WO2014122942A1 - 多層構造体およびその製造方法 - Google Patents
多層構造体およびその製造方法 Download PDFInfo
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- WO2014122942A1 WO2014122942A1 PCT/JP2014/000683 JP2014000683W WO2014122942A1 WO 2014122942 A1 WO2014122942 A1 WO 2014122942A1 JP 2014000683 W JP2014000683 W JP 2014000683W WO 2014122942 A1 WO2014122942 A1 WO 2014122942A1
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- multilayer structure
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- metal oxide
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D143/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
- C09D143/02—Homopolymers or copolymers of monomers containing phosphorus
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/50—Multilayers
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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
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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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
- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
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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
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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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
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/10—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of paper or cardboard
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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
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
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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
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
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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
- B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
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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
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/14—Protective coatings, e.g. hard coatings
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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
- B32B2255/00—Coating on the layer surface
- B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
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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
- B32B2255/00—Coating on the layer surface
- B32B2255/20—Inorganic coating
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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
- B32B2255/00—Coating on the layer surface
- B32B2255/20—Inorganic coating
- B32B2255/205—Metallic coating
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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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/724—Permeability to gases, adsorption
- B32B2307/7242—Non-permeable
- B32B2307/7244—Oxygen barrier
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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
- B32B2439/00—Containers; Receptacles
- B32B2439/40—Closed containers
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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
- B32B2439/00—Containers; Receptacles
- B32B2439/70—Food packaging
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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
- B32B2439/00—Containers; Receptacles
- B32B2439/80—Medical packaging
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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
- B32B2457/00—Electrical equipment
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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
- B32B2457/00—Electrical equipment
- B32B2457/12—Photovoltaic modules
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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
- B32B2457/00—Electrical equipment
- B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
-
- 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
- B32B2457/00—Electrical equipment
- B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
- B32B2457/202—LCD, i.e. liquid crystal displays
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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
- B32B2457/00—Electrical equipment
- B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
- B32B2457/206—Organic displays, e.g. OLED
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F230/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing phosphorus
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31678—Of metal
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31971—Of carbohydrate
- Y10T428/31993—Of paper
Definitions
- the present invention relates to a multilayer structure and a manufacturing method thereof.
- a laminate in which a film comprising aluminum and its oxide, alumina, as a constituent component is formed on a plastic film has been well known in the past, and is a gas barrier for protecting foods and other articles that are easily altered by oxygen. It is used as a packaging material having properties. Many of these gas barrier coatings are formed on plastic films by dry processes such as vacuum deposition, sputtering, ion plating, and chemical vapor deposition (CVD). Aluminum vapor deposited films have light shielding properties in addition to gas barrier properties, and are mainly used as packaging materials for dry foods.
- transparent alumina vapor-deposited film has the visibility of the contents, taking advantage of the features such as foreign object inspection with a metal detector and microwave heating, etc., and a wide range of applications including retort food packaging It is used as a packaging material.
- Patent Document 1 Japanese Patent Application Laid-Open No. 2003-251732.
- Japanese Patent Laid-Open No. 2003-251732 discloses a method of forming a transparent film having a gas barrier property on a plastic film by reactive sputtering using aluminum as a target and a mixed gas of hydrogen sulfide and oxygen as a reactive gas. Is disclosed.
- Patent Document 2 International Publication No. WO2011-1220366
- International Publication No. WO2011-122036 discloses a method of forming a transparent film having gas barrier properties on a plastic film by applying a coating liquid containing alumina particles and a phosphorus compound, followed by drying and heat treatment.
- the above conventional gas barrier coating has excellent initial gas barrier properties, defects such as cracks and pinholes may occur when subjected to physical stress such as deformation or impact. In some cases, sex was insufficient. For example, when it is used as a food packaging material, it is subjected to various physical stresses at each stage of printing, laminating, bag making, food filling, transportation, display, and consumption. Therefore, there is a demand for a multilayer structure that can maintain high gas barrier properties even under such physical stress.
- one of the objects of the present invention is to provide a multilayer structure that has excellent gas barrier properties and can maintain the gas barrier properties at a high level even when subjected to physical stress such as deformation or impact, and a method for manufacturing the same. Is to provide.
- the present inventors have excellent gas barrier properties by laminating a layer containing aluminum atoms and a layer containing a polymer having a plurality of phosphorus atoms adjacent to each other, It has been found that a multilayer structure capable of maintaining gas barrier properties at a high level even when subjected to physical stress such as deformation or impact can be obtained. That is, by laminating a layer containing a polymer having a plurality of phosphorus atoms not having gas barrier properties adjacent to a layer having aluminum atoms having gas barrier properties, the bending resistance of the resulting multilayer structure is greatly increased. I was able to improve. The present inventors have completed the present invention by further studying based on this new knowledge.
- the multilayer structure of the present invention is a multilayer structure having at least one substrate (X), layer (Y) and layer (Z), wherein the layer (Y) contains aluminum atoms,
- the layer (Z) contains a polymer (E) having a plurality of phosphorus atoms, and the polymer (E) is a polymer of at least one monomer containing vinylphosphonic acids, and at least one set of the layers (Y) and the layer (Z) are laminated adjacent to each other.
- At least one set of the substrate (X), the layer (Y), and the layer (Z) includes the substrate (X) / the layer (Y) / the layer (Z ) May be stacked in this order.
- the polymer (E) may be poly (vinyl phosphonic acid) represented by the following general formula (I).
- the layer (Y) may be a layer (YA) containing the reaction product (R).
- the reaction product (R) is a reaction product obtained by a reaction between a metal oxide (A) containing aluminum and a phosphorus compound (B).
- the infrared absorption spectrum of the layer (YA) is 800 to 1400 cm ⁇ .
- the wave number (n 1 ) that maximizes infrared absorption in the range of 1 may be in the range of 1080 to 1130 cm ⁇ 1 .
- the multilayer structure of the present invention in the infrared absorption spectrum of the layer (YA), and the wave number (n 1) the absorbance at (alpha 1), the absorbance at the wave number (n 2) ( ⁇ 2) and is, absorbance (alpha 2 ) / absorbance ( ⁇ 1 ) ⁇ 0.2 may be satisfied.
- the wave number (n 2 ) is a wave number that maximizes infrared absorption based on stretching vibration of hydroxyl groups in the range of 2500 to 4000 cm ⁇ 1 in the infrared absorption spectrum of the layer (YA).
- the half-value width of the absorption peak of the wave number (n 1 ) may be 200 cm ⁇ 1 or less.
- the metal oxide (A) may be a hydrolysis condensate of a compound (L) containing a metal atom (M) to which a hydrolyzable characteristic group is bonded
- the compound (L) may include at least one compound (L 1 ) represented by the following formula (II).
- AlX 1 m R 1 (3-m) (II) [In the formula (II), X 1 is selected from F, Cl, Br, I, R 2 O—, R 3 C ( ⁇ O) O—, (R 4 C ( ⁇ O)) 2 CH— and NO 3.
- R 1 , R 2 , R 3 and R 4 are each selected from the group consisting of an alkyl group, an aralkyl group, an aryl group and an alkenyl group.
- these X 1 when there are a plurality of X 1 , these X 1 may be the same or different from each other.
- these R 1 when a plurality of R 1 are present, these R 1 may be the same or different from each other.
- R 2 when a plurality of R 2 are present, these R 2 may be the same or different from each other.
- R 3 when a plurality of R 3 are present, these R 3 may be the same or different from each other.
- these R 4 when a plurality of R 4 are present, these R 4 may be the same as or different from each other.
- m represents an integer of 1 to 3.
- the compound (L 1 ) may be at least one compound selected from aluminum triisopropoxide and aluminum tris-butoxide.
- the phosphorus compound (B) may be at least one compound selected from the group consisting of phosphoric acid, polyphosphoric acid, phosphorous acid, phosphonic acid, and derivatives thereof.
- the multilayer structure of the present invention in the layer (YA), a number of moles N M of the metal atom (M) constituting the metal oxide (A), moles of phosphorus atoms derived from the phosphorus compound (B)
- the number N P may satisfy the relationship of 1.0 ⁇ (the number of moles N M ) / (the number of moles N P ) ⁇ 3.6.
- the layer (Y) may be an aluminum deposition layer or an aluminum oxide deposition layer.
- the substrate (X) may include at least one layer selected from the group consisting of a thermoplastic resin film layer, a paper layer, and an inorganic vapor deposition layer.
- the multilayer structure of the present invention may have an oxygen permeability of 2 ml / (m 2 ⁇ day ⁇ atm) or less at 20 ° C. and 85% RH.
- the multilayer structure of the present invention has an oxygen permeability of 4 ml / (m under the condition of 20 ° C. and 85% RH after being held for 5 minutes in a stretched state of 5% under the conditions of 23 ° C. and 50% RH. 2 ⁇ day ⁇ atm) or less.
- the production method of the present invention is a method for producing a multilayer structure having at least one substrate (X), layer (Y) and layer (Z), and the layer (Y) contains an aluminum atom.
- the layer (Z) contains a polymer (E) having a plurality of phosphorus atoms, and the polymer (E) is a polymer of at least one monomer containing vinylphosphonic acids, and at least one set Step (IV) in which the layer (Y) and the layer (Z) are laminated adjacent to each other, and the layer (Z) is formed by applying a coating liquid (V) containing the polymer (E). )including.
- the polymer (E) may be poly (vinyl phosphonic acid) represented by the following general formula (I).
- the layer (Y) may be a layer (YA) containing a reaction product (R), and the reaction product (R) is a metal oxide (A) containing aluminum. And a reaction product obtained by reacting the phosphorus compound (B).
- the production method of the present invention comprises mixing the metal oxide (A), at least one compound containing a site capable of reacting with the metal oxide (A), and a solvent.
- the method may further include a step (III) of forming the layer (YA) by heat-treating the precursor layer of the layer (YA) at a temperature of 110 ° C. or higher.
- the at least one compound may contain the phosphorus compound (B).
- the number of moles N M of metal atoms (M) constituting the metal oxide (A) and the number of moles N P of phosphorus atoms contained in the phosphorus compound (B) are 1
- the relationship of 0.0 ⁇ (the number of moles N M ) / (the number of moles N P ) ⁇ 3.6 may be satisfied.
- the step (IV) may be performed after the step (III).
- the layer (Y) may be an aluminum vapor deposition layer or an aluminum oxide vapor deposition layer.
- the present invention it is possible to obtain a multilayer structure that has excellent gas barrier properties and can maintain the gas barrier properties at a high level even when subjected to physical stress such as deformation or impact. Moreover, according to the manufacturing method of this invention, the said multilayer structure can be manufactured easily.
- the property of maintaining the gas barrier property at a high level even when subjected to physical stress such as deformation or impact may be expressed as “flexibility”.
- “gas barrier property after holding for 5 minutes in a stretched state of 5% under the conditions of 23 ° C. and 50% RH” was adopted as an index for evaluating the bending resistance. This is an evaluation condition that is severer than the physical stress that can occur under normal practical conditions, and a multilayer structure showing a good evaluation result with this index can be expected to show good performance even in actual use.
- a specific material such as a compound
- a material that exhibits a specific function may be exemplified as a material that exhibits a specific function.
- the present invention is not limited to an embodiment using such a material.
- the material illustrated may be used individually by 1 type, and may use 2 or more types together.
- the multilayer structure of the present invention is a multilayer structure having at least one substrate (X), layer (Y) and layer (Z), wherein the layer (Y) contains aluminum atoms and the layer (Z) Includes a polymer (E) having a plurality of phosphorus atoms, and the polymer (E) is a polymer of at least one monomer including vinylphosphonic acids, and includes at least one layer (Y) and a layer. (Z) is laminated adjacently.
- a multilayer structure is obtained by the method of the present invention for producing a multilayer structure.
- the layer (Y) of the multilayer structure of the present invention is a layer (YA) containing a reaction product (R) formed by a reaction of at least an aluminum-containing metal oxide (A) and a phosphorus compound (B). May be.
- the layer (Y) is a layer that is an aluminum deposition layer (hereinafter may be referred to as “layer (YB)”) or an aluminum oxide deposition layer (hereinafter may be referred to as “layer (YC)”).
- layer (YB) aluminum deposition layer
- layer (YC) aluminum oxide deposition layer
- the layer (Y) of the multilayer structure of the present invention is the layer (YA)
- the wave number maximum infrared absorption in the range of 800 to 1400 cm ⁇ 1 ( n 1 ) may be in the range of 1080 to 1130 cm ⁇ 1 .
- the wave number (n 1 ) may be referred to as “maximum absorption wave number (n 1 )”.
- the metal oxide (A) usually reacts with the phosphorus compound (B) in the form of particles of the metal oxide (A).
- the layer (YA) included in the multilayer structure of the present invention has a structure in which metal oxide (A) particles are bonded to each other via phosphorus atoms derived from the phosphorus compound (B).
- the form bonded via a phosphorus atom includes the form bonded via an atomic group containing a phosphorus atom, for example, bonded via an atomic group containing a phosphorus atom and not containing a metal atom. are included.
- the number of moles of metal atoms that are bonded to the metal oxide (A) particles and are not derived from the metal oxide (A) is metal. It is preferably in the range of 0 to 1 times the number of moles of phosphorus atoms bonding the particles of the oxide (A) (for example, in the range of 0 to 0.9 times), for example, 0.3 times or less, It may be 0.05 times or less, 0.01 times or less, or 0 times.
- the layer (YA) of the multilayer structure of the present invention may partially contain a metal oxide (A) and / or a phosphorus compound (B) that is not involved in the reaction.
- a metal atom and a phosphorus compound react to react a metal atom (M) constituting the metal compound and a phosphorus atom (P) derived from the phosphorus compound bonded via an oxygen atom (O).
- M metal atom
- P phosphorus atom
- O oxygen atom
- the absorption peak appears as an absorption peak of the maximum absorption wave number in a region of 800 to 1400 cm ⁇ 1 where absorption due to bonding between various atoms and oxygen atoms is generally observed, in the obtained multilayer structure Furthermore, it turned out that the outstanding gas-barrier property is expressed.
- grains are via the phosphorus atom derived from a phosphorus compound (B), and the metal atom which does not originate in a metal oxide (A) And a bond represented by M—O—P, in which the metal atom (M) and the phosphorus atom (P) constituting the metal oxide (A) are bonded through an oxygen atom (O).
- M—O—P a bond represented by M—O—P
- the absorption peak based on the M—O—P bond is 1080 in the infrared absorption spectrum of the layer (YA). It is considered that it appears as an absorption peak of the maximum absorption wave number in the region of 800 to 1400 cm ⁇ 1 in the range of ⁇ 1130 cm ⁇ 1 .
- the metal compound that does not form a metal oxide such as a metal alkoxide or a metal salt and a phosphorus compound (B) are mixed in advance and then hydrolytically condensed, the metal atom derived from the metal compound and A complex in which phosphorus atoms derived from the phosphorus compound (B) are mixed almost uniformly and reacted is obtained, and in the infrared absorption spectrum, the maximum absorption wave number (n 1 ) in the range of 800 to 1400 cm ⁇ 1 is 1080 to 1130 cm ⁇ . Beyond the range of 1 .
