present invention is to provide a protective sheet for an electronic device using a novel multilayer structure having excellent gas barrier properties and water vapor barrier properties and high interlayer adhesion even under high temperature and high humidity. It is in.
  • the present inventors have found that the above object can be achieved by a multilayer structure including a specific layer, and have reached the present invention.
  • the present invention is a multilayer structure comprising a substrate (X) and a layer (Y) laminated on the substrate (X), wherein the layer (Y) is a compound (A) containing aluminum and polyvinyl. and a alcohol-based resin phosphoric acid ester of (BP), phosphoric acid esterification rate R BP of the polyvinyl alcohol resin phosphoric acid ester of (BP) is 0.15 or more, provide a multilayer structure To do.
  • the compound (A) containing aluminum is a compound (Ab) containing a reaction product (D) of a metal oxide (Aa) containing aluminum and an inorganic phosphorus compound (BI). May be.
  • phosphoric acid esterification rate R BP of the polyvinyl alcohol resin phosphoric acid ester of (BP) may be 0.24 or more.
  • the phosphate ester product (BP) may contain 15.0 to 99.8 mol% of a phosphate esterified vinyl alcohol unit represented by the following general formula [III]. Good.
  • the substrate (X) may include at least one layer selected from the group consisting of a thermoplastic resin film and paper.
  • the present invention also provides a packaging material including any of the multilayer structures described above.
  • the packaging material may further have a layer formed by extrusion coating lamination.
  • the packaging material may be a vertical bag-filling sealing bag, a vacuum packaging bag, a pouch, a laminated tube container, an infusion bag, a paper container, a strip tape, a container lid, or an in-mold label container.
  • the present invention provides a product using at least part of any of the packaging materials described above.
  • the product may include a content, the content is a core material, the inside of the product is decompressed, and the product may function as a vacuum heat insulator.
  • the present invention also provides an electronic device protective sheet comprising any of the multilayer structures described above.
  • the protective sheet for the electronic device may be a protective sheet for protecting the surface of the photoelectric conversion device, the information display device, or the lighting device.
  • the present invention also provides an electronic device including any of the protective sheets described above.
  • a novel multilayer structure excellent in gas barrier property and water vapor barrier property and excellent in retort resistance and a packaging material using the same can be obtained. That is, according to the present invention, not only the gas barrier property and the water vapor barrier property are excellent, but also excellent gas barrier property and water vapor barrier property can be maintained after the retort treatment, and appearance defects such as delamination do not occur after the retort treatment.
  • a novel multilayer structure having a high interlayer adhesion (peel strength) and a packaging material using the same are obtained.
  • a protective sheet for an electronic device using a novel multilayer structure having excellent gas barrier properties and water vapor barrier properties and having high interlayer adhesion even under high temperature and high humidity can be obtained. That is, according to the present invention, not only the gas barrier property and the water vapor barrier property are excellent, but also excellent gas barrier property and water vapor barrier property can be maintained even after the dump heat test, and appearance defects such as delamination after the dump heat test can be maintained.
  • the electronic device which has a protective sheet containing the novel multilayer structure which does not arise and has high interlayer adhesive strength (peeling strength) is obtained.
  • the meaning of “lamination of a specific layer on a specific member (base material, layer, etc.)” means that the specific layer is in contact with the member.
  • the case where the specific layer is laminated above the member with another layer interposed therebetween is included.
  • a specific layer is formed on a specific member (base material, layer, etc.)” and “a specific layer is arranged on a specific member (base material, layer, etc.)”.
  • the meaning of “application of a liquid (coating liquid, etc.) on a specific member (base material, layer, etc.)” means that the liquid is applied directly to the member.
  • the case where the liquid is applied to another layer formed on the member is included.
  • a layer (Y) may be distinguished from other layers by attaching a symbol (Y), such as “layer (Y)”.
  • Y Unless otherwise noted, the symbol (Y) has no technical meaning.
  • the case where it is clear to show a specific element like a hydrogen atom (H) is excluded.
  • the multilayer structure of the present invention includes a substrate (X) and a layer (Y) containing aluminum.
  • the layer (Y) comprises a compound (A) containing aluminum (hereinafter also simply referred to as “compound (A)”) and a phosphoric acid ester (BP) of a polyvinyl alcohol resin (hereinafter simply referred to as “phosphoric acid ester (BP)”. ) includes also referred) and a "phosphoric acid ester ratio R BP of the polyvinyl alcohol resin phosphoric acid ester of (BP) is 0.15 or more.
  • the phrase “multilayer structure” means a multilayer structure including a substrate (X) and a layer (Y).
  • the layer (Y) at least a part of the compound (A) and at least a part of the phosphoric acid ester (BP) may be reacted. Further, when the layer (Y) contains an inorganic phosphorus compound (BI), at least a part of the compound (A) reacts with at least a part of the inorganic phosphorus compound (BI) and / or the phosphoric acid ester (BP). It may be. Even when the compound (A) is reacted in the layer (Y), the part of the compound (A) constituting the reaction product is regarded as the compound (A).
  • the mass of the compound (A) used for forming the reaction product (the mass of the compound (A) before the reaction) is included in the mass of the compound (A) in the layer (Y). Further, even when the inorganic phosphorus compound (BI) and / or the phosphate ester (BP) are reacted in the layer (Y), the inorganic phosphorus compound (BI) and / or phosphate ester which constitutes the reaction product
  • the part of (BP) is regarded as an inorganic phosphorus compound (BI) and / or a phosphoric acid ester (BP).
  • the mass of the inorganic phosphorus compound (BI) and / or phosphate esterified product (BP) used for forming the reaction product Is included in the mass of the inorganic phosphorus compound (BI) and / or the phosphoric acid ester (BP) in the layer (Y).
  • the material of the base material (X) is not particularly limited, and base materials made 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 and the like. Among these, a thermoplastic resin and a fiber assembly are preferable, and a thermoplastic resin is more preferable.
  • the form of the substrate (X) is not particularly limited, and may be a layered form such as a film or a sheet.
  • the substrate (X) preferably includes at least one selected from the group consisting of a thermoplastic resin film and paper, more preferably includes a thermoplastic resin film, and more preferably is a thermoplastic resin film. .
  • thermoplastic resin used for the substrate (X) examples include polyolefin resins such as polyethylene and polypropylene; polyethylene terephthalate (PET), polyethylene-2,6-naphthalate, polybutylene terephthalate, and copolymers thereof.
  • Polyester resins such as nylon-6, nylon-66, nylon-12, etc .; hydroxyl group-containing polymers such as polyvinyl alcohol and ethylene-vinyl alcohol copolymers; polystyrene; poly (meth) acrylic acid esters; polyacrylonitrile; Polyvinyl acetate; Polycarbonate; Polyarylate; Regenerated cellulose; Polyimide; Polyetherimide; Polysulfone; Polyethersulfone; Polyetheretherketone; Ionomer resin
  • the material of the substrate (X) is preferably at least one thermoplastic resin selected from the group consisting of polyethylene, polypropylene, polyethylene terephthalate, nylon-6, and nylon-66. .
  • the substrate (X) 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 substrate (X) include craft paper, fine paper, imitation paper, glassine paper, parchment paper, synthetic paper, white paperboard, Manila ball, milk carton base paper, cup base paper, ivory paper and the like. It is done. By using paper for the substrate (X), a multilayer structure for paper containers can be obtained.
  • the thickness is preferably 1 to 1,000 ⁇ m, more preferably 5 to 500 ⁇ m from the viewpoint of improving the mechanical strength and workability of the resulting multilayer structure. 9 to 200 ⁇ m is more preferable.
  • the layer (Y) contains a compound (A) and a phosphoric acid ester (BP).
  • the compound (A) is a compound containing aluminum.
  • the layer (Y) preferably further contains an inorganic phosphorus compound (BI).
  • the inorganic phosphorus compound (BI) and the phosphoric acid ester (BP) have a functional group containing a phosphorus atom.
  • the compound (A), inorganic phosphorus compound (BI), and phosphoric acid ester (BP) will be described below.
  • the compound (A) may be a metal oxide (Aa) containing aluminum, or a metal oxide (Aa) containing aluminum (hereinafter also simply referred to as “metal oxide (Aa)”) and an inorganic phosphorus compound. It may be a compound (Ab) containing a reaction product (D) formed by a reaction with (BI) (hereinafter also simply referred to as “compound (Ab)”).
  • Metal oxide containing aluminum (Aa) The metal oxide (Aa) containing aluminum is usually reacted with an inorganic phosphorus compound (BI) in the form of particles.
  • the metal atoms constituting the metal oxide (Aa) containing aluminum are at least one selected from metal atoms belonging to Groups 2 to 14 of the periodic table. It is a seed metal atom, but it contains at least aluminum.
  • the metal atom (M) may be aluminum alone or may contain aluminum and other metal atoms. Two or more metal oxides (Aa) may be used in combination as the metal oxide (Aa).
  • the proportion of aluminum in the metal atom (M) is usually 50 mol% or more, 60 to 100 mol%, or 80 to 100 mol%.
  • the metal oxide (Aa) include a metal oxide produced by a method such as a liquid phase synthesis method, a gas phase synthesis method, or a solid pulverization method.
  • the metal oxide (Aa) may be a hydrolysis condensate of the compound (E) containing a metal atom (M) to which a hydrolyzable characteristic group is bonded.
  • Examples of the characteristic group include R 1 of the general formula [I] described later.
  • the hydrolysis condensate of compound (E) can be substantially regarded as a metal oxide. Therefore, in this specification, the hydrolysis condensate of compound (E) may be referred to as “metal oxide (Aa)”. That is, in the present specification, “metal oxide (Aa)” can be read as “hydrolysis condensate of compound (E)”, and “hydrolysis condensate of compound (E)” is “metal oxidation condensate”. It can be read as “object (Aa)”.
  • the compound (E) is a compound (Ea) represented by the following general formula [I]. It is preferable to include at least one kind.
  • R 1 has a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), NO 3 , an optionally substituted alkoxy group having 1 to 9 carbon atoms, or a substituent.
  • R 2 represents an optionally substituted alkyl group having 1 to 9 carbon atoms, an optionally substituted aralkyl group having 7 to 10 carbon atoms, and an optionally substituted carbon.
  • k is an integer of 1 to 3.
  • Compound (E) may contain at least one compound (Eb) represented by the following general formula [II] in addition to compound (Ea).
  • M 1 is a metal atom other than an aluminum atom, and is at least one metal atom selected from metal atoms belonging to Groups 2 to 14 of the periodic table.
  • R 3 may have a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), NO 3 , an optionally substituted alkoxy group having 1 to 9 carbon atoms, or a substituent.
  • R 4 represents an optionally substituted alkyl group having 1 to 9 carbon atoms, an optionally substituted aralkyl group having 7 to 10 carbon atoms, and an optionally substituted carbon.
  • m is an integer of 1 to n.
  • n is equal to the valence of M 1 .
  • alkoxy group of R 1 and R 3 examples include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, benzyloxy group, diphenyl Methoxy group, trityloxy group, 4-methoxybenzyloxy group, methoxymethoxy group, 1-ethoxyethoxy group, benzyloxymethoxy group, 2-trimethylsilylethoxy group, 2-trimethylsilylethoxymethoxy group, phenoxy group, 4-methoxyphenoxy group Etc.
  • Examples of the acyloxy group for R 1 and R 3 include an acetoxy group, an ethylcarbonyloxy group, an n-propylcarbonyloxy group, an isopropylcarbonyloxy group, an n-butylcarbonyloxy group, an isobutylcarbonyloxy group, and a sec-butylcarbonyloxy group. Group, tert-butylcarbonyloxy group, n-octylcarbonyloxy group and the like.