- the maximum absorption wave numbers (n 1) since as a multilayer structure excellent in gas barrier properties, preferably in the range of 1085 ⁇ 1,120 cm -1, and more preferably in the range of 1090 ⁇ 1110 cm -1.
- the amount of the hydroxyl group present in the layer (YA) can be correlated with the absorbance ( ⁇ 2 ) at the maximum absorption wave number (n 2 ) based on the stretching vibration of the hydroxyl group in the range of 2500 to 4000 cm ⁇ 1 .
- the wave number (n 2 ) is a wave number that maximizes infrared absorption based on the stretching vibration of hydroxyl groups in the range of 2500 to 4000 cm ⁇ 1 in the infrared absorption spectrum of the layer (YA).
- the wave number (n 2 ) may be referred to as “maximum absorption wave number (n 2 )”.
- the density of the layer (YA) decreases, and as a result, gas barrier properties tend to decrease.
- the ratio of the absorbance ( ⁇ 1 ) and the absorbance ( ⁇ 2 ) at the maximum absorption wave number (n 1 ) [absorbance ( ⁇ 2 ). / Absorbance ( ⁇ 1 )] is smaller, it is considered that the metal oxide (A) particles are more effectively bonded to each other via the phosphorus atom derived from the phosphorus compound (B).
- the ratio [absorbance ( ⁇ 2 ) / absorbance ( ⁇ 1 )] is preferably 0.2 or less, and preferably 0.1 or less, from the viewpoint of highly expressing the gas barrier properties of the resulting multilayer structure. It is more preferable.
- the multilayer structure in which the layer (YA) has the above ratio [absorbance ( ⁇ 2 ) / absorbance ( ⁇ 1 )] is the number of moles of metal atoms (N M ) constituting the metal oxide (A) described later. And the ratio of the number of moles of phosphorus atoms derived from the phosphorus compound (B) (N P ), heat treatment conditions, and the like.
- the maximum absorbance ( ⁇ 2 ′) based on the stretching vibration of the hydroxyl group in the range may satisfy the relationship of absorbance ( ⁇ 2 ′) / absorbance ( ⁇ 1 ′)> 0.2.
- the half width of the absorption peak having a maximum at the maximum absorption wave number (n 1 ) is 200 cm ⁇ from the viewpoint of gas barrier properties of the resulting multilayer structure. preferably 1 or less, more preferably 150 cm -1 or less, more preferably 130 cm -1 or less, more preferably 110 cm -1 or less, further not more 100 cm -1 or less It is particularly preferably 50 cm ⁇ 1 or less.
- this invention is not limited at all, when the particles of the metal oxide (A) are bonded to each other via a phosphorus atom, the particles of the metal oxide (A) are phosphorous derived from the phosphorus compound (B).
- Metal atoms (M) and phosphorus atoms (P) constituting the metal oxide (A) are bonded with oxygen atoms (O) through atoms and without metal atoms not derived from the metal oxide (A).
- M-O—P bonded through the metal the maximum absorption wave number (n 1 ) is maximized due to the relatively fixed environment of the surface of the metal oxide (A) particles. It is considered that the half width of the absorption peak having a value falls within the above range.
- the half width of the absorption peak of the maximum absorption wave number (n 1 ) is the wave number of two points having an absorbance (absorbance ( ⁇ 1 ) / 2) that is half of the absorbance ( ⁇ 1 ) at the absorption peak. It can be obtained by calculating the difference.
- the infrared absorption spectrum of the layer (YA) is measured by the ATR method (total reflection measurement method), or the layer (YA) is scraped from the multilayer structure and the infrared absorption spectrum is measured by the KBr method. Obtainable.
- the shape of each particle of the metal oxide (A) is not particularly limited, and for example, a shape such as a spherical shape, a flat shape, a polyhedral shape, a fibrous shape, or a needle shape is used. A fibrous or needle-like shape is preferable because a multilayer structure having excellent gas barrier properties can be obtained.
- the layer (YA) may have only particles having a single shape, or may have particles having two or more different shapes.
- the size of the metal oxide (A) particles is not particularly limited, and examples include nanometer-size to submicron-size particles. The size of the particles (A) is preferably in the range of 1 to 100 nm as an average particle size.
- the fine structure as described above in the layer (YA) of the multilayer structure of the present invention can be confirmed by observing the cross section of the layer (YA) with a transmission electron microscope (TEM).
- the particle size of each particle of the metal oxide (A) in the layer (YA) is the maximum length of the longest axis of each particle in the cross-sectional observation image of the layer (YA) obtained by a transmission electron microscope (TEM).
- the average particle size can be obtained as an average value of the maximum lengths of the particles on an axis perpendicular to the average, and the average particle size of ten particles arbitrarily selected in the cross-sectional observation image is obtained. Can do.
- the layer (YA) included in the multilayer structure of the present invention is derived from the metal oxide (A) in which the particles of the metal oxide (A) are interposed via the phosphorus atom derived from the phosphorus compound (B). It has a structure bonded without intervening metal atoms. That is, in one example, the metal oxide (A) particles may be bonded to each other via a metal atom derived from the metal oxide (A), but are not bonded to any other metal atom.
- the structure bonded through the phosphorus atom derived from the phosphorus compound (B) and not through the metal atom not derived from the metal oxide (A) means the metal oxide (A) to be bonded.
- the layer (YA) of the multilayer structure of the present invention has a structure in which particles of the metal oxide (A) are bonded to each other through both phosphorus atoms and metal atoms derived from the phosphorus compound (B) (
- the main chain of the bond between the particles of the metal oxide (A) to be bonded may partially have a structure having both a phosphorus atom and a metal atom derived from the phosphorus compound (B).
- bonded through the oxygen atom (O) can be mentioned.
- the particles of the metal oxide (A) may be bonded to each other via a phosphorus atom (P) derived from one molecule of the phosphorus compound (B), but phosphorus derived from two or more molecules of the phosphorus compound (B). It may be bonded via an atom (P).
- a metal atom constituting one bonded metal oxide (A) particle is represented as (M ⁇ )
- the metal atom constituting the other metal oxide (A) particle is represented by (M ⁇ )
- (M ⁇ ) -OPO— (M ⁇ ) bond form for example, (M ⁇ ) -OPO— (M ⁇ ) bond form; (M ⁇ ) -OP— [O—P] n —O— (M ⁇ ) bond form; (M ⁇ ) —O—P—Z—P—O— (M ⁇ ) bond form; (M ⁇ ) —O—P—Z—P— [ And a bonding form of O—P—Z—P] n —O— (M ⁇ ).
- n represents an integer of 1 or more
- Z represents a constituent atomic group existing between two phosphorus atoms when the phosphorus compound (B) has two or more phosphorus atoms in the molecule.
- Z represents a constituent atomic group existing between two phosphorus atoms when the phosphorus compound (B) has two or more phosphorus atoms in the molecule.
- other substituents bonded to the phosphorus atom is omitted.
- the layer (YA) of the multilayer structure of the present invention it is possible to obtain a multilayer structure in which one metal oxide (A) particle is bonded to a plurality of other metal oxide (A) particles. From the viewpoint of gas barrier properties.
- the metal oxide (A) may be a hydrolysis condensate of the compound (L) containing a metal atom (M) to which a hydrolyzable characteristic group is bonded.
- Examples of the characteristic group include X 1 of the formula (II) described later.
- the hydrolysis condensate of the compound (L) can be substantially regarded as a metal oxide. Therefore, in this specification, the hydrolysis condensate of the compound (L) may be referred to as “metal oxide (A)”. That is, in this specification, “metal oxide (A)” can be read as “hydrolysis condensate of compound (L)”, and “hydrolysis condensate of compound (L)” can be referred to as “metal. It can be read as “oxide (A)”.
- Metal oxide (A) The metal atoms constituting the metal oxide (A) (sometimes collectively referred to as “metal atoms (M)”) have a valence of 2 or more (for example, 2 to 4 or 3 to 4).
- metals of Group 2 of the periodic table such as magnesium and calcium
- metals of Group 12 of the periodic table such as zinc
- metals of Group 13 of the periodic table such as aluminum
- metals of Group 14 of the periodic table such as silicon
- transition metals such as titanium and zirconium.
- Silicon may be classified as a semimetal, but in this specification, silicon is included in the metal.
- the metal atom (M) constituting the metal oxide (A) may be one kind or two or more kinds, but it is necessary to contain at least aluminum.
- the metal atom (M) that can be used in combination with aluminum is selected from the group consisting of titanium and zirconium because of ease of handling for producing the metal oxide (A) and excellent gas barrier properties of the resulting multilayer structure. It is preferable that there is at least one.
- the total proportion of aluminum, titanium and zirconium in the metal atom (M) was 60 mol% or more, 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 100 mol%. May be.
- the proportion of aluminum in the metal atom (M) may be 60 mol% or more, 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 100 mol%.
- metal oxide (A) those produced by a liquid phase synthesis method, a gas phase synthesis method, a solid pulverization method or the like can be used. In view of the controllability of the thickness and production efficiency, those produced by the liquid phase synthesis method are preferred.
- a hydrolyzable condensation product of the compound (L) is obtained by hydrolyzing and condensing the compound (L) having a hydrolyzable characteristic group bonded to the metal atom (M) as a raw material.
- a metal oxide (A) can be synthesized.
- the metal atom (M) included in the compound (L) needs to contain at least aluminum.
- the compound (L) which a partly hydrolyzed compound (L) other than the method of using the compound (L) itself as a raw material ( L) partial hydrolyzate, compound (L) completely hydrolyzed product obtained by completely hydrolyzing compound (L), compound (L) partially hydrolyzed and condensed part of compound (L) Metal oxidation can also be achieved by condensing or hydrolyzing a hydrolysis condensate, a product obtained by condensing a part of a complete hydrolyzate of compound (L), or a mixture of two or more of these as raw materials.
- a thing (A) can be manufactured.
- the metal oxide (A) thus obtained is also referred to as “hydrolysis condensate of compound (L)” in the present specification.
- the type of the functional group (functional group) that can be hydrolyzed include halogen atoms (F, Cl, Br, I, etc.), alkoxy groups, acyloxy groups, diacylmethyl groups, nitro groups, and the like.
- halogen atoms F, Cl, Br, I, etc.
- alkoxy groups alkoxy groups
- acyloxy groups acyloxy groups
- diacylmethyl groups nitro groups
- nitro groups nitro groups
- a halogen atom or an alkoxy group is preferable and an alkoxy group is more preferable because of excellent controllability of the reaction.
- the compound (L) preferably contains at least one compound (L 1 ) represented by the following formula (II) because the reaction is easily controlled and the resulting multilayer structure has excellent gas barrier properties.
- AlX 1 m R 1 (3-m) (II) [In the formula (II), X 1 is selected from F, Cl, Br, I, R 2 O—, R 3 C ( ⁇ O) O—, (R 4 C ( ⁇ O)) 2 CH— and NO 3. Selected from the group of R 1 , R 2 , R 3 and R 4 are each selected from the group consisting of an alkyl group, an aralkyl group, an aryl group and an alkenyl group.
- Examples of the alkyl group represented by R 1 , R 2 , R 3 and R 4 include a methyl group, an ethyl group, a normal propyl group, an isopropyl group, a normal butyl group, a s-butyl group, a t-butyl group, and 2-ethylhexyl. Groups and the like.
- Examples of the aralkyl group represented by R 1 , R 2 , R 3 and R 4 include a benzyl group, a phenethyl group and a trityl group.
- Examples of the aryl group represented by R 1 , R 2 , R 3 and R 4 include a phenyl group, a naphthyl group, a tolyl group, a xylyl group and a mesityl group.
- Examples of the alkenyl group represented by R 1 , R 2 , R 3 and R 4 include a vinyl group and an allyl group.
- R 1 is preferably, for example, an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms.
- X 1 is preferably F, Cl, Br, I, or R 2 O—.
- X 1 is a halogen atom (F, Cl, Br, I) or an alkoxy group having 1 to 4 carbon atoms (R 2 O—), and m is 3.
- X 1 is a halogen atom (F, Cl, Br, I) or an alkoxy group having 1 to 4 carbon atoms (R 2 O—), and m is 3.
- the compound (L) may include at least one compound represented by the following formula (III).
- M 1 X 1 m R 1 (nm) (III) [Wherein M 1 represents Ti or Zr.
- X 1 is selected from the group consisting of F, Cl, Br, I, R 2 O—, R 3 C ( ⁇ O) O—, (R 4 C ( ⁇ O)) 2 CH—, and NO 3 .
- R 1 , R 2 , R 3 and R 4 are each selected from the group consisting of an alkyl group, an aralkyl group, an aryl group and an alkenyl group.
- these X 1 may be the same or different from each other.
- n is equal to the valence of M 1 .
- m represents an integer of 1 to n. ]
- the compound (L 1 ) include, for example, aluminum chloride, aluminum triethoxide, aluminum trinormal propoxide, aluminum triisopropoxide, aluminum trinormal butoxide, aluminum tri-s-butoxide, aluminum tri-t-butoxide, Examples of the aluminum compound include aluminum triacetate, aluminum acetylacetonate, and aluminum nitrate.
- the compound (L 1 ) at least one compound selected from aluminum triisopropoxide and aluminum tris-butoxide is preferable.
- one type may be used alone, or two or more types may be used in combination.
- the ratio of the compound (L 1 ) to the compound (L) is not particularly limited.
- the proportion of the compound other than the compound (L 1 ) in the compound (L) is, for example, 20 mol% or less, 10 mol% or less, 5 mol% or less, or 0 mol%.
- the compound (L) consists only of the compound (L 1 ).
- the compound (L) other than the compound (L 1 ) is not particularly limited as long as the effects of the present invention can be obtained.
- the above-mentioned hydrolyzate may be added to a metal atom such as titanium, zirconium, magnesium, calcium, zinc, or silicon.
- a metal atom such as titanium, zirconium, magnesium, calcium, zinc, or silicon.
- Examples thereof include a compound having a decomposable characteristic group bonded thereto. Silicon may be classified as a semimetal, but in this specification, silicon is included in the metal.
- the compound (L) other than the compound (L 1 ) is preferably a compound having titanium or zirconium as a metal atom because the resulting multilayer structure is excellent in gas barrier properties.
- the compound (L) other than the compound (L 1 ) include, for example, titanium tetraisopropoxide, titanium tetranormal butoxide, titanium tetra (2-ethylhexoxide), titanium tetramethoxide, titanium tetraethoxide.
- titanium compounds such as titanium acetylacetonate; zirconium compounds such as zirconium tetranormal propoxide, zirconium tetrabutoxide and zirconium tetraacetylacetonate.
- 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 (A) thus formed.
- an oxygen atom bonded to only a metal atom (M), such as an oxygen atom (O) in a structure represented by MOM with respect to the number of moles of the metal atom (M) is excluded (excludes oxygen atoms bonded to metal atoms (M) and hydrogen atoms (H)).
- a compound in which the number of moles of oxygen atoms (O) bonded only to metal atoms (M) / [number of moles of metal atoms (M)]) is 0.8 or more is included in the metal oxide (A) And
- the ratio of the metal oxide (A) is preferably 0.9 or more, more preferably 1.0 or more, and further preferably 1.1 or more. Although the upper limit of the said ratio is not specifically limited, When the valence of a metal atom (M) is set to n, it will normally be represented by n / 2.
- the compound (L) has a hydrolyzable characteristic group (functional group).
- the hydrolysis condensation reaction does not occur or becomes extremely slow, making it difficult to prepare the target metal oxide (A).
- the hydrolysis-condensation product can be produced from a specific raw material by, for example, a method employed in a known sol-gel method.
- the raw materials include compound (L), partial hydrolyzate of compound (L), complete hydrolyzate of compound (L), partial hydrolyzed condensate of compound (L), and complete hydrolysis of compound (L). It is possible to use at least one selected from the group consisting of a part of the product condensed (hereinafter sometimes referred to as “compound (L) component”).
- compound (L) component a part of the product condensed
- These raw materials may be produced by a known method, or commercially available ones may be used.
- a condensate obtained by hydrolytic condensation of about 2 to 10 compounds (L) can be used as a raw material.
- a product obtained by hydrolyzing and condensing aluminum triisopropoxide into a dimer to 10-mer condensate can be used as a part of the raw material.
- the number of molecules condensed in the hydrolyzed condensate of compound (L) can be controlled by the conditions at the time of condensing or hydrolyzing the compound (L) component.
- the number of molecules to be condensed can be controlled by the amount of water, the type and concentration of the catalyst, the temperature and time for condensation or hydrolysis condensation, and the like.
- the layer (YA) of the multilayer structure of the present invention includes a reaction product (R), and the reaction product (R) includes at least an aluminum-containing metal oxide (A) and a phosphorus compound. It is a reaction product formed by reaction with (B). Such a reaction product can be formed by mixing and reacting the metal oxide (A) and the phosphorus compound (B).
- the metal oxide (A) used for mixing with the phosphorus compound (B) may be the metal oxide (A) itself or a composition containing the metal oxide (A). It may be in the form of a thing.
- the metal oxide (A) is mixed with the phosphorus compound (B) in the form of a liquid (solution or dispersion) obtained by dissolving or dispersing the metal oxide (A) in a solvent.
- a preferred method for producing a metal oxide (A) solution or dispersion is described below.
- a method for producing the dispersion liquid will be described by taking as an example the case where the metal oxide (A) does not contain a metal atom other than aluminum atoms, that is, the case where the metal oxide (A) is aluminum oxide (alumina).
- a similar production method can be adopted when producing a solution or dispersion containing other metal atoms.
- a preferred alumina dispersion is obtained by hydrolyzing and condensing aluminum alkoxide in an aqueous solution whose pH is adjusted with an acid catalyst as necessary to obtain an alumina slurry, which is peptized in the presence of a specific amount of acid. Can do.
- the temperature of the reaction system when the aluminum alkoxide is hydrolytically condensed is not particularly limited.
- the temperature of the reaction system is usually in the range of 2 to 100 ° C.
- the temperature of the reaction system is usually in the range of 2 to 100 ° C.
- the temperature of the liquid rises, but as the hydrolysis proceeds, alcohol is by-produced, and when the boiling point of the alcohol is lower than that of water, the alcohol volatilizes and the temperature of the reaction system is reduced. It may not rise above the vicinity of the boiling point of the alcohol. In such a case, since the growth of alumina may be slow, it is effective to remove the alcohol by heating to around 95 ° C.
- the reaction time varies depending on the reaction conditions (presence / absence of acid catalyst, amount, type, etc.).
- the reaction time is usually within a range of 0.01 to 60 hours, preferably within a range of 0.1 to 12 hours, and more preferably within a range of 0.5 to 6 hours.
- the reaction can be performed in an atmosphere of various gases such as air, carbon dioxide, nitrogen, and argon.
- the amount of water used in the hydrolytic condensation is preferably 1 to 200 mol times, more preferably 10 to 100 mol times with respect to the aluminum alkoxide.
- the amount of water is less than 1 mole, hydrolysis does not proceed sufficiently, such being undesirable.
- it exceeds 200 mol times since manufacturing efficiency falls or a viscosity becomes high, it is unpreferable.
- a component containing water for example, hydrochloric acid or nitric acid
- hydrochloric acid, sulfuric acid, nitric acid, p-toluenesulfonic acid, benzoic acid, acetic acid, lactic acid, butyric acid, carbonic acid, oxalic acid, maleic acid and the like can be used.
- hydrochloric acid, sulfuric acid, nitric acid, acetic acid, lactic acid, and butyric acid are preferable, and nitric acid and acetic acid are more preferable.
- an acid catalyst is used during hydrolysis condensation, it is preferable to use an amount suitable for the type of acid so that the pH before hydrolysis condensation is in the range of 2.0 to 4.0.
- the alumina slurry obtained by hydrolysis and condensation can be used as an alumina dispersion as it is, but the obtained alumina slurry is heated in the presence of a specific amount of acid to peptize and become transparent.
- An alumina dispersion having excellent viscosity stability can be obtained.
- nitric acid As the acid used at the time of peptization, monovalent inorganic acids and organic acids such as nitric acid, hydrochloric acid, perchloric acid, formic acid, acetic acid, and propionic acid can be used. Among these, nitric acid, hydrochloric acid, and acetic acid are preferable, and nitric acid and acetic acid are more preferable.
- the amount is preferably 0.001 to 0.4 mol times, preferably 0.005 to 0.3 mol times the aluminum atom. More preferred. When the amount is less than 0.001 mole times, peptization may not sufficiently proceed or a very long time may be required. On the other hand, when it exceeds 0.4 mole times, the temporal stability of the resulting alumina dispersion tends to be lowered.
- the amount is preferably 0.01 to 1.0 mol times, more preferably 0.05 to 0.5 mol times with respect to aluminum atoms. More preferred.
- the amount is less than 0.01 mole times, peptization may not proceed sufficiently, or problems such as a very long time may occur.
- it exceeds 1.0 mole times the temporal stability of the resulting alumina dispersion tends to be lowered.
- the acid to be present at the time of peptization may be added at the time of hydrolysis condensation, but when acid is lost when removing alcohol by-produced by hydrolysis condensation, the amount is in the above range. It is preferable to add it again.
- the peptization is carried out in a short time with an appropriate amount of acid used to produce an alumina dispersion having a predetermined particle size and excellent viscosity stability. be able to.
- the temperature during peptization is less than 40 ° C, it takes a long time for peptization, and when it exceeds 200 ° C, the increase in peptization rate by increasing the temperature is slight, while the high pressure vessel It is not preferable because it is economically disadvantageous.
- an alumina dispersion having a predetermined concentration can be obtained by performing dilution with a solvent or concentration by heating as necessary.
- the metal oxide (A) used for mixing with the phosphorus compound (B) contains substantially no phosphorus atom.
- the metal oxide (A) used for mixing with the phosphorus compound (B) contains substantially no phosphorus atom.
- it is used for mixing with the phosphorus compound (B) (a composition containing the phosphorus compound (B) when used as a composition).
- a small amount of phosphorus atoms may be mixed in the metal oxide (A). Therefore, the metal oxide (A) used for mixing with the phosphorus compound (B) (a composition containing the phosphorus compound (B) when used as a composition) within a range in which the effects of the present invention are not impaired.
- the phosphorus atom content contained in the metal oxide (A) used for mixing with the phosphorus compound (B) (a composition containing the phosphorus compound (B) when used as a composition) is more excellent in gas barrier properties. Since a multilayer structure can be obtained, it is preferably 30 mol% or less, based on the number of moles of all metal atoms (M) contained in the metal oxide (A) (100 mol%). % Or less, more preferably 5 mol% or less, further preferably 1 mol% or less, and may be 0 mol%.
- the metal oxide (A) particles have a specific structure bonded through phosphorus atoms derived from the phosphorus compound (B).
- Metal used for mixing the shape and size of the metal oxide (A) particles in the layer (YA) with the phosphorus compound (B) (a composition containing the phosphorus compound (B) when used as a composition)
- the shape and size of the oxide (A) particles may be the same or different from each other. That is, the shape and size of the metal oxide (A) particles used as the raw material for the layer (YA) may change during the process of forming the layer (YA).
- the phosphorus compound (B) contains a site capable of reacting with the metal oxide (A), and typically contains a plurality of such sites. In a preferred example, the phosphorus compound (B) contains 2 to 20 such sites (atomic groups or functional groups). Examples of such a part include a part capable of reacting with a functional group (for example, a hydroxyl group) present on the surface of the metal oxide (A). For example, examples of such a site include a halogen atom directly bonded to a phosphorus atom and an oxygen atom directly bonded to a phosphorus atom.
- halogen atoms and oxygen atoms can cause a condensation reaction (hydrolysis condensation reaction) with a hydroxyl group present on the surface of the metal oxide (A).
- the functional group for example, hydroxyl group
- present on the surface of the metal oxide (A) is usually bonded to the metal atom (M) constituting the metal oxide (A).
- the phosphorus compound (B) for example, a compound having a structure in which a halogen atom or an oxygen atom is directly bonded to a phosphorus atom can be used.
- a metal oxide (A) can be used. It can be combined by condensation (hydrolysis) with a hydroxyl group present on the surface.
- the phosphorus compound (B) may have one phosphorus atom, or may have two or more phosphorus atoms.
- the phosphorus compound (B) may be at least one compound selected from the group consisting of phosphoric acid, polyphosphoric acid, phosphorous acid, phosphonic acid, and derivatives thereof.
- polyphosphoric acid include pyrophosphoric acid, triphosphoric acid, polyphosphoric acid condensed with four or more phosphoric acids, and the like.
- the derivatives include salts of phosphoric acid, polyphosphoric acid, phosphorous acid, and phosphonic acid, (partial) ester compounds, halides (such as chlorides), dehydrates (such as niline pentoxide), and the like. .
- examples of phosphonic acid derivatives include a hydrogen atom directly bonded to a phosphorus atom of phosphonic acid (HP ( ⁇ O) (OH) 2 ) and an alkyl group which may have various functional groups.
- Substituted compounds eg, nitrilotris (methylenephosphonic acid), N, N, N ′, N′-ethylenediaminetetrakis (methylenephosphonic acid), etc.
- salts thereof, (partial) ester compounds, halides and dehydration Things are also included.
- organic polymers having a phosphorus atom such as phosphorylated starch and polymer (E) described later, can also be used as the phosphorus compound (B).
- These phosphorus compounds (B) may be used alone or in combination of two or more.
- these phosphorus compounds (B) the stability of the coating liquid (U) in the case of forming the layer (YA) using the coating liquid (U) described later and the gas barrier property of the resulting multilayer structure are more excellent. Therefore, it is preferable to use phosphoric acid alone or to use phosphoric acid and other phosphorus compounds in combination.
- the layer (YA) of the multilayer structure of the present invention includes the reaction product (R), and the reaction product (R) includes at least the metal oxide (A) and the phosphorus compound (B). It is a reaction product formed by the reaction.
- a reaction product can be formed by mixing and reacting the metal oxide (A) and the phosphorus compound (B).
- the phosphorus compound (B) used for mixing with the metal oxide (A) may be the phosphorus compound (B) itself or a form of a composition containing the phosphorus compound (B).
- the form of the composition containing the phosphorus compound (B) is preferable.
- the phosphorus compound (B) is mixed with the metal oxide (A) in the form of a solution obtained by dissolving the phosphorus compound (B) in a solvent.
- a solvent any solvent can be used at that time, water or a mixed solvent containing water is a preferable solvent.
- the phosphorus compound (B) used for mixing with the metal oxide (A) or the composition containing the phosphorus compound (B) has a low metal atom content, so that a multilayer structure excellent in gas barrier properties can be obtained.
- the phosphorus compound (B) or composition containing the phosphorus compound (B) to be mixed with the metal oxide (A) contains metal atoms in the phosphorus compound (B) or phosphorus compound (B). Is preferably 100 mol% or less, more preferably 30 mol% or less, and more preferably 5 mol% or less, based on the number of moles of all phosphorus atoms contained in the composition containing More preferably, it is particularly preferably 1 mol% or less, and may be 0 mol%.
- reaction product (R) includes a reaction product produced by reacting only the metal oxide (A) and the phosphorus compound (B).
- the reaction product (R) also includes a reaction product produced by reacting the metal oxide (A), the phosphorus compound (B), and another compound.
- the reaction product (R) can be formed by the method described in the production method described later.
- the number of moles N M of metal atoms constituting the metal oxide (A) and the number of moles N P of phosphorus atoms derived from the phosphorus compound (B) are 1.0 ⁇ (number of moles N M ) / (Number of moles N P ) ⁇ 3.6, more preferably 1.1 ⁇ (number of moles N M ) / (number of moles N P ) ⁇ 3.0.
- the said ratio can be adjusted with ratio of the quantity of a metal oxide (A) and the quantity of a phosphorus compound (B) in the coating liquid for forming a layer (YA).
- the ratio of the moles N M and the number of moles N P in the layer (YA) is generally constituted by a ratio in the coating solution moles of phosphorus compound of a metal atom constituting the metal oxide (A) and (B) It is the same as the ratio to the number of moles of phosphorus atoms to be made.
- the layer (YA) included in the multilayer structure of the present invention may further contain a specific polymer (C).
- the polymer (C) is a polymer having at least one functional group (f) selected from the group consisting of a hydroxyl group, a carboxyl group, a carboxylic anhydride group, and a carboxyl group salt.
- the polymer (C) has one or both of particles of the metal oxide (A) and a phosphorus atom derived from the phosphorus compound (B) depending on the functional group (f) it has. It may be bound directly or indirectly.
- the reaction product (R) is a polymer (C) portion produced by the reaction of the polymer (C) with the metal oxide (A) or the phosphorus compound (B). You may have.
- a polymer that satisfies the requirements as the phosphorus compound (B) and includes the functional group (f) is not included in the polymer (C) but is treated as the phosphorus compound (B). .
- a polymer containing a structural unit having a functional group (f) can be used as the polymer (C).
- specific examples of such structural units include 1 functional group (f) such as a vinyl alcohol unit, an acrylic acid unit, a methacrylic acid unit, a maleic acid unit, an itaconic acid unit, a maleic anhydride unit, and a phthalic anhydride unit.
- Examples include structural units having at least one unit.
- the polymer (C) may contain only one type of structural unit having the functional group (f), or may contain two or more types of structural units having the functional group (f).
- the proportion of the structural unit having the functional group (f) in the total structural units of the polymer (C) is 10 mol% or more. It is preferably 20 mol% or more, more preferably 40 mol% or more, particularly preferably 70 mol% or more, and may be 100 mol%.
- the type of the other structural unit is not particularly limited.
- examples of such other structural units are derived from (meth) acrylic acid esters such as methyl acrylate units, methyl methacrylate units, ethyl acrylate units, ethyl methacrylate units, butyl acrylate units, and butyl methacrylate units.