  • alkenyloxy group for R 1 and R 3 examples include allyloxy group, 2-propenyloxy group, 2-butenyloxy group, 1-methyl-2-propenyloxy group, 3-butenyloxy group, 2-methyl-2-propenyl Oxy group, 2-pentenyloxy group, 3-pentenyloxy group, 4-pentenyloxy group, 1-methyl-3-butenyloxy group, 1,2-dimethyl-2-propenyloxy group, 1,1-dimethyl-2- Propenyloxy group, 2-methyl-2-butenyloxy group, 3-methyl-2-butenyloxy group, 2-methyl-3-butenyloxy group, 3-methyl-3-butenyloxy group, 1-vinyl-2-propenyloxy group, And 5-hexenyloxy group.
  • Examples of the ⁇ -diketonato group for R 1 and R 3 include 2,4-pentandionato group, 1,1,1-trifluoro-2,4-pentandionato group, 1,1,1,5, 5,5-hexafluoro-2,4-pentanedionate group, 2,2,6,6-tetramethyl-3,5-heptanedionate group, 1,3-butanedionate group, 2-methyl-1,3-butanedionate Group, 2-methyl-1,3-butanedionato group, benzoylacetonato group and the like.
  • Examples of the acyl group of the diacylmethyl group of R 1 and R 3 include carbon numbers such as formyl group, acetyl group, propionyl group (propanoyl group), butyryl group (butanoyl group), valeryl group (pentanoyl group), hexanoyl group and the like. 1-6 aliphatic acyl groups; aromatic acyl groups (aroyl groups) such as benzoyl groups and toluoyl groups.
  • Examples of the alkyl group for R 2 and R 4 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, Examples include isopentyl group, n-hexyl group, isohexyl group, 3-methylpentyl group, 2-methylpentyl group, 1,2-dimethylbutyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group and the like.
  • Examples of the aralkyl group of R 2 and R 4 include a benzyl group and a phenylethyl group (phenethyl group).
  • alkenyl group for R 2 and R 4 examples include a vinyl group, 1-propenyl group, 2-propenyl group, isopropenyl group, 3-butenyl group, 2-butenyl group, 1-butenyl group, 1-methyl-2 -Propenyl group, 1-methyl-1-propenyl group, 1-ethyl-1-ethenyl group, 2-methyl-2-propenyl group, 2-methyl-1-propenyl group, 3-methyl-2-butenyl group, 4 -Pentenyl group and the like.
  • Examples of the aryl group for R 2 and R 4 include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group.
  • Examples of the substituent in R 1 , R 2 , R 3 and R 4 include alkyl groups having 1 to 6 carbon atoms; methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group , Sec-butoxy group, tert-butoxy group, n-pentyloxy group, isopentyloxy group, n-hexyloxy group, cyclopropyloxy group, cyclobutyloxy group, cyclopentyloxy group, cyclohexyloxy group, etc.
  • R 1 and R 3 include a halogen atom, NO 3 , an optionally substituted alkoxy group having 1 to 6 carbon atoms, an optionally substituted acyloxy group having 2 to 6 carbon atoms, A ⁇ -diketonato group having 5 to 10 carbon atoms which may have a substituent or a diacylmethyl group having an acyl group having 1 to 6 carbon atoms which may have a substituent is preferable.
  • An optionally substituted alkoxy group having 1 to 6 carbon atoms is more preferable.
  • R 2 and R 4 are preferably an alkyl group having 1 to 6 carbon atoms which may have a substituent.
  • K in the formula [I] is preferably 3.
  • M 1 is preferably a metal atom belonging to Group 4 of the periodic table, more preferably titanium or zirconium.
  • m in Formula [II] is preferably 4.
  • boron and silicon may be classified as semi-metals, but in this specification, these are included in the metal.
  • Examples of the compound (Ea) include aluminum chloride, aluminum nitrate, aluminum acetate, tris (2,4-pentanedionato) aluminum, trimethoxyaluminum, triethoxyaluminum, tri-n-propoxyaluminum, triisopropoxyaluminum, Tri-n-butoxyaluminum, tri-sec-butoxyaluminum, tri-tert-butoxyaluminum and the like can be mentioned, among which triisopropoxyaluminum and tri-sec-butoxyaluminum are preferable.
  • the compound (E) two or more kinds of compounds (Ea) may be used in combination.
  • Examples of the compound (Eb) include tetrakis (2,4-pentanedionato) titanium, tetramethoxytitanium, tetraethoxytitanium, tetraisopropoxytitanium, tetra-n-butoxytitanium, tetrakis (2-ethylhexoxy) titanium and the like. Titanium compounds; zirconium compounds such as tetrakis (2,4-pentanedionato) zirconium, tetra-n-propoxyzirconium, tetra-n-butoxyzirconium, and the like. These may be used alone or in combination of two or more compounds (Eb).
  • the ratio of the compound (Ea) in the compound (E) is not particularly limited as long as the effect of the present invention is obtained.
  • the proportion of the compound other than the compound (Ea) (for example, the compound (Eb)) in the compound (E) is, for example, preferably 20 mol% or less, more preferably 10 mol% or less, further preferably 5 mol% or less, It may be 0 mol%.
  • the hydrolyzate condenses to form a compound in which the metal atom (M) is bonded through the oxygen atom (O).
  • a compound that can be substantially regarded as a metal oxide is formed.
  • a hydroxyl group usually exists on the surface of the metal oxide (Aa) thus formed.
  • a compound having a ratio of [number of moles of oxygen atom (O) bonded only to metal atom (M)] / [number of moles of metal atom (M)] of 0.8 or more is metal It shall be included in oxide (Aa).
  • the oxygen atom (O) bonded only to the metal atom (M) is the oxygen atom (O) in the structure represented by MOM, and the structure represented by MOH.
  • Oxygen atoms bonded to metal atoms (M) and hydrogen atoms (H) such as oxygen atoms (O) in are excluded.
  • the ratio in the metal oxide (Aa) is preferably 0.9 or more, more preferably 1.0 or more, and further preferably 1.1 or more. Although the upper limit of this ratio is not particularly limited, it is usually represented by n / 2, where n is the valence of the metal atom (M).
  • the compound (E) In order for the hydrolysis condensation to occur, it is important that the compound (E) has a hydrolyzable characteristic 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 (Aa).
  • the hydrolyzed condensate of compound (E) may be produced from a specific raw material by, for example, a method adopted in a known sol-gel method.
  • the raw materials include compound (E), partial hydrolyzate of compound (E), complete hydrolyzate of compound (E), compound obtained by partially hydrolytic condensation of compound (E), and compound (E ) Can be used at least one selected from the group consisting of compounds obtained by condensing a part of the complete hydrolyzate.
  • the metal oxide (Aa) provided for mixing with an inorganic phosphorus compound (BI) -containing material substantially contains a phosphorus atom. It is preferable not to contain.
  • the reaction product (D) contained in the compound (Ab) is obtained by reacting the metal oxide (Aa) with the inorganic phosphorus compound (BI).
  • the compound produced by the reaction of the metal oxide (Aa), the inorganic phosphorus compound (BI), and another compound is also included in the reaction product (D).
  • the compound (Ab) may partially contain a metal oxide (Aa) and / or an inorganic phosphorus compound (BI) that are not involved in the reaction.
  • the molar ratio between the metal atom constituting the metal oxide (Aa) and the phosphorus atom derived from the inorganic phosphorus compound (BI) is [metal atom constituting the metal oxide (Aa)]: [ The phosphorus atom derived from the inorganic phosphorus compound (BI)] is preferably in the range of 1.0: 1.0 to 3.6: 1.0, and 1.1: 1.0 to 3.0: 1. More preferably, it is in the range of 0. Outside this range, the gas barrier performance decreases.
  • the molar ratio in the compound (Ab) can be adjusted by the mixing ratio of the metal oxide (Aa) and the inorganic phosphorus compound (BI) in the coating liquid for forming the compound (Ab). The molar ratio in the compound (Ab) is usually the same as that in the coating solution.
  • the maximum absorption wave number in the region of 800 to 1,400 cm ⁇ 1 is preferably in the range of 1,080 to 1,130 cm ⁇ 1 .
  • the metal atom (M) derived from the metal oxide (Aa) and the inorganic phosphorus compound (BI) And a phosphorus atom (P) derived from the above form a bond represented by MOP via an oxygen atom (O).
  • a characteristic absorption band derived from the bond is generated in the infrared absorption spectrum of the reaction product (D).
  • the obtained multilayer structure has an excellent gas barrier. It was found to express sex. In particular, when the characteristic absorption band is the strongest absorption in the region of 800 to 1,400 cm ⁇ 1 in which absorption derived from bonds between various atoms and oxygen atoms is generally observed, the obtained multilayer structure was found to exhibit even better gas barrier properties.
  • the layer (Y) In the infrared absorption spectrum of the layer (Y), 800 half-value width of the maximum absorption band in the region of ⁇ 1,400cm -1, from the gas barrier properties of the viewpoint of the resulting multilayer structure, 200 cm -1 or less is preferable, 150 cm -1 The following is more preferable, 100 cm ⁇ 1 or less is further preferable, and 50 cm ⁇ 1 or less is particularly preferable.
  • the infrared absorption spectrum of the layer (Y) can be measured by the method described in Examples. However, when measurement by the method described in Examples is not possible, reflection measurement such as reflection absorption method, external reflection method, attenuated total reflection method, etc., scraping the layer (Y) from the multilayer structure, Nujol method, tablet method, etc. Although it may measure by the method of transmission measurement, it is not limited to these.
  • the compound (Ab) may have a structure in which the metal oxide (Aa) particles are bonded to each other via a phosphorus atom derived from the inorganic phosphorus compound (BI).
  • the shape and size of the metal oxide (Aa) particles used as the raw material of the compound (Ab) may be changed in the process of forming the compound (Ab).
  • the inorganic phosphorus compound (BI) contains a site capable of reacting with the metal oxide (Aa), and typically contains a plurality of such sites.
  • the inorganic phosphorus compound (BI) is preferably a compound containing 2 to 20 such sites (atomic groups or functional groups). Examples of such a part include a part capable of performing a condensation reaction with a functional group (for example, a hydroxyl group) present on the surface of the metal oxide (Aa). Examples of such a site include a halogen atom directly bonded to a phosphorus atom, an oxygen atom directly bonded to a phosphorus atom, and the like.
  • the functional group (for example, hydroxyl group) present on the surface of the metal oxide (Aa) is usually bonded to the metal atom (M) constituting the metal oxide (Aa).
  • Examples of the inorganic phosphorus compound (BI) include phosphoric acid, diphosphoric acid, triphosphoric acid, polyphosphoric acid condensed with 4 or more molecules of phosphoric acid, phosphorous acid, phosphonic acid, phosphonous acid, phosphinic acid, and phosphine.
  • Phosphorus oxoacids such as acids, and salts thereof (eg, sodium phosphate), and derivatives thereof (eg, halides (eg, phosphoryl chloride), dehydrates (eg, diphosphorus pentoxide)), and the like It is done.
  • inorganic phosphorus compounds (BI) may be used alone or in combination of two or more.
  • inorganic phosphorus compounds (BI) it is preferable to use phosphoric acid alone or to use phosphoric acid and other inorganic phosphorus compounds (BI) in combination.
  • phosphoric acid By using phosphoric acid, the stability of the coating liquid (S) described later and the gas barrier properties of the resulting multilayer structure are improved.
  • the multilayer structure of the present invention preferably contains no polymer (BO) containing a phosphorus atom other than the phosphoric acid ester (BP) of a polyvinyl alcohol resin.
  • the functional group containing a phosphorus atom that the polymer (BO) containing a phosphorus atom has include a phosphoric acid group, a phosphorous acid group, a phosphonic acid group, a phosphonous acid group, a phosphinic acid group, and a phosphinic acid group.