- the polymer (C) contains two or more types of structural units, the polymer (C) is any of an alternating copolymer, a random copolymer, a block copolymer, and a tapered copolymer. Also good.
- polymer (C) having a hydroxyl group examples include polyvinyl alcohol, polyvinyl acetate partially saponified products, polyethylene glycol, polyhydroxyethyl (meth) acrylate, starch and other polysaccharides, polysaccharides derived from polysaccharides Derivatives and the like.
- polymer (C) having a carboxyl group, a carboxylic anhydride group or a carboxyl group salt include polyacrylic acid, polymethacrylic acid, poly (acrylic acid / methacrylic acid), and salts thereof. Can do.
- polymer (C) containing a structural unit not containing the functional group (f) include an ethylene-vinyl alcohol copolymer, an ethylene-maleic anhydride copolymer, and a styrene-maleic anhydride copolymer. And isobutylene-maleic anhydride alternating copolymer, ethylene-acrylic acid copolymer, saponified ethylene-ethyl acrylate copolymer, and the like.
- the polymer (C) comprises polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polysaccharide, polyacrylic acid, polyacrylic acid salt, It is preferably at least one polymer selected from the group consisting of polymethacrylic acid and polymethacrylic acid salts.
- the number average molecular weight of the polymer (C) is preferably 5,000 or more, and 8,000. More preferably, it is more preferably 10,000 or more.
- the upper limit of the number average molecular weight of the polymer (C) is not particularly limited, and is, for example, 1,500,000 or less.
- the content of the polymer (C) in the layer (YA) is preferably 50% by mass or less based on the mass of the layer (YA) (100% by mass). It is more preferably at most mass%, more preferably at most 30 mass%, and may be at most 20 mass%.
- the polymer (C) may or may not react with other components in the layer (YA).
- the case where the polymer (C) reacts with other components is also expressed as the polymer (C).
- the content of the polymer (C) is calculated by dividing the mass of the polymer (C) before bonding with the metal oxide (A) and / or the phosphorus atom by the mass of the layer (YA). To do.
- the layer (YA) of the multilayer structure has a reaction product (R) (provided that the polymer (C) portion is formed by the reaction of the metal oxide (A) containing at least aluminum with the phosphorus compound (B).
- the reaction product (R) and the non-reacted polymer (C) may further include other components. Also good.
- Examples of other components include inorganic acid metal salts such as carbonates, hydrochlorides, nitrates, hydrogen carbonates, sulfates, hydrogen sulfates, borates, and aluminates; oxalates, acetates, Organic acid metal salts such as tartrate and stearate; metal complexes such as acetylacetonate metal complexes (such as aluminum acetylacetonate), cyclopentadienyl metal complexes (such as titanocene), cyano metal complexes; layered clay compounds; Agents; polymer compounds other than the polymer (C); plasticizers; antioxidants; ultraviolet absorbers; flame retardants and the like.
- inorganic acid metal salts such as carbonates, hydrochlorides, nitrates, hydrogen carbonates, sulfates, hydrogen sulfates, borates, and aluminates
- oxalates such as tartrate and stearate
- metal complexes such as
- the content of the other components in the layer (YA) in the multilayer structure is preferably 50% by mass or less, more preferably 20% by mass or less, and further preferably 10% by mass or less. It is preferably 5% by mass or less, and may be 0% by mass (excluding other components).
- the thickness (YA) of the multilayer structure of the present invention (when the multilayer structure has two or more layers (YA), the total thickness of each layer (YA)) is 4.0 ⁇ m or less. Preferably, it is 2.0 ⁇ m or less, more preferably 1.0 ⁇ m or less, and may be 0.9 ⁇ m or less.
- the thickness of the layer (YA) By reducing the thickness of the layer (YA), the dimensional change of the multilayer structure during processing such as printing and laminating can be kept low, and the flexibility of the multilayer structure is further increased. It can be close to the mechanical characteristics of.
- the oxygen permeability under the conditions of 20 ° C. and 85% RH is 2 ml / ( m 2 ⁇ day ⁇ atm) or less.
- the thickness of the layer (YA) (when the multilayer structure has two or more layers (YA), the total thickness of each layer (YA)) is 0.1 ⁇ m or more (for example, 0.2 ⁇ m or more). It is preferable that The thickness per layer (YA) is preferably 0.05 ⁇ m or more (for example, 0.15 ⁇ m or more) from the viewpoint of improving the gas barrier properties of the multilayer structure of the present invention.
- the thickness of the layer (YA) can be controlled by the concentration of a coating liquid (U) described later used for forming the layer (YA) and the coating method.
- the layer (Y) of the multilayer structure of the present invention may be a layer (YB) that is an aluminum deposition layer or a layer (YC) that is an aluminum oxide deposition layer.
- vapor deposition layers can be manufactured by the same method as the inorganic vapor deposition layer mentioned later.
- the layer (Z) included in the multilayer structure of the present invention includes a polymer (E) having a plurality of phosphorus atoms. By forming the layer (Z) adjacent to the layer (Y), the bending resistance of the multilayer structure of the present invention can be greatly improved.
- the polymer (E) has a plurality of phosphorus atoms in the polymer.
- the phosphorus atom is contained in an acidic group or derivative thereof.
- the acidic group containing a phosphorus atom include a phosphoric acid group, a polyphosphoric acid group, a phosphorous acid group, and a phosphonic acid group.
- At least 1 phosphorus atom contains the site
- the polymer (E) contains about 10 to 1000 such phosphorus atoms.
- part of the structure described with respect to the phosphorus compound (B) can be mentioned as an example of the site
- the homopolymer or copolymer of vinylphosphonic acid containing a phosphoric acid group can be mentioned.
- the “vinyl phosphonic acids” mean those satisfying the following requirements.
- a part of the carbon chain may constitute a carbocyclic ring.
- C At least one hydroxyl group is bonded to the phosphorus atom in the molecule (phosphonic acid group, phosphinic acid group or phosphorus atom in their ester).
- vinyl phosphonic acids is a phosphonic acid and / or phosphinic acid having a substituent, and satisfies the requirement (b) above.
- an example phosphonic acid is a phosphonic acid having a substituent, and satisfies the requirement (b).
- the number of carbon atoms contained in the carbon chain of the substituent bonded to the phosphorus atom may be in the range of 2 to 30 (for example, in the range of 2 to 10).
- the substituent include a hydrocarbon chain having a carbon-carbon double bond (eg, vinyl group, allyl group, 1-propenyl group, isopropenyl group, 2-methyl-1-propenyl group, 2-methyl-2 -Propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 1-hexenyl, 1,3-hexadienyl, 1,5-hexadienyl, etc.).
- a hydrocarbon chain having a carbon-carbon double bond eg, vinyl group, allyl group, 1-propenyl group, isopropenyl group, 2-methyl-1-propenyl group, 2-methyl-2 -Propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 1-
- the hydrocarbon chain having a carbon-carbon double bond may contain one or more oxycarbonyl groups in the molecular chain.
- the carbocycle include a benzene ring, naphthalene ring, cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclopropene ring, cyclobutene ring, cyclopentene ring and the like.
- one or more saturated hydrocarbon chains for example, a methyl group, an ethyl group, a propyl group, etc. may be bonded.
- Examples of the substituent bonded to the phosphorus atom include a hydrocarbon chain having the carbon-carbon double bond, such as a vinyl group, and a carbon having the hydrocarbon chain bonded to the carbocycle, such as a 4-vinylbenzyl group. Includes a ring.
- the ester group constituting the ester is a structure in which a hydrogen atom of a hydroxyl group bonded to a phosphorus atom of phosphinic acid or phosphonic acid is substituted with an alkyl group.
- alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group.
- the polymer (E) can be obtained by polymerizing a monomer of vinylphosphonic acid or copolymerizing with another vinyl group-containing monomer.
- the polymer (E) can also be obtained by hydrolyzing a vinylphosphonic acid derivative such as a phosphonic acid halide or ester, either alone or copolymerized.
- Examples of monomers of vinylphosphonic acids that can be suitably used in the present invention include alkenylphosphonic acids such as vinylphosphonic acid and 2-propene-1-phosphonic acid; 4-vinylbenzylphosphonic acid, 4-vinyl Alkenyl aromatic phosphonic acids such as phenylphosphonic acid; 6-[(2-phosphonoacetyl) oxy] hexyl acrylate, phosphonomethyl methacrylate, 11-phosphonoundecyl methacrylate, 1,1-diphosphonoethyl methacrylate, etc.
- Examples include phosphono (meth) acrylic acid esters; phosphinic acids such as vinyl phosphinic acid and 4-vinylbenzyl phosphinic acid.
- poly (vinyl phosphonic acid) which is a homopolymer of vinyl phosphonic acid, is more preferable in that a multilayer structure excellent in bending resistance can be obtained.
- monomers that can be used in the present invention are not limited to these.
- the polymer (E) of the present invention may be a homopolymer of a monomer of the vinylphosphonic acid, or a copolymer using two or more monomers of the vinylphosphonic acid. Alternatively, it may be a copolymer of at least one monomer of the vinylphosphonic acid and another vinyl monomer.
- the other vinyl monomer that can be copolymerized with the vinyl phosphonic acid monomer is not particularly limited as long as it can be copolymerized with the vinyl phosphonic acid monomer, and known vinyl monomers can be used.
- vinyl monomers include acrylic acid, acrylic acid esters, methacrylic acid, methacrylic acid esters, acrylonitrile, methacrylonitrile, styrene, nucleus-substituted styrenes, alkyl vinyl ethers, alkyl vinyl esters, pars.
- Fluoro-alkyl vinyl ethers perfluoro-alkyl vinyl esters, maleic acid, maleic anhydride, fumaric acid, itaconic acid, maleimide, or phenylmaleimide.
- vinyl monomers those that can be particularly preferably used are methacrylic acid esters, acrylonitrile, styrenes, maleimide, and phenylmaleimide.
- the proportion of the structural unit derived from the monomer of the vinylphosphonic acid in the total structural units of the polymer (E) is 10 mol% or more.
- it is 20 mol% or more, more preferably 40 mol% or more, particularly preferably 70 mol% or more, and may be 100 mol%.
- the molecular weight of the polymer (E) is not particularly limited, but typically, the number average molecular weight of the polymer (E) is in the range of 1,000 to 100,000. When the number average molecular weight is in this range, the bending resistance improving effect by laminating the layer (Z) and the viscosity stability of the coating liquid (V) containing the polymer (E) described later are at a high level. Can be compatible. In addition, when the molecular weight of the polymer (E) per phosphorus atom is in the range of 100 to 500, it may be possible to further improve the bending resistance improvement effect by laminating the layer (Z). is there.
- the polymer (E) may be poly (vinyl phosphonic acid) represented by the following general formula (I).
- N is not particularly limited.
- n is a number that satisfies the number average molecular weight described above.
- the layer (Z) of the multilayer structure may be composed only of the polymer (E) having a plurality of phosphorus atoms, but may further contain other components.
- Examples of the other components include inorganic acid metal salts such as carbonate, hydrochloride, nitrate, hydrogen carbonate, sulfate, hydrogen sulfate, borate; oxalate, acetate, tartrate, stearin Organic acid metal salts such as acid salts; metal complexes such as acetylacetonate metal complexes (such as magnesium acetylacetonate), cyclopentadienyl metal complexes (such as titanocene), and cyano metal complexes; layered clay compounds; cross-linking agents; Polymer compounds other than (E); plasticizers; antioxidants; ultraviolet absorbers; flame retardants and the like.
- inorganic acid metal salts such as carbonate, hydrochloride, nitrate, hydrogen carbonate, sulfate, hydrogen sulfate, borate; oxalate, acetate, tartrate, stearin Organic acid metal salts such as acid salts; metal complexes such as
- the content of the other components in the layer (Z) in the multilayer structure is preferably 50% by mass or less, more preferably 20% by mass or less, and further preferably 10% by mass or less. It is preferably 5% by mass or less, and may be 0% by mass (excluding other components).
- the polymerization reaction for forming the polymer (E) can be performed using a polymerization initiator in a solvent in which both the monomer component as a raw material and the polymer to be produced are dissolved.
- polymerization initiators include 2,2-azobisisobutyronitrile, 2,2-azobis (2,4-dimethylvaleronitrile), dimethyl 2,2-azobis (2-methylpropionate), dimethyl Azo-based initiators such as 2,2-azobisisobutyrate and 2,2′-azobis (2-amidinopropane) dihydrochloride, peroxidation such as lauryl peroxide, benzoyl peroxide, and tert-butyl peroctoate Includes physical initiators.
- a solvent is appropriately selected depending on the combination of comonomers. You may use 2 or more types of mixed solvents as needed.
- An example of the polymerization reaction is carried out at a polymerization temperature of 50 to 100 ° C. while dropping a mixed solution consisting of a monomer, a polymerization initiator and a solvent into the solvent, and after the completion of the addition, the polymerization temperature is about 1 to 24 hours. The temperature is maintained and stirring is continued to complete the polymerization.
- the solvent is preferably used in a weight ratio of about 0.1 to 3.0, and the polymerization initiator is preferably used in a weight ratio of about 0.001 to 0.05. A more preferred weight ratio is 0.1 to 2.5 for the solvent. If the amount of the solvent and polymerization initiator used is not within the above ranges, the polymer may gel and become insoluble in various solvents, and problems such as the inability to apply using the solution may occur.
- the layer (Z) of the multilayer structure of the present invention can be formed by applying a polymer (E) solution.
- a polymer (E) solution any solvent can be used at that time, water, alcohols or a mixed solvent thereof can be mentioned as a preferred solvent.
- the thickness per layer of the layer (Z) is preferably 0.005 ⁇ m or more from the viewpoint of better bending resistance of the multilayer structure of the present invention.
- the upper limit of the thickness of the layer (Z) is not particularly limited, but the effect of improving the bending resistance reaches saturation when the thickness is 1.0 ⁇ m or more. Therefore, it is economical that the upper limit of the thickness of the layer (Z) is 1.0 ⁇ m. Is preferable.
- the thickness of the layer (Z) can be controlled by the concentration of a coating liquid (V) described later used for forming the layer (Z) and the coating method.
- the base material which consists of various materials can be used.
- the material of the substrate (X) include resins such as thermoplastic resins and thermosetting resins; fiber aggregates such as fabrics and papers; wood; glass; metals; metal oxides and the like.
- the base material may have a composite structure or a multilayer structure made of a plurality of materials.
- the form of the substrate (X) is not particularly limited, and may be a layered substrate such as a film or a sheet, or may be various molded bodies having a three-dimensional shape such as a sphere, a polyhedron, and a pipe.
- the layered base material is particularly useful when a multilayer structure (laminated structure) is used for a packaging material for packaging food or the like, a solar cell member, or the like.
- the layered substrate examples include a thermoplastic resin film layer, a thermosetting resin film layer, a fiber polymer sheet (fabric, paper, etc.) layer, a wood sheet layer, a glass layer, an inorganic vapor deposition layer, and a metal foil layer.
- a single-layer or multi-layer substrate including at least one layer selected from the group examples include a substrate including at least one layer selected from the group consisting of a thermoplastic resin film layer, a paper layer, and an inorganic vapor deposition layer is preferable.
- the substrate may be a single layer or a plurality of layers. It may be a layer.
- a multilayer structure (laminated structure) using such a substrate is excellent in processability to a packaging material and various properties required for use as a packaging material.
- thermoplastic resin film forming the thermoplastic resin film layer examples include polyolefin resins such as polyethylene and polypropylene; polyester resins such as polyethylene terephthalate, polyethylene-2,6-naphthalate, polybutylene terephthalate, and copolymers thereof.
- Polyamide resins such as nylon-6, nylon-66, nylon-12; hydroxyl group-containing polymers such as polyvinyl alcohol and ethylene-vinyl alcohol copolymer; polystyrene; poly (meth) acrylate; polyacrylonitrile; polyacetic acid Polyvinylate; Polyarylate; Regenerated cellulose; Polyimide; Polyetherimide; Polysulfone; Polyethersulfone; Polyetheretherketone; Ionomer resin, etc. It can be mentioned films obtained by molding a thermoplastic resin. As a base material of a laminate used for a packaging material for packaging food or the like, a film made of polyethylene, polypropylene, polyethylene terephthalate, nylon-6, or nylon-66 is preferable.
- the thermoplastic resin film may be a stretched film or an unstretched film.
- a stretched film, particularly a biaxially stretched film is preferred because the processability (printing, laminating, etc.) of the resulting multilayer structure is excellent.
- the biaxially stretched film may be a biaxially stretched film produced by any one of a simultaneous biaxial stretching method, a sequential biaxial stretching method, and a tubular stretching method.
- Examples of paper used for the paper layer include kraft 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.
- a base material including a paper layer By using a base material including a paper layer, a multilayer structure for a paper container can be obtained.
- the inorganic vapor deposition layer preferably has a barrier property against oxygen gas or water vapor.
- a light shielding property such as a metal vapor deposition layer such as aluminum or a material having transparency can be appropriately used.
- the inorganic vapor-deposited layer can be formed by vapor-depositing an inorganic substance on the substrate, and the entire laminate in which the inorganic vapor-deposited layer is formed on the substrate can be used as the base material (X) having a multilayer structure. .
- Examples of the inorganic deposited layer having transparency include a layer formed from an inorganic oxide such as aluminum oxide, silicon oxide, silicon oxynitride, magnesium oxide, tin oxide, or a mixture thereof; silicon nitride, silicon carbonitride, etc.
- a layer formed from aluminum oxide, silicon oxide, magnesium oxide, and silicon nitride is preferable from the viewpoint of excellent barrier properties against oxygen gas and water vapor.
- the preferred thickness of the inorganic vapor deposition layer varies depending on the type of components constituting the inorganic vapor deposition layer, but is usually in the range of 2 to 500 nm. Within this range, a thickness that improves the barrier properties and mechanical properties of the multilayer structure may be selected. If the thickness of the inorganic vapor deposition layer is less than 2 nm, the reproducibility of the barrier property development of the inorganic vapor deposition layer with respect to oxygen gas or water vapor tends to decrease, and the inorganic vapor deposition layer may not exhibit sufficient barrier properties. is there.
- the thickness of the inorganic vapor deposition layer exceeds 500 nm, the barrier property of the inorganic vapor deposition layer tends to be lowered when the multilayer structure is pulled or bent.
- the thickness of the inorganic vapor deposition layer is more preferably in the range of 5 to 200 nm, and still more preferably in the range of 10 to 100 nm.
- Examples of the method for forming the inorganic vapor deposition layer include vacuum vapor deposition, sputtering, ion plating, and chemical vapor deposition (CVD).
- the vacuum evaporation method is preferable from the viewpoint of productivity.
- a heating method in performing vacuum vapor deposition any of an electron beam heating method, a resistance heating method, and an induction heating method is preferable.
- in order to raise the transparency of an inorganic vapor deposition layer you may employ
- the thickness thereof is preferably in the range of 1 to 1000 ⁇ m from the viewpoint of improving the mechanical strength and workability of the resulting multilayer structure, and is preferably 5 to 500 ⁇ m. More preferably, it is in the range of 9 to 200 ⁇ m.
- the layer (Y) and / or the layer (Z) may be laminated so as to be in direct contact with the substrate (X), but the substrate (X) and the layer (Y) And / or the layer (Y) and / or the layer (Z) may be laminated
- the adhesive layer (H) may be formed of an adhesive resin.
- the adhesive layer (H) made of an adhesive resin can be formed by treating the surface of the substrate (X) with a known anchor coating agent or applying a known adhesive to the surface of the substrate (X).
- a two-component reactive polyurethane adhesive in which a polyisocyanate component and a polyol component are mixed and reacted is preferable.
- adhesiveness may be further improved by adding a small amount of additives such as a known silane coupling agent to the anchor coating agent or adhesive.
- the silane coupling agent include silane coupling agents having a reactive group such as an isocyanate group, an epoxy group, an amino group, a ureido group, and a mercapto group.
- the multilayer structure of the present invention is subjected to processing such as printing and laminating. In this case, the deterioration of gas barrier properties and appearance can be more effectively suppressed.
- the strength of the multilayer structure of the present invention can be increased.
- the thickness of the adhesive layer (H) is preferably in the range of 0.03 to 0.18 ⁇ m. According to this configuration, when the multilayer structure of the present invention is subjected to processing such as printing or laminating, it is possible to more effectively suppress deterioration of gas barrier properties and appearance, and further, the multilayer structure of the present invention.
- the drop strength of the packaging material using the body can be increased.
- the thickness of the adhesive layer (H) is more preferably in the range of 0.04 to 0.14 ⁇ m, and further preferably in the range of 0.05 to 0.10 ⁇ m.
- the multilayer structure (laminate) of the present invention may be constituted only by the base material (X), the layer (Y) and the layer (Z), or the base material (X), the layer (Y), and the layer (Z ) And the adhesive layer (H) alone.
- the multilayer structure of the present invention may include a plurality of layers (Y) and / or a plurality of layers (Z).
- the multilayer structure of the present invention includes a member other than the substrate (X), the layer (Y), the layer (Z) and the adhesive layer (H) (for example, a thermoplastic resin film layer, a paper layer, an inorganic vapor deposition layer). Etc.) may be further included.
- the multilayer structure of the present invention having such other members can be formed by, for example, attaching the layer (Y) and the layer (Z) directly to the substrate (X) or via the adhesive layer (H). After laminating, it can be produced by further bonding or forming other members (other layers, etc.) directly or via an adhesive layer.
- the characteristics of the multilayer structure can be improved or new characteristics can be imparted. For example, heat-sealability can be imparted to the multilayer structure of the present invention, and barrier properties and mechanical properties can be further improved.
- the outermost surface layer of the multilayer structure of the present invention is a polyolefin layer
- heat sealability can be imparted to the multilayer structure or the mechanical properties of the multilayer structure can be improved.
- the polyolefin is preferably polypropylene or polyethylene.
- at least one film selected from the group consisting of a film made of polyester, a film made of polyamide, and a film made of a hydroxyl group-containing polymer is laminated as another layer. It is preferable.
- the polyester is preferably polyethylene terephthalate (PET), the polyamide is preferably nylon-6, and the hydroxyl group-containing polymer is preferably an ethylene-vinyl alcohol copolymer.
- PET polyethylene terephthalate
- the polyamide is preferably nylon-6
- the hydroxyl group-containing polymer is preferably an ethylene-vinyl alcohol copolymer.
- the multilayer structure of the present invention can be formed by laminating at least one pair of layers (Y) and (Z) and at least one other layer (including a base material).
- other layers include polyester layers, polyamide layers, polyolefin layers (which may be pigment-containing polyolefin layers, heat-resistant polyolefin layers, or biaxially stretched heat-resistant polyolefin layers), hydroxyl-containing polymer layers (for example, ethylene- Examples include a vinyl alcohol copolymer layer (hereinafter sometimes abbreviated as “EVOH layer”), a paper layer, an inorganic vapor deposition film layer, a thermoplastic elastomer layer, and an adhesive layer.
- EVOH layer vinyl alcohol copolymer layer
- the multilayer structure includes a base material, a layer (Y) and a layer (Z), and at least one pair of the layer (Y) and the layer (Z) is laminated adjacently, these other layers and layers (Y), the number of layers (Z) and the order of lamination are not particularly limited.
- at least one set of the base material (X), the layer (Y), and the layer (Z) is laminated in the order of the base material (X) / layer (Y) / layer (Z).
- a multilayer structure having a structure may be mentioned.
- these other layers can also be replaced with a molded body (molded body having a three-dimensional shape) made of the material.
- each layer may be replaced with a molded body (molded body having a three-dimensional shape) made of the material.
- the multilayer structure may have an adhesive layer such as an adhesive layer (H), but the description of the adhesive layer is omitted in the following specific examples.
- the layer (YZ) means a structure in which the layer (Y) and the layer (Z) are adjacently stacked, and the order is layer (Y) / layer (Z) or layer. Either (Z) / layer (Y) may be used.
- the thickness of the layer (Y) (when the multilayer structure has two or more layers (Y), the total thickness of each layer (Y)) is 2.0 ⁇ m or less (for example, 0.01 ⁇ m or more).
- the multilayer structure having a thickness of 2.0 ⁇ m or less satisfies the following performance.
- the details of the measurement conditions for oxygen permeability will be described in Examples.
- (Performance 1) The oxygen permeability under the conditions of 20 ° C. and 85% RH is 2 ml / (m 2 ⁇ day ⁇ atm) or less.
- Performance 2 The oxygen permeability under the condition of 20 ° C. and 85% RH after holding for 5 minutes in the state of 5% stretching under the condition of 23 ° C. and 50% RH is 4 ml / (m 2 ⁇ day ⁇ atm) or less. is there.
- the multilayer structure of the present invention is excellent in gas barrier properties, and can maintain gas barrier properties at a high level even when subjected to physical stress such as deformation or impact. Moreover, according to the present invention, a multilayer structure having an excellent appearance can be obtained. Therefore, the multilayer structure of the present invention can be applied to various uses.
- the product including the multilayer structure of the present invention may be a product including the multilayer structure as a packaging material or a member of an electronic device that is a solar cell, a display, or a lighting device.
- the packaging material may be a molded product or may have a bag shape.
- the member of the electronic device is, for example, a protective sheet that protects the surface of the electronic device body.
- the multilayer structure of the present invention can also have a barrier property against water vapor.
- the water vapor barrier property even when subjected to physical stress such as deformation or impact. Can be maintained at a high level.
- this characteristic may greatly contribute to the durability of the product.
- the multilayer structure of the present invention is particularly preferably used as a packaging material.
- uses other than packaging materials include LCD substrate films, organic EL substrate films, electronic paper substrate films, electronic device sealing films, PDP film and other display members, LED films, and IC tag films.
- a display member for example, it is used as a low reflective film.
- the packaging material of the present invention can be applied to various applications, and is preferably used for applications that require barrier properties against oxygen and for applications in which the inside of the packaging material is replaced with various functional gases.
- the packaging material of the present invention is preferably used as a food packaging material. When used as a packaging material for food, it is particularly preferably used in a form having a fold, such as a stand-up pouch.
- the packaging material of the present invention is preferably used as a packaging material for packaging chemicals such as agricultural chemicals and pharmaceuticals; medical equipment; industrial materials such as machine parts and precision materials; and clothing. Can do.
- the packaging material of the present invention can be used after being processed into various molded products.
- a molded product may be a molded container, a vertical bag filling and sealing bag, a vacuum packaging bag, a pouch such as a pouch with a spout, a laminated tube container, an infusion bag, a container lid, a paper container or a vacuum insulator. Good.
- These packaging materials have a partition that separates the inside and the outside for holding the contents, and this partition includes the multilayer structure of the present invention.
- the molded container includes a base material molded in advance into a predetermined shape, more specifically, an interior (internal space) for containing contents, and a gas barrier coating formed on the base material.
- the base material and the gas barrier coating constitute a partition wall.
- the molded container typically has a shape such as a bottle or a tank.
- the base material is usually molded so as to have an opening for introducing the contents into the internal space.
- the vertical bag-filling sealing bag is a bag obtained by making a film material with a vertical bag-making and filling machine (also called a vertical bag-making and filling machine).
- the vertical bag making and filling machine forms, for example, a bag whose upper side is opened by sealing (joining) its side and bottom while holding the supplied film material so that the opposing surfaces are formed. An object is supplied from above the bag and filled therein. Subsequently, the vertical bag making and filling machine seals the upper part of the bag and then cuts the upper part of the bag, and discharges it as a vertical bag making and filling sealed bag.
- the vertical bag making and filling machine enables sanitary and efficient bag making with few opportunities for human involvement.
- 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 film material In the vertical bag-filling-seal bag, the film material has a multilayer structure and constitutes a partition wall.
- the vacuum packaging bag is a bag that is used in a state where the inside of the bag is decompressed. Since the inside of the bag is depressurized, the vacuum packaging bag is usually deformed so that the film material separating the inside of the bag and the outside of the bag is in contact with the contents contained in the bag.
- the contents are typically foods such as corn with shafts, beans, rice cakes, strawberries, chestnuts, tea leaves, meat, fish, confectionery and the like.
- the film material has a multilayer structure and constitutes a partition wall.
- a pouch is a container provided with a film material as a partition wall that separates the inside and the outside that contain the contents.
- Pouches are suitable for containing liquid or slurry contents, but can also be used to contain solid contents.
- the contents are typically beverages, seasonings, liquid foods and other foods, and detergents, liquid soaps and other daily necessities.
- the pouch with a spout includes a main body formed using a film material, and a spout with a lid attached to an upper portion of the main body.
- a pouch with a chuck seal in which a chuck seal is provided at the peripheral edge of the main body instead of the spout with a lid is also known.
- a pouch having a bottom wall that gives the pouch self-supporting properties is called a stand-up pouch (standing pouch).
- Gusseted pouches with gussets are also manufactured.
- the flat pouch is manufactured by bonding film materials to each other at the peripheral seal portion.
- two film materials may be joined at the four peripheral edges, or the three peripheral edges may be sealed in a state in which one film material is folded.
- the laminate tube container includes a body part provided with a laminate film as a partition wall that separates the inside and the outside of the container, and a pouring part for taking out the contents accommodated inside the container.
- the body portion of the laminate tube container has, for example, a cylindrical shape with one end closed, and a pouring portion is disposed on the other end side.
- a laminated film material film material has a multilayer structure.
- the infusion bag is a bag (bag) for containing infusions such as amino acid infusions, electrolyte infusions, saccharide infusions, and infusion fat emulsions as contents.
- the infusion bag may be provided with a plug member in addition to the bag body that contains the contents.
- the infusion bag may be provided with a hanging hole for hanging the bag.
- the film material that separates the inside and the outside for housing the infusion is provided with a multilayer structure.