  • Functional groups derived from these (for example, salts, (partial) ester compounds, halides (for example, chloride), dehydrates) and the like can be mentioned.
  • the polymer (BO) containing phosphorus atoms include polymer compounds containing 10 or more phosphorus atoms.
  • the multilayer structure may further include an inorganic vapor deposition layer.
  • An inorganic vapor deposition layer can be formed by vapor-depositing an inorganic substance.
  • the inorganic substance for example, metal (for example, aluminum), metal oxide (for example, silicon oxide, aluminum oxide), metal nitride (for example, silicon nitride), metal nitride oxide (for example, silicon oxynitride), or metal Examples thereof include carbonitrides (for example, silicon carbonitride).
  • the layer (Y) in the multilayer structure of the present invention may include an inorganic vapor deposition layer containing aluminum.
  • the layer (Y) may include an aluminum deposition layer (Ac) and / or an aluminum oxide deposition layer (Ad).
  • the method for forming the inorganic vapor deposition layer is not particularly limited, and physical vapor deposition methods such as vacuum vapor deposition methods (for example, resistance heating vapor deposition, electron beam vapor deposition, molecular beam epitaxy method, etc.), sputtering methods, ion plating methods, heat Chemical vapor deposition (for example, catalytic chemical vapor deposition), photochemical vapor deposition, plasma chemical vapor deposition (for example, capacitively coupled plasma, inductively coupled plasma, surface wave plasma, electron cyclotron resonance, dual magnetron, Chemical vapor deposition methods such as atomic layer deposition and the like, and metal organic chemical vapor deposition.
  • vacuum vapor deposition methods for example, resistance heating vapor deposition, electron beam vapor deposition, molecular beam epitaxy method, etc.
  • sputtering methods ion plating methods
  • heat Chemical vapor deposition for example, catalytic chemical vapor deposition
  • photochemical vapor deposition for example, plasma chemical vapor deposition
  • the thickness of the inorganic vapor deposition layer varies depending on the types of components constituting the inorganic vapor deposition layer, but is preferably 0.002 to 0.5 ⁇ m, more preferably 0.005 to 0.2 ⁇ m, and 0.01 to 0.1 ⁇ m. Further preferred. Within this range, a thickness that improves the barrier properties or mechanical properties of the multilayer structure may be selected.
  • the thickness of the inorganic vapor deposition layer is less than 0.002 ⁇ m, the reproducibility of the barrier property expression of the inorganic vapor deposition layer against oxygen or water vapor tends to decrease, and the inorganic vapor deposition layer does not exhibit sufficient barrier properties There is also.
  • the thickness of the inorganic vapor deposition layer exceeds 0.5 ⁇ m, the barrier property of the inorganic vapor deposition layer tends to be lowered when the multilayer structure is pulled or bent.
  • a phosphoric acid ester product (BP) of a polyvinyl alcohol resin is obtained by esterification of a polyvinyl alcohol resin and phosphoric acid.
  • the polyvinyl alcohol resin include polyvinyl alcohol, polyvinyl acetate partially saponified product, ethylene-vinyl alcohol copolymer, ethylene-vinyl acetate copolymer partially saponified product, and the like.
  • a vinyl alcohol copolymer is preferable, and polyvinyl alcohol is more preferable.
  • the phosphate ester product (BP) particularly preferably contains 15.0 to 99.8 mol% of a phosphate esterified vinyl alcohol unit represented by the following general formula [III].
  • the content of the phosphate esterified vinyl alcohol unit is more preferably 99.0 mol% or less, and further preferably 95.0 mol% or less. Further, in order to obtain a multilayer structure having excellent interlayer adhesion, the content of the phosphate esterified vinyl alcohol unit is more preferably 30.0 mol% or more, and 45.0 mol% or more. Is more preferably 60.0 mol% or more.
  • the saponification degree of the polyvinyl alcohol resin used in the present invention is preferably 75.0 to 99.85 mol%, and in order to obtain a multilayer structure having excellent interlayer adhesion, 80.0 to 99.5 mol% Is more preferably 85.0 to 99.3 mol%, particularly preferably 90.0 to 99.1 mol%.
  • the saponification degree is a value obtained according to JIS K 6726 (1994).
  • the viscosity average polymerization degree of the polyvinyl alcohol resin used in the present invention is preferably from 100 to 4,000, more preferably from 200 to 3,500, more preferably from 300 to 3 in order to obtain a multilayer structure having excellent interlayer adhesion. 1,000 is more preferable, and 500 to 2,800 is particularly preferable.
  • the viscosity average degree of polymerization is a value determined according to JIS K 6726 (1994).
  • the viscosity of the polyvinyl alcohol resin used in the present invention is preferably 1.0 to 200 mPa ⁇ s, more preferably 3.0 to 150 mPa ⁇ s, in order to obtain a multilayer structure having excellent interlayer adhesion, 90 mPa ⁇ s is more preferable, and 20 to 85 mPa ⁇ s is particularly preferable.
  • the viscosity is a value measured with a B-type rotational viscometer using a 4% by mass aqueous solution at 20 ° C. according to JIS K 6726 (1994).
  • the polyvinyl alcohol resin used in the present invention has a saponification degree of 85.0 to 99.3 mol%, a viscosity average polymerization degree of 200 to 3,500, and a viscosity of 11 to 90 mPa ⁇ s. More preferred are those having a saponification degree of 85.0 to 99.3 mol%, a viscosity average polymerization degree of 500 to 2,800, and a viscosity of 20 to 85 mPa ⁇ s.
  • the phosphoric acid ester (BP) may form a phosphoric ester group in the production process of the multilayer structure.
  • phosphorylation rate of the phosphoric acid ester compound (BP) R BP is 0.15 or more. Further, in order to obtain a multilayer structure having better interlayer adhesion, it is preferably 0.24 or more, more preferably 0.37 or more, and further preferably 0.54 or more.
  • the phosphoric esterification rate RBP is a value calculated from the charged amounts of the polyvinyl alcohol resin and phosphoric acid in the esterification reaction of the polyvinyl alcohol resin and phosphoric acid according to the following formula.
  • Esterification rate R BP [ ⁇ (degree of saponification / 100) ⁇ polyvinyl alcohol resin charge (g) ⁇ / 44.05] / ⁇ inorganic phosphorus compound (BI) charge (g) / inorganic phosphorus compound (BI ) Molecular weight ⁇
  • the layer (Y) included in the multilayer structure of the present invention may be composed only of a compound (A) containing aluminum, an inorganic phosphorus compound (BI), and a phosphoric acid ester (BP); It may be constituted only by the metal oxide (Aa), the inorganic phosphorus compound (BI), and the phosphoric acid ester (BP); the reaction between the metal oxide (Aa) containing aluminum and the inorganic phosphorus compound (BI) It may be constituted only by the compound (Ab) containing the product (D), the inorganic phosphorus compound (BI), and the phosphoric acid ester (BP); a metal oxide containing aluminum (Aa), a metal containing aluminum COMPOUND (Ab) CONTAINING REACTION PRODUCT (D) OF OXIDE (Aa) AND INORGANIC PHOSPHORUS COMPOUND (BI), INORGANIC PHOSPHORUS COMPOUND (BI), AND PHOSPHATE Product (BP) may be constituted by only.
  • the layer (Y) can further contain other components.
  • other components include inorganic acid metal salts such as carbonates, hydrochlorides, nitrates, hydrogen carbonates, sulfates, hydrogen sulfates, borates; oxalates, acetates, tartrate, stearates
  • Organic acid metal salts such as: metal complexes such as cyclopentadienyl metal complexes (for example, titanocene) and cyano metal complexes (for example, Prussian blue); layered clay compounds; crosslinking agents; polymer compounds (F): plasticizers; Antioxidants; ultraviolet absorbers; flame retardants and the like.
  • the content of the other component in the layer (Y) in the multilayer structure is preferably 50% by mass or less, more preferably 20% by mass or less, 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 layer (Y) may contain the polymer compound (F).
  • the polymer compound (F) is, for example, a polymer (Fa) having at least one functional group selected from the group consisting of an ether bond, a carbonyl group, a hydroxyl group, a carboxyl group, a carboxylic acid anhydride group, and a carboxyl group salt. ).
  • polymer (Fa) examples include polyethylene glycol; polyketone; polyvinyl alcohol, modified polyvinyl alcohol containing 1 to 50 mol% of ⁇ -olefin units having 4 or less carbon atoms, polyvinyl acetal (eg, polyvinyl butyral), and the like.
  • Alcohol polymers polysaccharides such as cellulose, starch, cyclodextrin; (meth) acrylic acid polymers such as hydroxyethyl poly (meth) acrylate, poly (meth) acrylic acid, and ethylene-acrylic acid copolymer; Examples include hydrolysates of ethylene-maleic anhydride copolymer, hydrolysates of styrene-maleic anhydride copolymer, and hydrolysates of alternating isobutylene-maleic anhydride copolymer. .
  • polyvinyl alcohol polymers are preferable, and specifically, polyvinyl alcohol and modified polyvinyl alcohol containing 1 to 15 mol% of ⁇ -olefin units having 4 or less carbon atoms are preferable.
  • the polymer (Fa) may be a homopolymer of a monomer having a polymerizable group (for example, vinyl acetate or acrylic acid), or may be a copolymer of two or more monomers. It may be a copolymer of a monomer having a hydroxyl group and / or a carboxyl group and a monomer having no such group. In addition, as a polymer (Fa), you may use 2 or more types of polymers (Fa) together.
  • a polymerizable group for example, vinyl acetate or acrylic acid
  • the molecular weight of the polymer (Fa) is not particularly limited, but the number average molecular weight of the polymer (Fa) should be 5,000 or more in order to obtain a multilayer structure having better gas barrier properties and mechanical strength. Is preferably 8,000 or more, more preferably 10,000 or more.
  • the upper limit of the number average molecular weight of a polymer (Fa) is not specifically limited, For example, it is 1,500,000 or less.
  • the content of the polymer (Fa) in the layer (Y) is preferably 85% by mass or less, based on the mass of the layer (Y) (100% by mass). More preferably, it is more preferably 20% by mass or less, particularly preferably 10% by mass or less.
  • the polymer (Fa) may or may not react with the component in the layer (Y).
  • the thickness of the layer (Y) (when the multilayer structure has two or more layers (Y), the total thickness of each layer (Y)) may be in the range of 0.05 to 4.0 ⁇ m. Preferably, it is in the range of 0.1 to 2.0 ⁇ m.
  • the thickness per layer (Y) is preferably 0.05 ⁇ m or more from the viewpoint of gas barrier properties.
  • the thickness of the layer (Y) can be controlled by the concentration of a coating liquid (T) described later used for forming the layer (Y) or its coating method.
  • the thickness of the layer (Y) can be measured by observing the cross section of the multilayer structure with a scanning electron microscope or a transmission electron microscope.
  • Examples of the method for producing a multilayer structure of the present invention include a precursor layer forming step (i), a phosphoric acid ester (BP) -containing coating solution (T) coating step (ii), and a gas barrier layer (Y).
  • a production method including the forming step (iii) is exemplified. Since the compound (A), the inorganic phosphorus compound (BI), the phosphoric acid ester product (BP), and the mass ratio thereof have been described above, duplicate descriptions are omitted in the manufacturing method.
  • Step (i) In the step (i), a precursor layer of the layer (Y) is formed on the base material (X) by applying the coating liquid (S) containing the compound (A) containing aluminum onto the base material (X). To do.
  • a structure including the base material (X) and the precursor layer of the layer (Y) is obtained.
  • the layer (Y) includes an aluminum vapor deposition layer (Ac) or an aluminum oxide vapor deposition layer (Ad)
  • these layers can be formed by the general vapor deposition method described above. Therefore, below, the formation method of the precursor layer of the layer (Y1) containing a compound (Ab) is demonstrated in detail.
  • the coating liquid (S) (first coating liquid) can be prepared by mixing and reacting a metal oxide (Aa) and an inorganic phosphorus compound (BI) in a solvent.
  • the coating liquid (S) is a method of mixing a dispersion of a metal oxide (Aa) and a solution containing an inorganic phosphorus compound (BI); an inorganic phosphorus compound in a dispersion of a metal oxide (Aa) It can be prepared by adding (BI) and mixing.
  • the temperature at the time of mixing is preferably 50 ° C. or less, more preferably 30 ° C. or less, and further preferably 20 ° C. or less.
  • the coating liquid (S) may contain other compounds (for example, the polymer compound (F)), and is selected from the group consisting of acetic acid, hydrochloric acid, nitric acid, trifluoroacetic acid, and trichloroacetic acid as necessary. And at least one acid compound (Q).
  • other compounds for example, the polymer compound (F)
  • the dispersion of the metal oxide (Aa) is prepared, for example, by mixing a compound (E), water, and an acid catalyst or an organic solvent as necessary in accordance with a method adopted in a known sol-gel method.
  • E) can be prepared by condensation or hydrolysis condensation.
  • a dispersion of the metal oxide (Aa) is obtained by condensing or hydrolytically condensing the compound (E)
  • a specific treatment is applied to the obtained dispersion as necessary.
  • the solvent to be used is not particularly limited, but alcohols such as methanol, ethanol and isopropanol; water; or a mixed solvent thereof is preferable.
  • the solution containing the inorganic phosphorus compound (BI) can be prepared by dissolving the inorganic phosphorus compound (BI) in a solvent.
  • the solvent may be appropriately selected according to the type of inorganic phosphorus compound (BI), but preferably contains water.
  • the solvent may contain an organic solvent (for example, alcohols such as methanol) as long as it does not hinder the dissolution of the inorganic phosphorus compound (BI).
  • the solid content concentration of the coating liquid (S) is preferably 1 to 20% by mass, more preferably 2 to 15% by mass, from the viewpoint of storage stability of the coating liquid and coating properties with respect to the substrate (X). More preferred is 10% by mass.
  • the solid content concentration can be calculated, for example, by dividing the mass of the solid content remaining after the solvent of the coating liquid (S) is distilled off by the mass of the coating liquid (S) subjected to the treatment.
  • the coating solution (S) has a viscosity measured with a Brookfield rotational viscometer (SB type viscometer: rotor No. 3, rotation speed 60 rpm) of 3,000 mPa ⁇ s or less at the coating temperature. Is preferably 2,500 mPa ⁇ s or less, and more preferably 2,000 mPa ⁇ s or less. When the viscosity is 3,000 mPa ⁇ s or less, the leveling property of the coating liquid (S) is improved, and a multilayer structure having a better appearance can be obtained. Further, the viscosity of the coating liquid (S) is preferably 50 mPa ⁇ s or more, more preferably 100 mPa ⁇ s or more, and further preferably 200 mPa ⁇ s or more.
  • the molar ratio of aluminum atoms to phosphorus atoms can be calculated by performing a fluorescent X-ray analysis of the dried solid of the coating liquid (S).
  • the coating liquid (S) may be applied directly on at least one surface of the substrate (X), or may be applied on the substrate (X) through another layer (J). Good. Further, before coating the coating liquid (S), 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). By doing so, the adhesive layer (I) may be formed on the surface of the substrate (X).
  • Coating of the coating liquid (S) is not particularly limited, and a known method can be adopted. Coating methods include, 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, metalling bar coating method, chamber doctor combined coating Method, curtain coating method, bar coating method and the like.
  • the precursor layer of the layer (Y1) is formed by removing the solvent in the coating liquid (S).
  • a well-known drying method is applicable. Examples of the drying method include a hot air drying method, a hot roll contact method, an infrared heating method, and a microwave heating method. It is preferable that a drying temperature is below the flow start temperature of a base material (X).
  • the drying temperature after application of the coating liquid (S) may be, for example, about 80 to 180 ° C. or about 90 to 150 ° C.
  • the drying time is not particularly limited, but for example, 0.1 second to 1 hour is preferable, 1 second to 15 minutes is more preferable, and 5 to 300 seconds is more preferable. Moreover, it is preferable to perform a heat treatment after the drying treatment.
  • the heat treatment temperature may be, for example, about 100 to 200 ° C. or about 120 to 180 ° C., but is preferably higher than the drying temperature.
  • the heat treatment time is not particularly limited. For example, the heat treatment time is preferably 1 second to 1 hour, more preferably 1 second to 15 minutes, and further preferably 5 to 300 seconds.
  • a coating liquid (T) (second coating liquid) containing a phosphoric acid ester (BP) is applied on the precursor layer of the layer (Y) obtained in the step (i).
  • the coating liquid (T) can be prepared by mixing a phosphoric acid ester (BP) and a solvent.
  • the solvent used in the coating liquid (T) may be appropriately selected according to the type of phosphoric acid ester (BP), and is not particularly limited; however, alcohols such as methanol, ethanol and isopropanol; water; or a mixture thereof A solvent is preferred.
  • the concentration of the solid content in the coating liquid (T) is preferably 0.01 to 60% by mass, more preferably 0.1 to 50% by mass, more preferably 0.2 to More preferred is 40% by mass.
  • the solid content concentration can be determined by a method similar to the method described for the coating liquid (S).
  • coating liquid (T) may also contain the other component (For example, high molecular compound (F)) contained in the layer (Y) mentioned above.
  • the precursor layer of the layer (Y) is formed by removing the solvent after coating the coating liquid (T).
  • the method for applying the coating liquid (T) is not particularly limited, and a known method can be employed.
  • the method for removing the solvent of the coating liquid (T) is not particularly limited, and a known drying method can be applied.
  • the drying method include a hot air drying method, a hot roll contact method, an infrared heating method, and a microwave heating method. It is preferable that a drying temperature is below the flow start temperature of a base material (X).
  • the drying temperature after coating of the coating liquid (T) may be, for example, about 90 to 240 ° C., and preferably 100 to 200 ° C.
  • step (iii) the layer (Y1) is formed by heat-treating the precursor layer of the layer (Y1) formed in steps (i) and (ii) at a temperature of 140 ° C. or higher.
  • This heat treatment temperature is preferably higher than the drying temperature after coating of the coating liquid (T).
  • step (iii) a reaction in which the metal oxide (Aa) particles are bonded to each other via a phosphorus atom (a phosphorus atom derived from an inorganic phosphorus compound (BI)) proceeds.
  • a reaction for generating the reaction product (D) proceeds.
  • the temperature of the heat treatment is 140 ° C. or higher, preferably 170 ° C. or higher, more preferably 180 ° C. or higher, and further 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).
  • the heat treatment temperature is preferably 270 ° C. or lower.
  • the temperature of heat processing is 240 degrees C or less.
  • the heat treatment may be performed in an air atmosphere, a nitrogen atmosphere, an argon atmosphere, or the like.
  • the heat treatment time is preferably 0.1 second to 1 hour, more preferably 1 second to 15 minutes, and even more preferably 5 to 300 seconds.
  • a drying process (first drying process) is performed, followed by a heat treatment (first heat treatment) to form a precursor layer.
  • first drying process first heat treatment
  • second drying process a drying process
  • second heat treatment second heat treatment
  • the temperature of the first heat treatment is higher than the temperature of the first drying treatment
  • the temperature of the second heat treatment is higher than the temperature of the second drying treatment
  • the temperature of the second heat treatment is higher than the temperature of the first heat treatment. High is preferred.
  • the layer (Y) may be laminated so as to be in direct contact with the substrate (X), and the layer (Y) may be another member (for example, an adhesive layer (I). ) Or another layer (J)) and may be laminated on the substrate (X).
  • extruded coat laminate In the multilayer structure of the present invention, for example, after the layer (Y) is laminated on the substrate (X) directly or via the adhesive layer (I), another layer (J) is directly or directly adhered to the adhesive layer (I). ) Through an extrusion coat laminating method, it can further have a layer formed by extrusion coat lamination.
  • the extrusion coat laminating method There is no particular limitation on the extrusion coat laminating method that can be used in the present invention, and a known method may be used.
  • a typical extrusion coat laminating method a laminated film is produced by sending a molten thermoplastic resin to a T-die and cooling the thermoplastic resin taken out from the flat slit of the T-die.
  • FIG. 5 is a diagram schematically showing only the main part of the apparatus, which is different from the actual apparatus.
  • the apparatus 50 of FIG. 5 includes an extruder 51, a T die 52, a cooling roll 53, and a rubber roll 54.
  • the cooling roll 53 and the rubber roll 54 are disposed with their roll surfaces in contact with each other.
  • thermoplastic resin is heated and melted in an extruder and is extruded from the flat slit of the T-die 52 to become a resin film 502.
  • a laminated body 501 is fed from a sheet feeding device (not shown) and is sandwiched between the cooling roll 53 and the rubber roll 54 together with the resin film 502.
  • a laminated film (multilayer structure) in which the laminated body 501 and the resin film 502 are integrated by sandwiching the laminated body 501 and the resin film 502 between the cooling roll 53 and the rubber roll 54. 503 is manufactured.
  • Extrusion coat lamination methods other than the single lamination method include sandwich lamination method and tandem lamination method.
  • the sandwich lamination method is a method of producing a laminate by extruding a molten thermoplastic resin onto one base material, supplying a second base material from another unwinder (unwinding machine), and bonding them together.
  • the tandem laminating method is a method in which two single laminating machines are connected to produce a laminate having a five-layer structure at a time.
  • a multilayer structure can be obtained that maintains high barrier performance even after extrusion coating lamination and has a small decrease in light transmission.
  • the adhesion between the substrate (X) and the layer (Y) may be improved by using the adhesive layer (I).
  • the adhesive layer (I) may be made of an adhesive resin.
  • the adhesive layer (I) composed of an adhesive resin is obtained by treating the surface of the base material (X) with a known anchor coating agent or by applying a known adhesive to the surface of the base material (X). Can be formed.
  • the adhesive is preferably a two-component reactive polyurethane adhesive in which a polyisocyanate component and a polyol component are mixed and reacted.
  • the adhesion may be further improved by adding a small amount of an additive such as a known silane coupling agent to the anchor coating agent or adhesive.
  • an additive such as a known silane coupling agent
  • the silane coupling agent include, but are not limited to, a silane coupling agent having a reactive group such as an isocyanate group, an epoxy group, an amino group, a ureido group, or a mercapto group.
  • the multilayer structure of the present invention may include other layers (J) in order to improve various properties (for example, heat sealability, barrier properties, and mechanical properties).
  • Such a multilayer structure of the present invention is obtained by, for example, laminating the layer (Y) directly on the substrate (X) or via the adhesive layer (I), and then directly or directly deposit the other layer (J). It can be produced by bonding or forming via the adhesive layer (I).
  • the other layer (J) include, but are not limited to, an ink layer; a thermoplastic resin layer such as a polyolefin layer and an ethylene-vinyl alcohol copolymer resin layer.
  • the multilayer structure of the present invention may include an ink layer for printing a trade name or a pattern.
  • Such a multilayer structure of the present invention is produced, for example, by directly forming the ink layer after laminating the layer (Y) directly on the substrate (X) or via the adhesive layer (I). it can.
  • the ink layer for example, a film obtained by drying a liquid in which a polyurethane resin containing a pigment (for example, titanium dioxide) in a solvent is dispersed may be used.
  • a film obtained by drying a resist for forming an electronic circuit wiring may be used.
  • Examples of the coating method of the ink layer on the layer (Y) include various coating methods such as a wire bar, a spin coater, and a die coater in addition to the gravure printing method.
  • the thickness of the ink layer is preferably 0.5 to 10.0 ⁇ m, more preferably 1.0 to 4.0 ⁇ m.