- the container lid material includes a film material that functions as part of a partition wall that separates the inside of the container from the outside of the container in a state where the container is formed in combination with the container body.
- the container lid material is a container (with a lid) that has a space sealed inside by being combined with the container body so as to seal the opening of the container body by heat sealing, bonding (sealing) using an adhesive, or the like.
- Container The container lid is usually joined to the container main body at the peripheral edge thereof. In this case, the center part surrounded by the peripheral part faces the internal space of the container.
- the container body is, for example, a molded body having a cup shape, a tray shape, or other shapes, and includes a flange portion, a wall surface portion, and the like for sealing the container lid.
- the paper container is a container in which a partition that separates the inside and the outside containing the contents includes a paper layer.
- the paper container has, for example, a shape such as a gable top type or a brick type. These shapes are provided with a bottom wall portion for self-supporting the paper container.
- the vacuum heat insulator is a heat insulator that includes a covering material and a core material disposed inside the covering material, and the inside where the core material is disposed is decompressed.
- the core material that can be used include powders such as pearlite powder, fiber materials such as glass wool, resin foams such as urethane foam, hollow containers, and honeycomb structures.
- the covering material that functions as a partition includes a multilayer structure.
- heat sealing may be performed.
- the seal of the body portion is usually a palm-sealed seal.
- the seal of the body part is usually an envelope sticker.
- a polyolefin layer hereinafter sometimes referred to as “PO layer” is preferable.
- the product including the multilayer structure of the present invention may be an electronic device provided with a protective sheet.
- This product includes an electronic device body and a protective sheet that protects the surface of the electronic device body.
- the electronic device may include an electronic device body, a sealing material for sealing the electronic device body, and a protective sheet for protecting the surface of the electronic device body.
- the sealing material covers the entire surface of the electronic device body 1.
- the protective sheet is disposed on at least one surface of the electronic device body via the sealing material.
- a protective sheet may be disposed on the surface of the electronic device body opposite to the surface via a sealing material.
- an electronic device main body is not specifically limited, For example, it is lighting apparatuses, such as photoelectric conversion apparatuses, such as a solar cell, information display apparatuses, such as an organic EL display, a liquid crystal display, and electronic paper, and an organic EL light emitting element.
- the sealing material is an arbitrary member that is appropriately added according to the type and application of the electronic device body, and EVA (ethylene-vinyl acetate resin), PVB (polyvinyl butyral), or the like is used.
- the multilayer film including the base material (X) and the layer (YZ) laminated on the base material (X) may be referred to as a barrier multilayer film.
- This barrier multilayer film is also a kind of multilayer structure of the present invention. Layers for imparting various characteristics (for example, heat sealability) may be laminated on the barrier multilayer film.
- the multilayer structure of the present invention may have a configuration of barrier multilayer film / adhesive layer / polyolefin layer or polyolefin layer / adhesive layer / barrier multilayer film / adhesive layer / polyolefin layer. That is, the multilayer structure of the present invention may include a polyolefin layer disposed on one outermost surface.
- the multilayer structure of the present invention may include a first polyolefin layer disposed on one outermost surface and a second polyolefin layer disposed on the other outermost surface.
- the first polyolefin layer and the second polyolefin layer may be the same or different.
- the vertical bag-filling seal bag may be formed by laminating at least one barrier multilayer film and at least one other layer.
- other layers include a polyester layer, a polyamide layer, a polyolefin layer, a paper layer, an inorganic vapor deposition film layer, an EVOH layer, and an adhesive layer.
- the number of these layers and the order of lamination are not particularly limited, but when heat sealing is performed, a configuration for that is adopted.
- the structure of the multilayer structure particularly preferable as the vertical bag-filling-seal bag is a structure of barrier multilayer film / polyamide layer / PO layer, barrier multilayer film / PO layer, PO layer / barrier multilayer film / PO layer. It is done.
- a polyamide film can be used as the base material of the barrier multilayer film.
- the vertical bag-filling-sealed seal bag maintains its gas barrier property even when subjected to physical stress such as deformation or impact.
- An adhesive layer may be provided between the layers constituting the vertical bag-filling seal bag.
- the layer (YZ) of the multilayer structure of the present invention is on one side of the base material, the layer (YZ) may face either the outside or the inside of the vertical bag-filling sealing bag.
- the molded product containing the multilayer structure of the present invention may be a vacuum packaging bag for packaging food containing solids.
- the vacuum packaging bag has excellent gas barrier properties, and the gas barrier properties are maintained even when subjected to physical stress such as deformation or impact. Therefore, the vacuum packaging bag has almost no deterioration in gas barrier properties over a long period of time. Since the vacuum packaging bag is flexible and easily adheres to foods containing solids, it can be easily deaerated during vacuum packaging. Therefore, the vacuum packaging bag can reduce the residual oxygen in the vacuum packaging body, and is excellent in food long-term storage. In addition, after vacuum packaging, a squared or bent portion is less likely to occur, so that defects such as pinholes and cracks are less likely to occur.
- this vacuum packaging bag can suppress that pinhole generate
- the vacuum packaging bag has excellent gas barrier properties, and even when subjected to physical stress such as deformation or impact, the gas barrier properties are maintained, so that deterioration of the quality of the contents (for example, food) can be suppressed over a long period of time. it can.
- the vacuum packaging bag may be formed by laminating at least one barrier multilayer film and at least one other layer.
- other layers include a polyester layer, a polyamide layer, a polyolefin layer, an inorganic vapor deposition film layer, an EVOH layer, and an adhesive layer.
- the number of these layers and the order of lamination are not particularly limited, but when heat sealing is performed, a configuration for that is adopted.
- Examples of the structure of the multilayer structure particularly preferable as a vacuum packaging bag include a structure of barrier multilayer film / polyamide layer / PO layer and polyamide layer / barrier multilayer film / PO layer.
- a polyamide film can be used as the base material of the barrier multilayer film.
- a vacuum packaging bag using such a multilayer structure is particularly excellent in gas barrier properties after vacuum packaging or after vacuum packaging and heat sterilization.
- An adhesive layer may be provided between the layers.
- the molded product containing the multilayer structure of the present invention may be a pouch with a spout that wraps various liquid substances.
- the pouch with a spout can be used as a container for liquid drinks (for example, soft drinks), jelly drinks, yogurts, fruit sauces, seasonings, functional water, and liquid foods.
- the pouch with spout can also be preferably used as a container for liquid pharmaceuticals such as amino acid infusions, electrolyte infusions, saccharide infusions, and fat emulsions for infusion.
- the pouch with a spout is excellent in gas barrier properties, and the gas barrier properties are maintained even when subjected to physical stress such as deformation or impact.
- the pouch with a spout it is possible to prevent the contents from being altered even after transportation and after long-term storage. Moreover, since this pouch with a spout is excellent in transparency, it is easy to check the contents and the quality of the contents due to deterioration.
- the pouch with a spout may be formed by laminating at least one barrier multilayer film and at least one other layer.
- other layers include a polyester layer, a polyamide layer, a polyolefin layer, an inorganic vapor deposition film layer, an EVOH layer, and an adhesive layer.
- the number of these layers and the order of lamination are not particularly limited, but when heat sealing is performed, a configuration for that is adopted.
- Examples of the structure of the multilayer structure particularly preferable as a pouch with a spout include a structure of barrier multilayer film / polyamide layer / PO layer and polyamide layer / barrier multilayer film / PO layer.
- An adhesive layer may be provided between the layers.
- a layer (YZ) may be in the outer side of a pouch with a spout with respect to a base material, and may exist inside.
- the molded product including the multilayer structure of the present invention may be a laminated tube container for packaging cosmetics, drugs, pharmaceuticals, foods, toothpastes and the like.
- the laminated tube container has excellent gas barrier properties, and the gas barrier properties are maintained even when subjected to physical stress such as deformation or impact.
- the laminated tube container has good transparency, it is easy to confirm the contents and the deterioration of the contents due to deterioration.
- the laminate tube container may be formed by laminating at least one barrier multilayer film and at least one other layer.
- other layers include a polyamide layer, a polyolefin layer (which may be a pigment-containing polyolefin layer), an inorganic vapor deposition film layer, an EVOH layer, and an adhesive layer.
- the number of these layers and the order of lamination are not particularly limited, but when heat sealing is performed, a configuration for that is adopted.
- Particularly preferred configurations for the laminate tube container include PO layer / barrier multilayer film / PO layer and PO layer / pigment-containing PO layer / PO layer / barrier multilayer film / PO layer.
- An adhesive layer may be disposed between the layers.
- a layer (YZ) may be in the outer side of a laminate tube container with respect to a base material, and may exist inside.
- the molded article containing the multilayer structure of the present invention may be an infusion bag.
- an infusion bag filled with a liquid medicine such as an amino acid infusion, an electrolyte infusion, a saccharide infusion, or a fat emulsion for infusion. It may be.
- the infusion bag has excellent gas barrier properties, and the gas barrier properties are maintained even when subjected to physical stress such as deformation or impact. Therefore, according to the infusion bag, it is possible to prevent the filled liquid medicine from being deteriorated before the heat sterilization treatment, during the heat sterilization treatment, after the heat sterilization treatment, after transportation, and after storage.
- the infusion bag may be formed by laminating at least one barrier multilayer film and at least one other layer.
- other layers include polyamide layers, polyolefin layers, inorganic vapor deposition film layers, EVOH layers, thermoplastic elastomer layers, and adhesive layers.
- the number of these layers and the order of lamination are not particularly limited, but when heat sealing is performed, a configuration for that is adopted.
- Examples of the structure of the multilayer structure particularly preferable as an infusion bag include a structure of barrier multilayer film / polyamide layer / PO layer and polyamide layer / barrier multilayer film / PO layer.
- An adhesive layer may be disposed between the layers.
- a layer (YZ) may exist in the outer side of an infusion bag with respect to a base material, and may exist inside.
- the molded product including the multilayer structure of the present invention may be a lid material for a container filled with food products such as processed meat products, processed vegetable products, processed fishery products, and fruits.
- the container lid material is excellent in gas barrier properties, and the gas barrier properties are maintained even when subjected to physical stress such as deformation or impact, so that deterioration of the quality of food as a content can be suppressed over a long period of time.
- cover material is preferably used as a lid
- the container lid may be formed by laminating at least one barrier multilayer film and at least one other layer.
- other layers include a polyamide layer, a polyolefin layer, an inorganic vapor deposition film layer, an EVOH layer, a polyester layer, a paper layer, and an adhesive layer.
- the number of these layers and the order of lamination are not particularly limited, but when heat sealing is performed, a configuration for that is adopted.
- a configuration of barrier multilayer film / polyamide layer / PO layer and barrier multilayer film / PO layer may be mentioned.
- a polyamide film can be used as the base material of the barrier multilayer film.
- An adhesive layer may be provided between the layers.
- the layer (YZ) of the multilayer structure is on one side of the base material, the layer (YZ) may be on the inner side (container side) than the base material, or on the outer side of the base material. Good.
- the molded product including the multilayer structure of the present invention may be a paper container. Even when the paper container is bent, the gas barrier property is hardly lowered. Moreover, since the transparency of a layer (YZ) is favorable, this paper container is preferably used for a container with a window. Furthermore, the paper container is suitable for heating by a microwave oven.
- the paper container may be formed by laminating at least one barrier multilayer film and at least one other layer.
- other layers include polyester layers, polyamide layers, polyolefin layers (which may be heat resistant polyolefin layers or biaxially stretched heat resistant polyolefin layers), inorganic vapor deposited film layers, hydroxyl group-containing polymer layers, paper layers, and Includes an adhesive layer.
- the number of these layers and the order of lamination are not particularly limited, but when heat sealing is performed, a configuration for that is adopted.
- the multilayer structure particularly preferable as a paper container
- a configuration of heat resistant polyolefin layer / paper layer / heat resistant polyolefin layer / barrier multilayer film / heat resistant polyolefin layer may be mentioned.
- An adhesive layer may be disposed between the layers.
- the heat resistant polyolefin layer is composed of, for example, either a biaxially stretched heat resistant polyolefin film or an unstretched heat resistant polyolefin film.
- the heat-resistant polyolefin layer disposed in the outermost layer of the multilayer structure is preferably an unstretched polypropylene film.
- the heat-resistant polyolefin layer disposed inside the outermost layer of the multilayer structure is preferably an unstretched polypropylene film.
- all heat-resistant polyolefin layers constituting the multilayer structure are unstretched polypropylene films.
- the molded product including the multilayer structure of the present invention may be a vacuum heat insulator that can be used for various applications that require cold insulation or heat insulation. Since the vacuum insulator can maintain a heat insulating effect over a long period of time, it is a heat insulating material for homes used for household appliances such as a refrigerator, a hot water supply facility, and a rice cooker, a heat insulating material for a house, a wall portion, a ceiling portion, an attic portion and a floor portion. It can be used for heat insulation panels such as wood, vehicle roofing and vending machines.
- the vacuum heat insulator may be formed by laminating at least one barrier multilayer film and at least one other layer.
- other layers include a polyester layer, a polyamide layer, a polyolefin layer, and an adhesive layer.
- the number of these layers and the order of lamination are not particularly limited, but when heat sealing is performed, a configuration for that is adopted.
- Examples of the structure of the multilayer structure particularly preferable as the vacuum heat insulator include the structures of barrier multilayer film / polyamide layer / PO layer and polyamide layer / barrier multilayer film / PO layer.
- An adhesive layer may be provided between the layers.
- a layer (YZ) may exist in the outer side of a vacuum heat insulating body with respect to a base material, and may exist inside.
- the manufacturing method of the multilayer structure of this invention is demonstrated. According to this method, the multilayer structure of the present invention can be easily produced. Since the materials used in the method for producing a multilayer structure of the present invention, the configuration of the multilayer structure, and the like are the same as those described above, description of overlapping portions may be omitted.
- the multilayer of the present invention is applied to the substrate (X), the layer (Y), the layer (Z), the metal oxide (A), the phosphorus compound (B), the polymer (C) and the polymer (E). The description in the description of the structure can be applied.
- the matter which demonstrated this manufacturing method is applicable to the multilayer structure of this invention. The matters described for the multilayer structure of the present invention can be applied to the production method of the present invention.
- the production method of the present invention is a method for producing a multilayer structure having one or more base materials (X), layers (Y) and layers (Z).
- Layer (Y) contains aluminum atoms.
- the layer (Z) includes a polymer (E) having a plurality of phosphorus atoms. At least one set of layer (Y) and layer (Z) are laminated adjacent to each other.
- the production method of the present invention includes a step (IV) of forming a layer (Z) by applying a coating liquid (V) containing a polymer (E) having a plurality of phosphorus atoms.
- the layer (Y) included in the multilayer structure of the present invention is a layer (YB) that is an aluminum deposition layer or a layer (YC) that is an aluminum oxide deposition layer
- the layer (YB) and the layer Since (YC) can be formed by the general vapor deposition method described above, detailed description thereof is omitted.
- the layer (Y) of the multilayer structure of the present invention is a layer (YA) containing a reaction product (R) formed by reacting a metal oxide (A) containing at least aluminum with a phosphorus compound (B). ) Will be described in detail.