  • the phosphate ester (BP) has a high affinity between the phosphate group having a high affinity with the compound (A) and the adhesive layer (I) or other layer (J). Since it has both hydroxyl groups, the adhesion between the layer (Y) and other layers is improved. For this reason, it is possible to maintain the interlayer adhesive force even after the retorting process, and it is possible to suppress appearance defects such as delamination.
  • the polyolefin layer As the outermost surface layer of the multilayer structure of the present invention, heat sealability can be imparted to the multilayer structure or the mechanical properties of the multilayer structure can be improved.
  • the polyolefin is preferably polypropylene or polyethylene.
  • the polyester is preferably polyethylene terephthalate
  • the polyamide is preferably nylon-6.
  • the hydroxyl group-containing polymer is preferably an ethylene-vinyl alcohol copolymer.
  • the multilayer structure may have a member other than the substrate (X) and the layer (Y) (for example, the adhesive layer (I) and the other layer (J)). The description of other members is omitted.
  • a plurality of specific examples may be laminated or combined.
  • any one of the structures (1) to (8), (11) to (33), and (49) to (54) is preferable.
  • the multilayer structure of the present invention has an oxygen permeability of 2.0 mL / (m 2 ⁇ day ⁇ atm) or less at 20 ° C. and 85% RH before and after the retort treatment. What is 5 mL / (m 2 ⁇ day ⁇ atm) or less is preferable, and one that is 0.3 mL / (m 2 ⁇ day ⁇ atm) or less is more preferable.
  • the conditions for the retort treatment, the method for measuring oxygen permeability, and the measurement conditions are as described in the examples described later.
  • the multilayer structure of the present invention preferably has a water vapor transmission rate of 0.5 g / (m 2 ⁇ day) or less at 40 ° C. and 90% RH before and after the retort treatment. What is 3 g / (m 2 ⁇ day) or less is more preferable.
  • the conditions for the retort treatment, the method for measuring moisture permeability, and the measurement conditions are as described in the examples described later.
  • the multilayer structure of the present invention has a peel strength between the layer (Y) after retort treatment and the adhesive layer (I) or other layer (J) (for example, ink layer) exceeding 100 g / 15 mm.
  • the adhesive layer (I) or other layer (J) for example, ink layer
  • 110 g / 15 mm or more is more preferable.
  • the conditions for the retort treatment, the method for measuring the peel strength, and the measurement conditions are as described in the examples described later.
  • the multilayer structure and protective sheet of the present invention have an oxygen permeability of 2.0 mL / (m 2 ⁇ day ⁇ atm) or less at 20 ° C. and 85% RH before and after the dump heat test. And preferably 0.5 mL / (m 2 ⁇ day ⁇ atm) or less, more preferably 0.3 mL / (m 2 ⁇ day ⁇ atm) or less.
  • the conditions of the dump heat test, the measurement method of oxygen permeability, and the measurement conditions are as described in the examples described later.
  • the multilayer structure and protective sheet of the present invention have a moisture permeability of 0.5 g / (m 2 ⁇ day) or less before and after the dump heat test under the conditions of 40 ° C. and 90% RH. Is preferable, and what is 0.3 g / (m 2 ⁇ day) or less is more preferable.
  • the conditions for the dump heat test, the method for measuring moisture permeability, and the measurement conditions are as described in the examples described later.
  • the multilayer structure and protective sheet of the present invention have a peel strength of 170 g / 15 mm between the layer (Y) after the dump heat test and the adhesive layer (I) or other layer (J) (for example, an ink layer). More than 200 g / 15 mm or more is more preferable, and 260 g / 15 mm or more is more preferable.
  • the conditions of the dump heat test, the measurement method of peel strength, and the measurement conditions are as described in the examples described later.
  • the multilayer structure of the present invention and a packaging material using the multilayer structure are excellent in gas barrier properties and water vapor barrier properties, and are excellent in gas barrier properties and water vapor barrier properties even after retorting, and do not cause appearance defects such as delamination and are high. Interlayer adhesion (peel strength). Therefore, the multilayer structure of the present invention and the packaging material using the same can be applied to various uses.
  • the packaging material of the present invention includes a multilayer structure including a base material (X) and a layer (Y) laminated on the base material (X).
  • the packaging material may be constituted only by a multilayer structure. That is, in the following description, “packaging material” may be read as “multilayer structure”. Typically, “packaging material” can be read as “packaging”.
  • the packaging material may be composed of a multilayer structure and other members.
  • the packaging material includes an inorganic gas (eg, hydrogen, helium, nitrogen, oxygen, carbon dioxide), natural gas, water vapor, and an organic compound that is liquid at normal temperature and pressure (eg, ethanol, gasoline vapor). It has a barrier property against.
  • an inorganic gas eg, hydrogen, helium, nitrogen, oxygen, carbon dioxide
  • natural gas e.g., hydrogen, helium, nitrogen, oxygen, carbon dioxide
  • water vapor e.g, ethanol, gasoline vapor
  • a multilayer structure may be used for all of the packaging bags, or a multilayer structure may be used for a part of the packaging bag.
  • 50% to 100% of the area of the packaging bag may be constituted by a multilayer structure.
  • the packaging material is other than a packaging bag (for example, a container or a lid).
  • the packaging material of the present invention can be produced by various methods.
  • a container is produced by joining a sheet-like multilayer structure or a film material containing the multilayer structure (hereinafter simply referred to as “film material”) and forming it into a predetermined container shape. May be.
  • the molding method include thermoforming, injection molding, and extrusion blow molding.
  • the container produced as described above may be referred to as a “packaging container” in the present specification.
  • the packaging material according to the present invention is preferably used as a packaging material for food.
  • the packaging material according to 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; Can do.
  • the packaging material containing the multilayer structure of the present invention can be used after being secondarily processed into various molded products.
  • molded products include vertical bag-filled sealing bags, vacuum packaging bags, pouches, laminated tube containers, infusion bags, paper containers, strip tapes, container lids, in-mold label containers, vacuum insulators, or electronic devices. It may be. In these molded articles, heat sealing may be performed.
  • the packaging material including the multilayer structure of the present invention may be a vertical bag-filling seal bag.
  • An example is shown in FIG.
  • a vertical bag-filling-seal bag 10 shown in FIG. 1 is formed by sealing a multilayer structure 11 of the present invention on three sides of two end portions 11a and a body portion 11b.
  • the vertical bag filling and sealing bag 10 can be manufactured by a vertical bag making and filling machine. Various methods are applied to bag making by a vertical bag making and filling machine. In either method, the contents are supplied from the upper opening of the bag to the inside, and then the opening is sealed. A vertical bag filling and sealing bag is manufactured.
  • the vertical bag-filling-seal bag is made of, for example, a single film material that is heat-sealed on the three sides of the upper end, the lower end, and the side.
  • the vertical bag-filling sealing bag as a packaging container according to the present invention is excellent in gas barrier properties and water vapor barrier properties and maintains barrier performance even after retorting. Quality deterioration can be suppressed over a long period.
  • the packaging material including the multilayer structure of the present invention may be a pouch.
  • An example is shown in FIG.
  • the flat pouch 20 in FIG. 2 is formed by joining two multilayer structures 11 to each other at the peripheral edge portion 11c.
  • the phrase “pouch” means a container having a film material as a wall member mainly containing food, daily necessities or pharmaceuticals.
  • Examples of the pouch include a pouch with a spout, a pouch with a chuck seal, a flat pouch, a stand-up pouch, a horizontal bag-filling seal pouch, and a retort pouch depending on the shape and use.
  • the pouch may be formed by laminating a multilayer structure and at least one other layer (J).
  • the pouch as a packaging container according to the present invention is excellent in gas barrier properties and water vapor barrier properties, and the barrier performance is maintained even after retorting. Therefore, by using the pouch, it is possible to prevent the contents from being altered even after transportation or long-term storage. In addition, since an example of the pouch can maintain good transparency, it is easy to check the contents and confirm the deterioration of the contents due to deterioration.
  • the packaging material including the multilayer structure of the present invention may be an infusion bag.
  • the infusion bag is a container having an infusion preparation as its contents, and includes a film material as a partition that separates the inside and the outside for containing the infusion preparation.
  • An example is shown in FIG.
  • the infusion bag may include a plug member 432 at the peripheral edge 412 of the bag main body 431 in addition to the bag main body 431 that stores the contents.
  • the plug member 432 functions as a path for taking out the infusion contained in the bag body 431.
  • the infusion bag may be provided with the suspension hole 433 in the peripheral part 411 on the opposite side of the peripheral part 412 to which the plug member 432 is attached.
  • the bag body 431 is formed by joining two film materials 410a and 410b to each other at the peripheral edge portions 411, 412, 413, and 414.
  • the film materials 410 a and 410 b function as a partition wall 420 that separates the inside of the bag from the outside of the bag at the center portion surrounded by the peripheral edge portions 411, 412, 413, and 414 of the bag body 431.
  • the infusion bag as a packaging container according to the present invention has excellent gas barrier properties, and the gas barrier properties are maintained even after heat treatment such as hot water treatment. Therefore, according to the infusion bag, it is possible to prevent the filled liquid 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 packaging material including the multilayer structure of the present invention may be an in-mold label container.
  • the in-mold label container includes a container body and the multilayer label (multilayer structure) of the present invention disposed on the surface of the container body.
  • the container body is formed by injecting molten resin into the mold.
  • the shape of the container body is not particularly limited, and may be a cup shape, a bottle shape, or the like.
  • An example of the method of the present invention for manufacturing a container includes a first step of placing a multilayer label of the present invention in a cavity between a female mold part and a male mold part, and injecting molten resin into the cavity
  • a second step of simultaneously forming the container body and applying the multilayer label of the present invention to the container body is included. Except for using the multilayer label of the present invention, each step can be performed in a known manner.
  • FIG. 4 shows a cross-sectional view of an example of the container of the present invention.
  • the container 360 includes a cup-shaped container main body 370 and multilayer labels 361 to 363 attached to the surface of the container main body 370.
  • the multilayer labels 361 to 363 are multilayer labels of the present invention.
  • the container body 370 includes a flange portion 371, a body portion 372, and a bottom portion 373.
  • the flange portion 371 has a convex portion 371a projecting up and down at the tip thereof.
  • the multilayer label 361 is disposed so as to cover the outer surface of the bottom 373. In the center of the multilayer label 361, a through hole 361a for injecting resin at the time of in-mold label molding is formed.
  • the multilayer label 362 is disposed so as to cover the outer surface of the body portion 372 and the lower surface of the flange portion 371.
  • the multilayer label 363 is disposed so as to cover a part of the inner surface of the body portion 372 and the upper surface of the flange portion 371.
  • the multilayer labels 361 to 363 are fused to the container main body 370 by an in-mold label molding method, and are integrated with the container main body 360. As shown in FIG. 4, the end surface of the multilayer label 363 is fused to the container body 360 and is not exposed to the outside.
  • the product of the present invention using at least a part of the packaging material described above may be a vacuum heat insulator.
  • a vacuum heat insulating body is a heat insulating body provided with a coating material and a core material disposed inside the coating material, and the inside where the core material is disposed is decompressed.
  • the vacuum insulator makes it possible to achieve a heat insulation characteristic equivalent to that of a heat insulator made of urethane foam with a thinner and lighter heat insulator.
  • the vacuum heat insulating material of the present invention is a heat insulating material for household appliances such as a refrigerator, a hot water supply facility, and a rice cooker; a heat insulating material for a house, a vehicle roofing material used for a wall, a ceiling, an attic, a floor, etc., vending It can be used for heat transfer panels such as heat storage panels and heat pump applied equipment.
  • the multilayer structure of the present invention used as a coating material preferably includes an ethylene-vinyl alcohol copolymer resin layer and an inorganic vapor deposition layer.
  • polyester layer / layer (Y) / polyester layer / layer (Y) / You may have the structure of an inorganic vapor deposition layer / ethylene-vinyl alcohol copolymer layer / polyolefin layer.
  • FIG. 6 An example of the vacuum heat insulator of the present invention is shown in FIG.
  • a vacuum heat insulating body 601 in FIG. 6 includes a particulate core material 651 and two multilayer structures 631 and 632 of the present invention as covering materials covering the core material 651.
  • the two multilayer structures 631 and 632 are joined to each other at the peripheral edge 611.
  • An internal space formed by the two multilayer structures 631 and 632 is filled with a core material 651, and the internal space is decompressed.
  • the multilayer structures 631 and 632 function as a partition that separates the inside and the outside in which the core material 651 is accommodated, and are in close contact with the core material 651 due to a pressure difference between the inside and the outside of the vacuum heat insulating body 601.
  • the inside where the core member 652 is disposed is depressurized.
  • FIG. 7 shows another example of the vacuum insulator according to the present invention.
  • the vacuum heat insulator 602 has the same configuration as the vacuum heat insulator 601 except that the vacuum heat insulator 602 includes a core material 652 that is integrally formed instead of the core material 651.
  • the core material 652 that is a molded body is typically a resin foam.
  • the material and shape of the core material are not particularly limited as long as it is suitable for heat insulation.
  • the core material include pearlite powder, silica powder, precipitated silica powder, diatomaceous earth, calcium silicate, glass wool, rock wool, artificial (synthetic) wool, resin foam (eg, styrene foam, urethane foam), and the like. Is mentioned.
  • a hollow container, a honeycomb structure or the like molded into a predetermined shape can also be used.
  • FIG. 8 shows a partial cross-sectional view of an example of the electronic device of the present invention.
  • An electronic device 40 in FIG. 8 includes an electronic device main body 41, a sealing material 42 for sealing the electronic device main body 41, and a protective sheet (multilayer structure) 43 for protecting the surface of the electronic device main body 41. .
  • the sealing material 42 covers the entire surface of the electronic device body 41.
  • the protective sheet 43 is disposed on one surface of the electronic device main body 41 via a sealing material 42.
  • the protective sheet 43 may also be disposed on the surface opposite to the surface on which the protective sheet 43 is disposed.
  • the protective sheet disposed on the opposite surface may be the same as or different from the protective sheet 43.
  • the protective sheet 43 may be disposed on the electronic device main body 41 via another member such as the sealing material 42, or may be directly disposed on the surface of the electronic device main body 41.
  • the electronic device body 41 is not particularly limited, and examples thereof include a photoelectric conversion device such as a solar cell; an information display device such as an organic EL display, a liquid crystal display, and electronic paper; and an illumination device such as an organic EL light emitting element.
  • the sealing material 42 is an arbitrary member that is appropriately added according to the type and application of the electronic device body 41. Examples of the sealing material 42 include an ethylene-vinyl acetate copolymer and polyvinyl butyral.
  • a preferred example of the electronic device body 41 is a solar cell.
  • the solar battery include a silicon solar battery, a compound semiconductor solar battery, and an organic thin film solar battery.
  • the silicon-based solar cell include a single crystal silicon solar cell, a polycrystalline silicon solar cell, and an amorphous silicon solar cell.
  • compound semiconductor solar cells include III-V compound semiconductor solar cells, II-VI group compound semiconductor solar cells, and I-III-VI group compound semiconductor solar cells.
  • the solar cell may be an integrated solar cell in which a plurality of unit cells are connected in series, or may not be an integrated solar cell.
  • the multilayer structure of the present invention and a packaging material including the same include a display member such as an LCD substrate film, an organic EL substrate film, an electronic paper substrate film, an electronic device sealing film, and a PDP film; IC tag film It is suitably used as a solar cell member such as a solar cell module, a solar cell backsheet, and a solar cell protective film.
  • a display member such as an LCD substrate film, an organic EL substrate film, an electronic paper substrate film, an electronic device sealing film, and a PDP film
  • IC tag film It is suitably used as a solar cell member such as a solar cell module, a solar cell backsheet, and a solar cell protective film.
  • the multilayer structure is used, for example, as a low reflective film.
  • the translucent layer (Y) is used as the layer (Y).
  • the electronic device main body 41 can be manufactured by a so-called roll-to-roll method depending on the type.
  • a flexible substrate for example, a stainless steel substrate, a resin substrate, etc.
  • an electronic device body 41 is produced by forming elements on this substrate.
  • the electronic device body 41 is taken up by a take-up roll.
  • the protective sheet 43 may be prepared in the form of a long sheet having flexibility, more specifically in the form of a wound body of a long sheet.
  • the protective sheet 43 delivered from the delivery roll is stacked on the electronic device main body 41 before being taken up by the take-up roll, and taken up together with the electronic device main body 41.
  • the electronic device main body 41 wound around the winding roll may be sent out from the roll again and laminated with the protective sheet 43.
  • the electronic device itself is flexible.
  • the protective sheet 43 includes the multilayer structure of the present invention.
  • the protective sheet 43 may be composed of only a multilayer structure.
  • the protective sheet 43 may include a multilayer structure and other members (for example, other layers (J)) laminated on the multilayer structure.
  • the thickness and material of the protective sheet 43 are not particularly limited as long as the protective sheet 43 is a layered laminate suitable for protecting the surface of the electronic device and includes the multilayer structure.
  • the protective sheet may include, for example, a surface protective layer disposed on one surface or both surfaces of the multilayer structure.
  • the surface protective layer is preferably a layer made of a resin that is not easily damaged.
  • the surface protective layer of the device which may be utilized outdoors like a solar cell consists of resin with high weather resistance (for example, light resistance).
  • a surface protective layer with high translucency is preferable.
  • Examples of the material for the surface protective layer include poly (meth) acrylate, polycarbonate, polyethylene terephthalate, polyethylene-2,6-naphthalate, polyvinyl fluoride (PVF), polyvinylidene fluoride (PVDF), Polytetrafluoroethylene (PTFE), polychlorotrifluoroethylene (PCTFE), ethylene-tetrafluoroethylene copolymer (ETFE), ethylene-chlorotrifluoroethylene copolymer (ECTFE), tetrafluoroethylene-perfluoroalkyl vinyl ether Examples thereof include a copolymer (PFA) and a tetrafluoroethylene-hexafluoropropylene copolymer (FEP).
  • An example of the protective sheet includes a poly (meth) acrylate layer disposed on one surface.
  • various additives for example, ultraviolet absorbers
  • a preferable example of the surface protective layer having high weather resistance is an acrylic resin layer to which an ultraviolet absorber is added.
  • the ultraviolet absorber include, but are not limited to, benzotriazole-based, benzophenone-based, salicylate-based, cyanoacrylate-based, nickel-based, and triazine-based ultraviolet absorbers.
  • other stabilizers, light stabilizers, antioxidants and the like may be used in combination.
  • the multilayer structure was cut using the focused ion beam (FIB), and the slice for cross-sectional observation was produced.
  • the prepared section was fixed to the sample base with carbon tape, and platinum ion sputtering was performed at an acceleration voltage of 30 kV for 30 seconds.
  • the cross section of the multilayer structure was observed using a field emission type transmission electron microscope, and the thickness of each layer was calculated.
  • the measurement conditions were as follows. Apparatus: JEM-2100F manufactured by JEOL Ltd. Accelerating voltage: 200kV Magnification: 250,000 times
  • Adhesiveness was evaluated by T-type peel strength measurement (adhesive strength per 15 mm width). The measurement was performed 5 times and the average value was adopted. The measurement conditions were as follows. Equipment: Autograph AGS-H manufactured by Shimadzu Corporation Peeling speed: 250 mm / min Temperature: 23 ° C Humidity: 50% RH
  • a dispersion was obtained by adding 54.29 parts by mass of distilled water and 18.80 parts by mass of methanol to 22.50 parts by mass of the solution thus obtained and stirring the mixture uniformly. Subsequently, 4.41 parts by mass of an 85% by mass phosphoric acid aqueous solution was added dropwise while stirring the dispersion while maintaining the liquid temperature at 15 ° C., and the viscosity was maintained at 15 ° C. until the viscosity reached 1,500 mPa ⁇ s. Stirring was continued to obtain the desired coating solution (S-1).
  • the target PPEM was obtained by vacuum drying at 50 ° C. for 24 hours.
  • the number average molecular weight of the polymer was 2,950 in terms of polystyrene.
  • a dried solid product was obtained by reducing the pressure at 40 ° C. for 12 hours using a rotary evaporator.
  • the dried product was heated at 120 ° C. for 3 minutes using a hot air dryer to obtain the target phosphoric acid ester (BP-1) as a white solid.
  • BP-1 target phosphoric acid ester
  • T-1) Phosphate esterified product (BP-1) was dissolved in a mixed solvent of 69.30 parts by mass of water and 29.70 parts by mass of methanol to obtain a coating solution (T-1) having a solid content concentration of 1.0% by mass. .
  • coating liquid (T-2) 85 mass% phosphoric acid aqueous solution 0.71 mass part and 5 mass% polyvinyl alcohol (Kuraray Co., Ltd. “Kuraray Poval (registered trademark) PVA124”; degree of saponification 98.5 mol%, viscosity average degree of polymerization 2,400, 20 8.0 mass parts of a 4 mass% aqueous solution viscosity at 60 ° C.) is dissolved in a mixed solvent of 61.59 mass parts of water and 29.70 mass parts of methanol, and the solid content concentration is 1.0 mass%.
  • a coating solution (T-2) was obtained.
  • PET12 Stretched polyethylene terephthalate film; manufactured by Toray Industries, Inc., “Lumirror P60” (trade name), thickness 12 ⁇ m 2)
  • PET50 Polyethylene terephthalate film with improved adhesion to ethylene-vinyl acetate copolymer; “Shinebeam Q1A15” (trade name), 50 ⁇ m thickness, manufactured by Toyobo Co., Ltd.
  • ONY stretched nylon film; manufactured by Unitika Ltd., “Emblem ONBC” (trade name), thickness 15 ⁇ m 4)
  • CPP60 unstretched polypropylene film; “RXC-21” (trade name), thickness 60 ⁇ m, manufactured by Mitsui Chemicals, Inc. 5)
  • CPP70 unstretched polypropylene film; “RXC-21” (trade name), 70 ⁇ m thickness, manufactured by Mitsui Chemicals, Inc. 6)
  • CPP100 unstretched polypropylene film; “RXC-21” (trade name), 100 ⁇ m thickness, manufactured by Mitsui Chemicals, Inc.
  • Example 1 ⁇ Example 1-1> First, as a base material (X), PET12 (hereinafter sometimes abbreviated as “X-1”) was prepared. On this substrate, the coating liquid (S-1) was applied using a bar coater so that the thickness after drying was 0.3 ⁇ m. The coated film was dried at 110 ° C. for 5 minutes, and then heat-treated at 160 ° C. for 1 minute to form a layer (Y-1-1) precursor on the substrate. Further, the coating liquid (S-1) was applied using a bar coater so that the coating amount of the phosphoric acid ester (BP) was 30 mg / m 2 and dried at 110 ° C. for 3 minutes.
  • BP phosphoric acid ester
  • a layer (Y-1-1) was formed by heat treatment at 220 ° C. for 1 minute. In this way, a multilayer structure (1-1-1) having a structure of base material (X-1) / layer (Y-1-1) was obtained.
  • the maximum absorption wave number in the region of 800 to 1,400 cm ⁇ 1 is 1,108 cm ⁇ 1
  • the half width of the maximum absorption band is 37 cm. -1 .