- the formation method (process (IV) mentioned later) of a layer (Z) when the layer (Y) is any of a layer (YA), a layer (YB), and a layer (YC), the same formation method Can be adopted.
- the layer (Y) of the multilayer structure of the present invention is a layer (YA) containing a reaction product (R) formed by a reaction between a metal oxide (A) containing at least aluminum and a phosphorus compound (B).
- the method for producing a multilayer structure of the present invention includes steps (I), (II), (III) and (IV).
- a metal oxide (A) containing at least aluminum, at least one compound containing a site capable of reacting with the metal oxide (A), and a solvent are mixed with each other to obtain a metal oxide.
- a coating liquid (U) containing the at least one compound and the solvent is prepared.
- step (II) a coating layer (U) is applied on the substrate (X) to form a precursor layer of the layer (YA) on the substrate (X).
- step (III) the precursor layer is heat-treated at a temperature of 110 ° C. or higher to form a layer (YA) on the substrate (X).
- step (IV) the layer (Z) is formed by applying a coating liquid (V) containing a polymer (E) having a plurality of phosphorus atoms.
- step (IV) may be carried out before step (II). Further, as will be described later, step (III) can be performed after step (IV).
- the at least one compound containing a site capable of reacting with the metal oxide (A) used in the step (I) may be referred to as “at least one compound (Z)”.
- at least the metal oxide (A), at least one compound (Z), and a solvent are mixed.
- a raw material containing the metal oxide (A) and at least one compound (Z) is reacted in a solvent.
- the raw material may contain other compounds in addition to the metal oxide (A) and at least one compound (Z).
- the metal oxide (A) is mixed in the form of particles.
- the number of moles N M of metal atoms (M) constituting the metal oxide (A) and the number of moles N P of phosphorus atoms contained in the phosphorus compound (B) are 1.0 ⁇
- the relationship of (number of moles N M ) / (number of moles N P ) ⁇ 3.6 is satisfied. Since the preferable range of the value of (number of moles N M ) / (number of moles N P ) has been described above, redundant description is omitted.
- the at least one compound (Z) includes a phosphorus compound (B).
- the number of moles of metal atoms contained in at least one compound (Z) is preferably in the range of 0 to 1 times the number of moles of phosphorus atoms contained in the phosphorus compound (B).
- the at least one compound (Z) is a compound containing a plurality of sites capable of reacting with the metal oxide (A), and the number of moles of metal atoms contained in the at least one compound (Z). Is in the range of 0 to 1 times the number of moles of phosphorus atoms contained in the phosphorus compound (B).
- the ratio of (number of moles of metal atoms contained in at least one compound (Z)) / (number of moles of phosphorus atoms contained in phosphorus compound (B)) is in the range of 0 to 1 (for example, from 0 to 0.9 By setting the range, a multilayer structure having more excellent gas barrier properties can be obtained.
- This ratio is preferably 0.3 or less, more preferably 0.05 or less, further preferably 0.01 or less, in order to further improve the gas barrier properties of the multilayer structure. It may be.
- at least one compound (Z) consists only of the phosphorus compound (B). In step (I), the ratio can be easily reduced.
- Step (I) preferably includes the following steps (a) to (c).
- Step (a) A step of preparing a liquid (S) containing the metal oxide (A).
- Step (b) A step of preparing a solution (T) containing the phosphorus compound (B).
- Step (c) A step of mixing the liquid (S) obtained in the steps (a) and (b) and the solution (T).
- Step (b) may be performed prior to step (a), may be performed simultaneously with step (a), or may be performed after step (a).
- step (a) may be performed prior to step (a), may be performed simultaneously with step (a), or may be performed after step (a).
- a liquid (S) containing a metal oxide (A) is prepared.
- the liquid (S) is a solution or a dispersion.
- the liquid (S) can be prepared, for example, by a technique adopted in a known sol-gel method.
- the above-mentioned compound (L) component, water, and an acid catalyst or an organic solvent as necessary are mixed, and the compound (L) component is condensed or hydrolyzed by a method employed in a known sol-gel method.
- the dispersion of the metal oxide (A) obtained by condensing or hydrolyzing the compound (L) component can be used as it is as the liquid (S) containing the metal oxide (A).
- a specific treatment such as peptization as described above, addition or subtraction of a solvent for concentration control
- Step (a) may include a step of condensing (for example, hydrolytic condensation) at least one selected from the group consisting of compound (L) and a hydrolyzate of compound (L).
- the step (a) includes compound (L), partial hydrolyzate of compound (L), complete hydrolyzate of compound (L), partial hydrolyzed condensate of compound (L), and compound (L
- a step of condensing or hydrolyzing at least one selected from the group consisting of a part of the complete hydrolyzate of L) condensed may be included.
- another example of the method for preparing the liquid (S) includes a method including the following steps. First, metal is vaporized as a metal atom by thermal energy, and the metal atom is brought into contact with a reactive gas (oxygen) to generate metal oxide molecules and clusters. Then, the metal oxide (A) particle
- the bulk metal oxide (A) is pulverized using a pulverizer such as a ball mill or a jet mill, and dispersed in water or an organic solvent.
- a pulverizer such as a ball mill or a jet mill
- the method of setting it as liquid (S) can be mentioned.
- alcohol such as methanol, ethanol, isopropanol, and normal propanol, is used suitably.
- the content of the metal oxide (A) in the liquid (S) is preferably in the range of 0.1 to 40% by mass, more preferably in the range of 1 to 30% by mass. More preferably, it is within the range of 20% by mass.
- a solution (T) containing the phosphorus compound (B) is prepared.
- the solution (T) can be prepared by dissolving the phosphorus compound (B) in a solvent.
- dissolution may be promoted by heat treatment or ultrasonic treatment.
- the solvent used for preparing the solution (T) may be appropriately selected according to the type of the phosphorus compound (B), but preferably contains water.
- the solvent is alcohol such as methanol and ethanol; ether such as tetrahydrofuran, dioxane, trioxane and dimethoxyethane; ketone such as acetone and methyl ethyl ketone; glycol such as ethylene glycol and propylene glycol, as long as the dissolution of the phosphorus compound (B) is not hindered.
- Glycol derivatives such as methyl cellosolve, ethyl cellosolve, n-butyl cellosolve; glycerin; acetonitrile; amides such as dimethylformamide; dimethyl sulfoxide; sulfolane and the like.
- the content of the phosphorus compound (B) in the solution (T) is preferably in the range of 0.1 to 99% by mass, more preferably in the range of 0.1 to 95% by mass, More preferably, it is in the range of 1 to 90% by mass. Further, the content of the phosphorus compound (B) in the solution (T) may be in the range of 0.1 to 50% by mass, in the range of 1 to 40% by mass, It may be in the range of 30% by mass.
- step (c) the liquid (S) and the solution (T) are mixed.
- the solution (T) may be added to the stirring liquid (S), or the liquid (S) may be added to the stirring solution (T).
- the temperature of the liquid (S) and the temperature of the solution (T) are both preferably 50 ° C. or less, more preferably 30 ° C. or less, and both 20 ° C. More preferably, it is as follows. By setting the temperature at the time of mixing to 50 ° C.
- the metal oxide (A) and the phosphorus compound (B) are uniformly mixed, and the gas barrier properties of the resulting multilayer structure can be improved. Furthermore, the coating liquid (U) excellent in storage stability may be obtained by continuing stirring for about 30 minutes after the completion of mixing.
- the coating liquid (U) may contain a polymer (C).
- the method for including the polymer (C) in the coating liquid (U) is not particularly limited.
- the polymer (C) may be dissolved in the liquid (S), the solution (T), or the liquid mixture of the liquid (S) and the solution (T) after being added in the form of powder or pellets.
- the polymer (C) solution may be added to and mixed with the liquid (S), the solution (T), or the liquid mixture of the liquid (S) and the solution (T).
- the liquid (S) and the solution (T) are mixed in the step (c) by containing the polymer (C) in either the liquid (S) or the solution (T).
- the reaction rate between the metal oxide (A) and the phosphorus compound (B) is relaxed, and as a result, a coating liquid (U) having excellent temporal stability may be obtained.
- the coating liquid (U) contains the polymer (C)
- a multilayer structure including the layer (YA) containing the polymer (C) can be easily produced.
- the coating liquid (U) may contain at least one acid compound (D) selected from acetic acid, hydrochloric acid, nitric acid, trifluoroacetic acid, and trichloroacetic acid, if necessary.
- the at least one acid compound (D) may be simply referred to as “acid compound (D)”.
- the method for including the acid compound (D) in the coating liquid (U) is not particularly limited.
- the acid compound (D) may be added as it is to the liquid (S), the solution (T), or the liquid mixture of the liquid (S) and the solution (T) and mixed.
- the acid compound (D) solution may be added to and mixed with the liquid (S), the solution (T), or the liquid mixture of the liquid (S) and the solution (T).
- you may add and mix the liquid (S), the solution (T), or the liquid mixture of a liquid (S) and a solution (T) to the solution of an acid compound (D).
- the liquid (S) or the solution (T) contains the acid compound (D), whereby the liquid (S) and the solution (T) are mixed in the step (c).
- the reaction rate between the metal oxide (A) and the phosphorus compound (B) is relaxed, and as a result, a coating liquid (U) having excellent temporal stability may be obtained.
- the coating liquid (U) containing the acid compound (D) In the coating liquid (U) containing the acid compound (D), the reaction between the metal oxide (A) and the phosphorus compound (B) is suppressed, and the precipitation and aggregation of the reaction product in the coating liquid (U) are suppressed. can do. Therefore, the appearance of the obtained multilayer structure may be improved by using the coating liquid (U) containing the acid compound (D). Moreover, since the boiling point of the acid compound (D) is 200 ° C. or less, the acid compound (D) can be easily removed from the layer (YA) by volatilizing the acid compound (D) in the production process of the multilayer structure. Can be removed.
- the content of the acid compound (D) in the coating liquid (U) is preferably in the range of 0.1 to 5.0% by mass, and preferably in the range of 0.5 to 2.0% by mass. More preferred. Within these ranges, the effect of adding the acid compound (D) can be obtained, and the acid compound (D) can be easily removed. When the acid component remains in the liquid (S), the addition amount of the acid compound (D) may be determined in consideration of the residual amount.
- the liquid obtained by mixing in the step (c) can be used as it is as the coating liquid (U).
- the solvent contained in the liquid (S) or solution (T) is usually the solvent for the coating liquid (U).
- the coating liquid (U) may be prepared by treating the liquid obtained by mixing in the step (c). For example, treatments such as addition of an organic solvent, pH adjustment, viscosity adjustment, and additive addition may be performed.
- An organic solvent may be added to the liquid obtained by mixing in the step (c) as long as the stability of the resulting coating liquid (U) is not inhibited.
- the addition of the organic solvent may facilitate the application of the coating liquid (U) to the substrate (X) in the step (II).
- an organic solvent what is mixed uniformly in the coating liquid (U) obtained is preferable.
- preferable organic solvents include, for example, alcohols such as methanol, ethanol, n-propanol and isopropanol; ethers such as tetrahydrofuran, dioxane, trioxane and dimethoxyethane; ketones such as acetone, methyl ethyl ketone, methyl vinyl ketone and methyl isopropyl ketone; Examples include glycols such as ethylene glycol and propylene glycol; glycol derivatives such as methyl cellosolve, ethyl cellosolve, and n-butyl cellosolve; glycerin; acetonitrile; amides such as dimethylformamide and dimethylacetamide; dimethyl sulfoxide;
- the solid content concentration of the coating liquid (U) is preferably in the range of 1 to 20% by mass. It is more preferably in the range of 2 to 15% by mass, and further preferably in the range of 3 to 10% by mass.
- the solid content concentration of the coating liquid (U) is determined by, for example, adding a predetermined amount of the coating liquid (U) to the petri dish, removing volatiles such as a solvent at 100 ° C. together with the petri dish, and calculating the mass of the remaining solid content. It can be calculated by dividing by the mass of the coating liquid (U) added first.
- the solid content concentration is defined as the mass of the remaining solids when the mass difference between the two consecutive masses reaches a negligible level. It is preferable to calculate.
- the pH of the coating liquid (U) is preferably in the range of 0.1 to 6.0, preferably 0.2 to 5.0. More preferably, it is in the range of 0.5 to 4.0.
- the pH of the coating liquid (U) can be adjusted by a known method, for example, by adding an acidic compound or a basic compound.
- acidic compounds include hydrochloric acid, nitric acid, sulfuric acid, acetic acid, butyric acid, and ammonium sulfate.
- basic compounds include sodium hydroxide, potassium hydroxide, ammonia, trimethylamine, pyridine, sodium carbonate, and sodium acetate.
- the state of the coating liquid (U) changes with time, and eventually becomes a gel-like composition or tends to precipitate.
- the time until the state changes as such depends on the composition of the coating liquid (U).
- the viscosity of the coating liquid (U) is stable over a long period of time.
- the solution (U) had a viscosity measured with a Brookfield viscometer (B-type viscometer: 60 rpm) even after standing at 25 ° C. for 2 days, with the viscosity at the completion of step (I) as the reference viscosity. It is preferable to prepare so that it may become within 5 times the viscosity.
- a multilayer structure having excellent storage stability and more excellent gas barrier properties is often obtained.
- a method of adjusting the viscosity of the coating liquid (U) to be within the above range for example, a method of adjusting the concentration of solid content, adjusting pH, or adding a viscosity modifier can be employed.
- viscosity modifiers include carboxymethyl cellulose, starch, bentonite, tragacanth gum, stearate, alginate, methanol, ethanol, n-propanol, and isopropanol.
- the coating liquid (U) may contain a substance other than the substances described above.
- the coating liquid (U) is an inorganic metal salt such as carbonate, hydrochloride, nitrate, hydrogen carbonate, sulfate, hydrogen sulfate, borate, aluminate; oxalate, acetate, tartrate Organic acid metal salts such as stearates; metal complexes such as acetylacetonate metal complexes (such as aluminum acetylacetonate), cyclopentadienyl metal complexes (such as titanocene), cyano metal complexes; layered clay compounds; It may contain a polymer compound other than the polymer (C); a plasticizer; an antioxidant; an ultraviolet absorber;
- a coating layer (U) is applied on the substrate (X) to form a precursor layer of the layer (YA) on the substrate (X).
- the coating liquid (U) may be applied directly on at least one surface of the substrate (X).
- 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).
- the adhesive layer (H) may be formed on the surface of the substrate (X).
- the precursor of a layer (YA) is formed on a layer (Z) by apply
- a body layer can also be formed.
- the coating liquid (U) may be deaerated and / or defoamed as necessary.
- a method of deaeration and / or defoaming treatment for example, there are methods by evacuation, heating, centrifugation, ultrasonic waves, etc., but a method including evacuation can be preferably used.
- the viscosity of the coating liquid (U) applied in step (II) and measured with a Brookfield rotational viscometer (SB type viscometer: rotor No. 3, rotational speed 60 rpm)
- the temperature is preferably 3000 mPa ⁇ s or less, and more preferably 2000 mPa ⁇ s or less.