  • An ink layer was formed on the obtained multilayer structure (1-1-1) and allowed to stand at 40 ° C. for 1 day for aging. Thereafter, an adhesive layer was formed, and ONY was laminated on the adhesive layer to obtain a laminate. Next, an adhesive layer was formed on the ONY of the laminate, and then CPP70 was laminated on the adhesive layer and left to stand at 40 ° C. for 5 days for aging. In this way, a multilayer structure (1-1-2) having a structure of substrate (X-1) / layer (Y-1-1) / ink layer / adhesive layer / ONY / adhesive layer / CPP is obtained. It was.
  • Each of the two adhesive layers was formed by applying a two-component adhesive using a bar coater so that the thickness after drying was 3 ⁇ m and drying.
  • Two-component adhesives include “Takelac” (registered trademark) “A-525S” (brand name) manufactured by Mitsui Chemicals, Inc. and “Takenate” (registered trademark) “A-50” manufactured by Mitsui Chemicals, Inc.
  • a two-component reactive polyurethane adhesive composed of (brand) was used.
  • the ink layer was formed by coating using a bar coater such that the thickness after drying was 2 ⁇ m and drying.
  • the ink used was “Fine Star” (registered trademark) “R641AT White” (brand) manufactured by Toyo Ink Co., Ltd. and “LP Super Curing Agent” (brand) manufactured by Toyo Ink Co., Ltd.
  • the oxygen permeability and moisture permeability of the multilayer structure (1-1-2) were measured. The results are shown in Table 1.
  • a pouch was produced by heat-sealing the multilayer structure (1-1-2), and 100 g of water was filled in the pouch. Subsequently, the obtained pouch was subjected to a retort treatment (hot water storage type) under the following conditions.
  • Retort treatment equipment Flavor Ace RSC-60 manufactured by Nisaka Manufacturing Co., Ltd. Temperature: 130 ° C Time: 30 minutes Pressure: 0.21 MPaG
  • a measurement sample was cut out from the pouch, and the oxygen permeability, moisture permeability, and T-type peel strength of the sample were measured by the above methods. Further, in the multilayer structure (1-1-2), no appearance defect such as delamination was observed.
  • Examples 1-2 to 1-6 Except for changing the phosphate esterification rate RBP and the coating amount of the phosphoric acid ester (BP) according to Table 1, the same method as in the multilayer structure (1-1-2) of Example 1-1 was used. Multilayer structures (1-2-2) to (1-6-2) were prepared and evaluated. As in Example 1-1, the multilayer structures (1-2-2) to (1-6-2) did not show appearance defects such as delamination.
  • Example 1-1 The multilayer structure of Example 1-1 according to Table 1 except that the phosphoric ester (BP) was changed to poly (2-phosphonooxyethyl methacrylate) (PPEM) and poly (vinylphosphonic acid) (PVPA) Multilayer structures (C1-1-2) to (C1-3-2) were produced and evaluated by the same method as that for the body (1-1-2).
  • PPEM poly (2-phosphonooxyethyl methacrylate
  • Table 1 shows the manufacturing conditions for the multilayer structures of the examples and comparative examples.
  • Example 2 Vertical bag filling and sealing bag ⁇ Example 2-1> The multilayer structure (1-1-2) produced in Example 1-1 is cut into a width of 400 mm, and a vertical bag making and filling machine (manufactured by ORIHIRO Co., Ltd.) so that the CPP layers are in contact with each other and heat sealed. ).
  • a vertical bag-filling and sealing bag (2-1-3) (width 160 mm, length 470 mm) as shown in FIG. 1 was produced by a vertical bag-filling and packaging machine. The oxygen permeability and moisture permeability before retorting of the vertical bag-filled seal bag (2-1-3) were measured. The results are shown in Table 2.
  • a pouch was prepared by heat-sealing the vertical bag filling and sealing bag (2-1-3), and 300 mL of water was filled in the pouch. Subsequently, the obtained pouch was subjected to a retort process (hot water storage type) under the same conditions as in Example 1-1. Immediately after the hot water treatment, a measurement sample was cut out from the pouch, and the oxygen permeability, moisture permeability, and T-type peel strength of the sample were measured by the above methods. The results are shown in Table 2. Further, no appearance defect such as delamination was observed in the sample after the hot water treatment.
  • Examples 2-2 to 2-6 and Comparative Examples 2-1 to 2-3> instead of the multilayer structure (1-1-2), the multilayer structures (1-2-2) to (1-6-) of Examples 1-2 to 1-6 and Comparative Examples 1-1 to 1-3 2) and (C1-1-2) to (C1-3-2), except that the vertical bag-filling and sealing bag (2-1-3) of Example 2-1 was used. Vertical bag-filled seal bags (2-2-3) to (2-6-3) and (C2-1-3) to (C2-3-3) were produced. Each item was measured in the same manner as in Example 2-1, for each of the obtained vertical bag making and sealing bags. The results are shown in Table 2.
  • Example 3 Flat pouch ⁇ Example 3-1> The multilayer structure (1-1-2) produced in Example 1-1 was cut into a width of 200 mm ⁇ 130 mm, and the two multilayer structures were overlaid so that the CPP layer was inside, and the outer periphery of the rectangle was 5 mm. Heat-sealed with a width of. Next, a Teflon (registered trademark) sheet having a width of 30 mm was inserted into the end of the opening, and heat sealing was performed in this state. After heat sealing, a flat pouch (3-1-3) was prepared by extracting a Teflon sheet. The oxygen permeability and moisture permeability of the flat pouch (3-1-3) before the retort treatment were measured. The results are shown in Table 3.
  • Teflon registered trademark
  • Example 1-1 100 mL of water was filled in the flat pouch (3-1-3), and retort treatment (hot water storage type) was performed under the same conditions as in Example 1-1. Immediately after the hot water treatment, a measurement sample was cut from the flat pouch, and the oxygen permeability, moisture permeability, and T-type peel strength of the sample were measured by the above methods. The results are shown in Table 3. At this time, no appearance defect such as delamination was observed in the sample after the hot water treatment.
  • Examples 3-2 to 3-6 and Comparative Examples 3-1 to 3-3> instead of the multilayer structure (1-1-2), the multilayer structures (1-2-2) to (1-) manufactured in Examples 1-2 to 1-6 and Comparative Examples 1-1 to 1-3 were used. 6-2) and (C1-1-2) to (C1-3-2) except that the flat pouch (3-1-3) was produced in the same manner as in the production of the flat pouch (3-1-3) of Example 3-1. (3-2-3) to (3-6-3) and (C3-1-3) to (C3-3-3) were produced. About each obtained flat pouch, each item was measured like Example 3-1. The results are shown in Table 3.
  • Example 4 Infusion bag ⁇ Example 4-1> Two 120 mm ⁇ 100 mm multilayer structures were cut out from the multilayer structure (1-1-2) produced in Example 1-1. Subsequently, the two multilayer structures cut out were overlapped so that the CPP layer was inside, and the periphery was heat sealed, and a polypropylene spout (plug member) was attached by heat sealing. In this way, an infusion bag (4-1-3) having the same structure as that shown in FIG. 3 was produced. The oxygen permeability and moisture permeability of the infusion bag (4-1-3) before retorting were measured. The results are shown in Table 4.
  • the infusion bag (4-1-3) was filled with 100 mL of water, and retort treatment (hot water storage type) was performed under the same conditions as in Example 2-1.
  • retort treatment hot water storage type
  • a measurement sample was cut out from the infusion bag, and the oxygen permeability, moisture permeability, and T-type peel strength of the sample were measured by the above methods. The results are shown in Table 4. At this time, no appearance defect such as delamination was observed in the sample.
  • Examples 4-2 to 4-6 and Comparative Examples 4-1 to 4-3> instead of the multilayer structure (1-1-2), the multilayer structures (1-2-2) to (1-) manufactured in Examples 1-2 to 1-6 and Comparative Examples 1-1 to 1-3 were used. 6-2) and (C1-1-2) to (C1-3-2), except that the infusion bag (4-1-3) of Example 4-1 was used. (4-2-3) to (4-6-3) and (C4-1-3) to (C4-3-3) were produced. For each infusion bag obtained, each item was measured in the same manner as in Example 4-1. The results are shown in Table 4.
  • Example 5 Container lid ⁇ Example 5-1> A circular multilayer structure having a diameter of 100 mm was cut out from the multilayer structure (1-1-2) produced in Example 1-1, and used as a container lid.
  • a flanged container manufactured by Toyo Seikan Co., Ltd., “High Reflex” (registered trademark), “HR78-84” (trade name)
  • This container has a cup shape with an upper surface diameter of 78 mm and a height of 30 mm.
  • the upper surface of the container is open, and the width of the flange portion formed on the periphery thereof is 6.5 mm.
  • the container is constituted by a laminate of three layers of olefin layer / steel layer / olefin layer.
  • the container body was filled with water almost completely, and the lid material was heat-sealed to the flange portion to obtain a lidded container (5-1-3).
  • the lid material was heat sealed by placing the lid so that the CPP layer of the lid material was in contact with the flange portion.
  • a square measurement sample having a side length of 4.5 cm was cut out from the lid of the lidded container (5-1-3) and opened into a 10 cm square aluminum foil (thickness 30 ⁇ m). The sample was placed on top and sealed between the sample and the aluminum foil with a two-component curable epoxy adhesive. The sample was used to measure oxygen permeability and moisture permeability before retorting. The results are shown in Table 5.
  • a retort treatment (hot water storage type) was performed on the container with a lid (5-1-3) under the same conditions as in Example 1-1.
  • a measurement sample was cut out from the lid, and the oxygen permeability and moisture permeability of the sample were measured in the same manner as before the retort treatment. Further, the T-type peel strength was measured by the above method. The results are shown in Table 5. At this time, no appearance defect such as delamination was observed in the sample.
  • Examples 5-2 to 5-6 and Comparative Examples 5-1 to 5-3> instead of the multilayer structure (1-1-2), the multilayer structures (1-2-2) to (1-) manufactured in Examples 1-2 to 1-6 and Comparative Examples 1-1 to 1-3 were used. 6-2) and (C1-1-2) to (C1-3-2) were used except that the lidded container (5-1-3) of Example 5-1 was used. The attached containers (5-2-3) to (5-6-3) and (C5-1-3) to (C5-3-3) were prepared. For each obtained container with a lid, each item was measured in the same manner as in Example 5-1. The results are shown in Table 5.
  • Example 6 In-mold label container ⁇ Example 6-1> A two-component adhesive was applied to each of the two CPPs 100 using a bar coater so that the thickness after drying was 3 ⁇ m and dried.
  • the two-component adhesive consists of “Takelac” (registered trademark) “A-525S” manufactured by Mitsui Chemicals, Inc. and “Takenate” (registered trademark) “A-50” manufactured by Mitsui Chemicals, Inc.
  • a two-component reactive polyurethane adhesive was used.
  • two CPPs 100 and the multilayer structure (1-1-1) of Example 1-1 were laminated and aged by standing at 40 ° C. for 5 days.
  • the multilayer label (6-1-2) was cut in accordance with the shape of the inner wall surface of the female mold part of the container mold and attached to the inner wall surface of the female mold part.
  • the male part was pushed into the female part.
  • melted polypropylene (“EA7A” of “NOVATEC” (registered trademark) manufactured by Nippon Polypro Co., Ltd.) was injected into the cavity between the male part and the female part at 220 ° C. In this way, injection molding was performed, and the target container (6-1-3) was molded.
  • the container body had a thickness of 700 ⁇ m and a surface area of 83 cm 2 .
  • the whole outside of the container is covered with the multilayer label (6-1-2), the joint is overlapped with the multilayer label (6-1-2), and the part where the multilayer label (6-1-2) does not cover the outside of the container is There wasn't. At this time, no delamination of the multilayer label was observed, and the appearance of the container (6-1-3) was good.
  • Examples 6-2 to 6-6 and Comparative Examples 6-1 to 6-3> instead of the multilayer structure (1-1-1), the multilayer structures (1-2-1) to (1-) manufactured in Examples 1-2 to 1-6 and Comparative Examples 1-1 to 1-3 are used. 6-1) and (C1-1-1) to (C1-3-1) were used except that the multilayer label (6-1-2) of Example 6-1 was used. (6-2-2) to (6-6-2) and (C6-1-2) to (6-3-2) were produced.
  • Example 7 Extrusion coat laminate ⁇ Example 7-1>
  • an adhesive layer was formed on the layer (Y) on the multilayer structure (1-1-1), and then a polyethylene resin (density: 0.917 g / cm 3 , melt flow rate: 8 g / 10 Min) was extruded and laminated at 295 ° C. on the adhesive layer so as to have a thickness of 20 ⁇ m.
  • a laminate (7-1-2) having a structure of base material (X-1) / layer (Y-1-1) / adhesive layer (I-1) / polyethylene was obtained.
  • the adhesive layer (I-1) was formed by applying a two-part adhesive using a bar coater so that the thickness after drying was 0.3 ⁇ m and drying.
  • This two-part adhesive includes “Takelac” (registered trademark) “A-3210” manufactured by Mitsui Chemicals, Inc. and “Takenate” (registered trademark) “A-3070” manufactured by Mitsui Chemicals, Inc. A two-component reactive polyurethane adhesive was used.
  • Examples 7-2 to 7-6 and Comparative Examples 7-1 to 7-3> instead of the multilayer structure (1-1-1), the multilayer structures (1-2-1) to (1-6-) of Examples 1-2 to 1-6 and Comparative Examples 1-1 to 1-3 1) and laminates (7-2-2) to (7-6-2) in the same manner as in Example 7-1 except that (C1-1-1) to (C1-3-1) were used. ) And (C7-1-2) to (C7-3-2). The laminates (C7-1-2) to (C7-3-2) were partially delaminated during winding. For each obtained laminate, each item was measured in the same manner as in Example 7-1. The results are shown in Table 7.
  • Example 8 Effect of packing ⁇ Example 8-1>
  • the flat pouch (3-1-3) produced in Example 3-1 was filled with 500 mL of a 1.5% aqueous ethanol solution, and a retort treatment apparatus (manufactured by Nisaka Seisakusho, Flavor Ace RCS-60) was used.
  • a retort treatment was performed in hot water at 0.15 MPaG for 30 minutes.
  • a sample for measurement was cut out from the flat pouch after the retort treatment, and the oxygen permeability of the sample was measured.
  • the oxygen permeability of the sample was 0.2 mL / (m 2 ⁇ day ⁇ atm).
  • Examples 8-2 to 8-9 A retort treatment was performed in the same manner as in Example 8-1 except that another 500 mL of filling material was filled in the flat pouch (3-1-3) instead of 500 mL of the 1.5% ethanol aqueous solution. And the sample for a measurement was cut out from the flat pouch after a retort process, and the oxygen permeability of this sample was measured.
  • Other fillings include 1.0% aqueous ethanol (Example 8-2), vinegar (Example 8-3), pH 2 aqueous citric acid (Example 8-4), edible oil (Example 8-5). ), Ketchup (Example 8-6), soy sauce (Example 8-7), and ginger paste (Example 8-8).
  • the oxygen permeability of the sample after the retort treatment was 0.2 mL / (m 2 ⁇ day ⁇ atm).
  • the lidded container (5-1-3) produced in Example 5-1 was almost completely filled with mandarin syrup, and the retort treatment was performed in the same manner as in Example 8-1 (Example 8-9).
  • a sample for measurement was cut out from the lid material of the lidded container after the retort treatment, and the oxygen permeability of the sample was measured.
  • the oxygen permeability was 0.2 mL / (m 2 ⁇ day ⁇ atm).
  • the packaging material of the present invention showed good barrier performance even after retorting with various foods filled.
  • Example 9 Vacuum insulator ⁇ Example 9-1> On the CPP 60, the two-component adhesive used in Example 6-1 was applied to a thickness of 3 ⁇ m after drying, and dried to form an adhesive layer. A laminate (9-1-1) was obtained by laminating this CPP and the PET layer of the multilayer structure (1-1-2) produced in Example 1-1. Subsequently, the adhesive layer was formed by applying the two-component reactive polyurethane adhesive on the ONY so that the thickness after drying was 3 ⁇ m and drying. Then, by laminating this ONY and the laminate (9-1-1), a multilayer structure (9-1-2) having a structure of CPP / adhesive layer / multilayer structure / adhesive layer / ONY is obtained. Obtained.
  • the multilayer structure (9-1-2) was cut to obtain two laminates having a size of 70 cm ⁇ 30 cm.
  • the two laminates were overlapped so that the CPP layers were the inner surfaces, and the three sides were heat-sealed with a width of 10 mm to produce a three-sided bag.
  • the heat insulating core material was filled from the opening of the three-sided bag, and the three-sided bag was sealed at 20 ° C. and an internal pressure of 10 Pa using a vacuum packaging machine.
  • a vacuum heat insulator (9-1-3) was obtained.
  • Silica fine powder was used for the heat insulating core material.
  • the vacuum insulator (9-1-3) was allowed to stand for 360 days under conditions of 40 ° C. and 15% RH, and then the pressure inside the vacuum insulator was measured using a Pirani vacuum gauge. As a result, it was 37.0 Pa. It was.
  • a sample for measurement was cut out from the vacuum insulator (9-1-3), and the oxygen permeability and water vapor permeability of the sample were measured.
  • Examples 9-2 to 9-6 and Comparative Examples 9-1 to 9-3> instead of the multilayer structure (1-1-2), the multilayer structures (1-2-2) to (1-6-) of Examples 1-2 to 1-6 and Comparative Examples 1-1 to 1-3 2) and (C1-1-2) to (C1-3-2) were used in the same manner as in the preparation of the vacuum heat insulator (9-1-3) of Example 9-1 except that the vacuum heat insulator was used. (9-2-3) to (9-6-3) and (C9-1-3) to (C9-3-3) were produced. About each obtained vacuum heat insulating body, each item was measured similarly to Example 9-1. The results are shown in Table 8.
  • Example 10 Protective sheet ⁇ Example 10-1> An adhesive layer was formed on the multilayer structure (1-1-1) produced in Example 1-1, and an acrylic resin film (thickness 50 ⁇ m) was laminated on the adhesive layer to obtain a laminate. Subsequently, an adhesive layer was formed on the multilayer structure (1-1-1) of the laminate, and then the laminate and PET 50 were laminated. In this way, a protective sheet (10-1-2) having a configuration of PET / adhesive layer / base material (X-1) / layer (Y-1-1) / adhesive layer / acrylic resin film was obtained. . Each of the two adhesive layers was formed by applying a two-component adhesive so that the thickness after drying was 3 ⁇ m and drying.
  • the two-component adhesive consists of “Takelac” (registered trademark) “A-1102” manufactured by Mitsui Chemicals, Inc. and “Takenate” (registered trademark) “A-3070” manufactured by Mitsui Chemicals, Inc.
  • a two-component reactive polyurethane adhesive was used.
  • the obtained protective sheet (10-1-2) was measured for oxygen permeability and moisture permeability. The results are shown in Table 9.
  • Example 10-2 to 10-6 and Comparative Examples 10-1 to 10-3> instead of the multilayer structure (1-1-1), the multilayer structures (1-2-1) to (1-6-) of Examples 1-2 to 1-6 and Comparative Examples 1-1 to 1-3 1) and protective sheets (10-2-2) to (10-6-2) in the same manner as in Example 10-1, except that (C1-1-1) to (C1-3-1) were used. ) And (C10-1-2) to (C10-3-2) were prepared, and the obtained protective sheets were evaluated. The results are shown in Table 9. Similar to Example 10-1, the protective sheets (10-2-2) to (10-6-2) showed no appearance defects such as delamination after the dump heat test. On the other hand, as a result of the dump heat test, the protective sheets (C10-1-2) to (C10-3-2) were partially separated from each other and had a poor appearance.
  • Example 10-7 A solar cell module was produced using the protective sheet (10-1-2) obtained in Example 10-1. Specifically, first, an amorphous silicon solar battery cell placed on a 10 cm square tempered glass was sandwiched between ethylene / vinyl acetate copolymer films having a thickness of 450 ⁇ m. Next, the protective sheet (10-1-2) was bonded onto the film so that the polyethylene terephthalate layer of the protective sheet (10-1-2) was on the outside, thereby producing a solar cell module. 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 exhibited good electrical output characteristics over a long period of time.
  • the present invention can be used for a multilayer structure, a packaging material using the multilayer structure, and a method for manufacturing the multilayer structure.
  • ADVANTAGE OF THE INVENTION According to this invention, it is possible to obtain the multilayer structure which is excellent in interlayer adhesiveness, and does not produce appearance defects, such as delamination, even after retorting. Further, by using the multilayer structure of the present invention, an excellent packaging material can be obtained.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Food Science & Technology (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Evolutionary Biology (AREA)
  • General Health & Medical Sciences (AREA)
  • Marine Sciences & Fisheries (AREA)
  • Toxicology (AREA)
  • Zoology (AREA)
  • Laminated Bodies (AREA)
  • Wrappers (AREA)

Abstract

L'invention concerne une structure multicouche qui contient un matériau de base (X) et une couche (Y) stratifiée sur ledit matériau de base (X). Ladite couche (Y) contient un composé (A) contenant un aluminium, et un produit d'estérification (BP) de phosphate d'une résine à base de polyalcool de vinyle. Le rapport d'estérification de phosphate (ＲＢＰ) dudit produit d'estérification (BP) de phosphate d'une résine à base de polyalcool de vinyle, est supérieur ou égal à 0,15.
PCT/JP2015/006456 2014-12-24 2015-12-24 Structure multicouche, matériau d'emballage ainsi que marchandise mettant en œuvre celle-ci, et feuille protectrice pour dispositif électronique WO2016103717A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11944093B2 (en) * 2018-03-08 2024-04-02 Kuraray Co., Ltd. Spreading agent for agrochemicals, and agrochemical spray solution

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JP2006142139A (ja) * 2004-11-16 2006-06-08 Uni-Chemical Co Ltd リン酸エステル化ビニル系重合体からなる分散剤
WO2013051287A1 (fr) * 2011-10-05 2013-04-11 株式会社クラレ Structure composite, produit l'utilisant et procédé pour production de structure composite
WO2013051288A1 (fr) * 2011-10-05 2013-04-11 株式会社クラレ Structure composite et son procédé de production, matériau d'emballage et article moulé l'utilisant, et liquide d'enrobage

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WO2008026672A1 (fr) * 2006-08-30 2008-03-06 Unitika Ltd. Matériau de revêtement destiné à former une couche barrière contre les gaz et corps multicouche barrière contre les gaz
WO2011122036A1 (fr) * 2010-03-30 2011-10-06 株式会社クラレ Structure composite, matériau d'emballage et article moulé produits chacun à l'aide de celle-ci, procédé pour la production d'une structure composite, et solution de revêtement

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Publication number Priority date Publication date Assignee Title
JP2006142139A (ja) * 2004-11-16 2006-06-08 Uni-Chemical Co Ltd リン酸エステル化ビニル系重合体からなる分散剤
WO2013051287A1 (fr) * 2011-10-05 2013-04-11 株式会社クラレ Structure composite, produit l'utilisant et procédé pour production de structure composite
WO2013051288A1 (fr) * 2011-10-05 2013-04-11 株式会社クラレ Structure composite et son procédé de production, matériau d'emballage et article moulé l'utilisant, et liquide d'enrobage

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11944093B2 (en) * 2018-03-08 2024-04-02 Kuraray Co., Ltd. Spreading agent for agrochemicals, and agrochemical spray solution

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