- the viscosity of the coating liquid (U) when applied in the step (II) can be adjusted by the concentration, temperature, stirring time after mixing in the step (c) and stirring strength. For example, in some cases, the viscosity can be lowered by lengthening the stirring after mixing in the step (c).
- the method for applying the coating liquid (U) on the substrate (X) is not particularly limited, and a known method can be adopted.
- Preferred methods include, for example, a casting method, a dipping method, a roll coating method, a gravure coating method, a screen printing method, a reverse coating method, a spray coating method, a kiss coating method, a die coating method, a metalling bar coating method, and a chamber doctor combined coating method. , Curtain coating method, bar coating method and the like.
- the precursor layer of the layer (YA) is formed by removing the solvent in the coating liquid (U).
- a well-known drying method is applicable. Specifically, drying methods such as a hot air drying method, a hot roll contact method, an infrared heating method, and a microwave heating method can be applied alone or in combination.
- the drying temperature is preferably 0 to 15 ° C. or lower than the flow start temperature of the substrate (X).
- the coating liquid (U) contains the polymer (C)
- the drying temperature is preferably 15 to 20 ° C. lower than the thermal decomposition start temperature of the polymer (C).
- the drying temperature is preferably in the range of 70 to 200 ° C, more preferably in the range of 80 to 180 ° C, and further preferably in the range of 90 to 160 ° C.
- the removal of the solvent may be carried out under normal pressure or reduced pressure. Further, the solvent may be removed by a heat treatment in step (III) described later.
- the coating liquid (U) is applied to one surface of the substrate (X), and then the first layer ( First layer (YA) precursor layer) and then applying the coating liquid (U) to the other surface of the substrate (X), and then removing the solvent to remove the second layer (first layer). 2 layers (YA) precursor layers) may be formed.
- the composition of the coating liquid (U) applied to each surface may be the same or different.
- a layer (a precursor layer of the layer (YA)) may be formed for each surface by the above method. Or you may form a several layer (precursor layer of a layer (YA)) simultaneously by apply
- step (III) the layer (YA) is formed by heat-treating the precursor layer (precursor layer of layer (YA)) formed in step (II) at a temperature of 110 ° C. or higher.
- step (III) a reaction in which the metal oxide (A) particles are bonded via phosphorus atoms (phosphorus atoms derived from the phosphorus compound (B)) proceeds.
- a reaction for generating the reaction product (R) proceeds.
- the temperature of the heat treatment is 110 ° C. or higher, preferably 120 ° C. or higher, more preferably 140 ° C. or higher, more preferably 170 ° C. or higher, and preferably 190 ° C. or higher. Further preferred. 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 190 ° C. or lower.
- the temperature of heat processing is 220 degrees C or less.
- the heat treatment can be performed in air, a nitrogen atmosphere, an argon atmosphere, or the like.
- the heat treatment time is preferably in the range of 0.1 second to 1 hour, more preferably in the range of 1 second to 15 minutes, and still more preferably in the range of 5 to 300 seconds.
- An example of the heat treatment is performed in a range of 110 to 220 ° C. (for example, a range of 140 ° C. to 220 ° C.) for 0.1 second to 1 hour.
- the heat treatment is performed in the range of 170 to 200 ° C. for 5 to 300 seconds (for example, 10 to 300 seconds).
- the method of the present invention for producing a multilayer structure may include a step of irradiating the precursor layer of the layer (YA) or the layer (YA) with ultraviolet rays.
- the ultraviolet irradiation may be performed at any stage after the step (II) (for example, after the removal of the solvent of the applied coating liquid (U) is almost completed).
- the method is not particularly limited, and a known method can be applied.
- the wavelength of the irradiated ultraviolet light is preferably in the range of 170 to 250 nm, more preferably in the range of 170 to 190 nm and / or in the range of 230 to 250 nm.
- radiation such as an electron beam or ⁇ -ray may be irradiated. By performing ultraviolet irradiation, the gas barrier performance of the multilayer structure may be expressed more highly.
- the surface of the substrate (X) is coated with a known anchor coating agent before applying the coating liquid (U).
- an aging treatment is preferably performed. Specifically, after applying the coating liquid (U) and before the heat treatment step of the step (III), the base material (X) to which the coating liquid (U) is applied is kept at a relatively low temperature for a long time. It is preferable to leave.
- the temperature of the aging treatment is preferably less than 110 ° C, more preferably 100 ° C or less, and further preferably 90 ° C or less.
- the temperature of the aging treatment is preferably 10 ° C or higher, more preferably 20 ° C or higher, and further preferably 30 ° C or higher.
- the aging time is preferably in the range of 0.5 to 10 days, more preferably in the range of 1 to 7 days, and further preferably in the range of 1 to 5 days.
- step (IV) a layer (Z) is formed on the substrate (X) (or on the layer (Y)) by applying a coating liquid (V) containing a polymer (E) having a plurality of phosphorus atoms.
- the coating liquid (V) is a solution in which the polymer (E) is dissolved in a solvent.
- the coating solution (V) may be prepared by dissolving the polymer (E) in a solvent, or the solution obtained when the polymer (E) is produced may be used as it is.
- dissolution may be promoted by heat treatment or ultrasonic treatment.
- the solvent used in the coating liquid (V) may be appropriately selected according to the type of the polymer (E), but is preferably water, alcohols or a mixed solvent thereof.
- the solvent is ether such as tetrahydrofuran, dioxane, trioxane, dimethoxyethane; ketone such as acetone and methyl ethyl ketone; glycol such as ethylene glycol and propylene glycol; methyl cellosolve, ethyl cellosolve, It may contain glycol derivatives such as n-butyl cellosolve; glycerin; acetonitrile; amides such as dimethylformamide; dimethyl sulfoxide; sulfolane and the like.
- the solid content concentration of the polymer (E) in the coating liquid (V) is preferably in the range of 0.01 to 60% by mass from the viewpoint of storage stability and coating properties of the solution, The content is more preferably in the range of 50% by mass, further preferably in the range of 0.2 to 40% by mass.
- the solid content concentration can be determined by the same method as described for the coating liquid (U).
- the pH of the solution of the polymer (E) is preferably in the range of 0.1 to 6.0, preferably 0.2 to 5 More preferably, it is in the range of 0.0, and more preferably in the range of 0.5 to 4.0.
- the pH of the coating liquid (V) can be adjusted by a known method, for example, by adding an acidic compound or a basic compound.
- acidic compounds include hydrochloric acid, nitric acid, sulfuric acid, acetic acid, butyric acid, and ammonium sulfate.
- basic compounds include sodium hydroxide, potassium hydroxide, ammonia, trimethylamine, pyridine, sodium carbonate, and sodium acetate.
- viscosity modifiers include carboxymethyl cellulose, starch, bentonite, tragacanth gum, stearate, alginate, methanol, ethanol, n-propanol, and isopropanol.
- the coating liquid (V) may be deaerated and / or defoamed as necessary.
- a method of deaeration and / or defoaming treatment for example, there are methods by evacuation, heating, centrifugation, ultrasonic waves, etc., but a method including evacuation can be preferably used.
- the viscosity of the coating liquid (V) applied in step (IV) and measured with a Brookfield type rotational viscometer (SB type viscometer: rotor No. 3, rotation speed 60 rpm)
- the temperature is preferably 1000 mPa ⁇ s or less, more preferably 500 mPa ⁇ s or less.
- the viscosity of the coating liquid (V) when applied in the step (IV) can be adjusted by the concentration, temperature and the like.
- the method of applying the coating liquid (V) solution on the substrate (X) or the layer (Y) is not particularly limited, and a known method can be adopted.
- Preferred methods include, for example, a casting method, a dipping method, a roll coating method, a gravure coating method, a screen printing method, a reverse coating method, a spray coating method, a kiss coating method, a die coating method, a metalling bar coating method, and a chamber doctor combined coating method. , Curtain coating method, bar coating method and the like.
- the layer (Z) is formed by removing the solvent in the coating liquid (V).
- a well-known drying method is applicable. Specifically, drying methods such as a hot air drying method, a hot roll contact method, an infrared heating method, and a microwave heating method can be applied alone or in combination.
- the drying temperature is preferably 0 to 15 ° C. or lower than the flow start temperature of the substrate (X).
- the drying temperature is preferably in the range of 70 to 200 ° C, more preferably in the range of 80 to 180 ° C, and further preferably in the range of 90 to 160 ° C.
- the removal of the solvent may be carried out under normal pressure or reduced pressure.
- step (IV) is performed after step (II)
- the solvent may be removed by the heat treatment in step (III) described above.
- the solvent is removed after applying the coating liquid (V) on one side.
- the first layer (Z) may be formed by applying the coating liquid (V) to the other surface, and then the solvent may be removed to form the second layer (Z).
- the composition of the coating liquid (V) applied to each surface may be the same or different.
- a layer (Z) is laminated on a plurality of surfaces of a substrate (X) having a three-dimensional shape with or without a layer (Y), the layer (Z) is formed for each surface by the above method. May be. Or you may form a some layer (Z) simultaneously by apply
- step (IV) may be performed before step (II), and step (III) may be performed after step (IV). From the viewpoint of obtaining a multilayer structure having an excellent appearance, it is preferable to carry out step (IV) after step (III).
- the multilayer structure thus obtained can be used as it is as the multilayer structure of the present invention.
- another member (such as another layer) may be further bonded or formed on the multilayer structure as described above to form the multilayer structure of the present invention.
- the member can be bonded by a known method.
- the production method of the present invention includes a step (W) of forming a layer (Y) containing aluminum atoms and a coating liquid (V) containing a polymer (E) having a plurality of phosphorus atoms.
- the step (W) may include steps (I), (II), and (III).
- the step (W) may include a step of forming those layers by a vapor deposition method.
- an infrared absorption spectrum of the layer (YA) laminated on the base material (X) was measured using a Fourier transform infrared spectrophotometer (manufactured by Perkin Elmer, “Spectrum One”).
- the infrared absorption spectrum was measured in the range of 700 to 4000 cm ⁇ 1 in ATR (total reflection measurement) mode.
- ATR total reflection measurement
- the infrared absorption spectrum of only the substrate (X) was separately measured, and only the peak derived from the layer (X) was extracted by subtracting it.
- a similar method can also be adopted when the layer (YA) is laminated on the layer (Z).
- the layer (YA) is formed inside the multilayer structure (for example, in the case of having a stacking order of base material (X) / layer (YA) / layer (Z))
- the layer (YA) The infrared absorption spectrum is measured before forming the layer (Z), or after the layer (Z) is formed, it is peeled off at the interface of the layer (YA), and the infrared absorption spectrum of the exposed layer (YA) is measured. Can be obtained.
- the half width of the absorption peak of the maximum absorption wave number (n 1 ) is obtained by calculating the wave number of two points having an absorbance (absorbance ( ⁇ 1 ) / 2) half of the absorbance ( ⁇ 1 ) at the absorption peak. Obtained by calculating the difference in wave numbers.
- the absorption peak with the maximum absorption wave number (n 1 ) overlaps with the absorption peak derived from other components, it is separated into absorption peaks derived from the respective components by the least square method using a Gaussian function. After that, the half width of the absorption peak of the maximum absorption wave number (n 1 ) was obtained in the same manner as described above.
- Oxygen permeability (Os) under conditions of 20 ° C. and 85% RH The oxygen transmission rate was measured using an oxygen transmission amount measuring device (“MOCON OX-TRAN 2/20” manufactured by Modern Control). Specifically, the multilayer structure is set so that the layer (YZ) (or layer (YZ)) faces the oxygen supply side and the base material (X) faces the carrier gas side, the temperature is 20 ° C., and the oxygen supply Oxygen permeability (unit: ml / (m 2 ⁇ day ⁇ atm) under conditions of 85% RH on the side, 85% RH on the carrier gas side, oxygen pressure of 1 atm, and carrier gas pressure of 1 atm ) was measured. Nitrogen gas containing 2% by volume of hydrogen gas was used as the carrier gas.
- a multilayer structure having a size of 21 cm ⁇ 30 cm was produced. And after leaving the multilayer structure to stand for 24 hours or more under the conditions of 23 ° C. and 50% RH, it is stretched 5% in the major axis direction under the same conditions, and the stretched state is maintained for 5 minutes.
- a multilayer structure was obtained.
- the oxygen transmission rate was measured using an oxygen transmission amount measuring device (“MOCON OX-TRAN 2/20” manufactured by Modern Control).
- the multilayer structure is set so that the layer (YZ) faces the oxygen supply side and the base material (X) faces the carrier gas side, the temperature is 20 ° C., and the humidity on the oxygen supply side is 85% RH.
- the oxygen permeability (unit: ml / (m 2 ⁇ day ⁇ atm)) was measured under conditions where the humidity on the carrier gas side was 85% RH, the oxygen pressure was 1 atm, and the carrier gas pressure was 1 atm. Nitrogen gas containing 2% by volume of hydrogen gas was used as the carrier gas.
- Example of production of coating liquid (U) The manufacture example of the coating liquid (U) used in order to manufacture a layer (YA) is shown. The temperature was raised to 70 ° C. while stirring 230 parts by mass of distilled water. In the distilled water, 88 parts by mass of aluminum isopropoxide was added dropwise over 1 hour, the liquid temperature was gradually raised to 95 ° C., and the generated isopropanol was distilled off to carry out hydrolysis and condensation. After adding 4.0 parts by mass of a 60% by mass nitric acid aqueous solution to the obtained liquid and stirring the mixture at 95 ° C.
- the solution (T1) was dropped while stirring the dispersion (S1) to obtain a coating liquid (U1). While maintaining the obtained coating liquid (U1) at 15 ° C., stirring was continued until the viscosity reached 1500 mPa ⁇ s.
- the number of moles of metal atoms (N M ) constituting the metal oxide (A) (alumina) and the number of moles of phosphorus atoms constituting the phosphorus compound (B) (phosphoric acid) ( N p ) (number of moles (N M ) / number of moles (N p )) was 1.15.
- the coating solution (U2), the coating solution (U3) and the coating solution (U4) were respectively changed in the same manner except that the ratio of N M / N P was changed to 4.48, 1.92 and 0.82, respectively. Obtained.
- the reaction mixture is diluted with 15 g of water and filtered through a cellulose membrane (Spectra / Por (trade name) manufactured by Spectrum Laboratories). did.
- the solvent of the filtrate was distilled off with an evaporator, and a white polymer was obtained by vacuum drying at 50 ° C. for 24 hours.
- this polymer was measured by gel permeation chromatography using a 1.2 wt% NaCl aqueous solution as a solvent and a polymer concentration of 0.1 wt%, the number average molecular weight was about 10,000 in terms of polyethylene glycol. Met.
- the purified polymer was dissolved in a mixed solvent of water and methanol at a concentration of 10 wt% to obtain a coating liquid (V1).
- a coating liquid (V2) composed of a homopolymer of 4-vinylbenzylphosphonic acid (hereinafter sometimes abbreviated as “VBPA”) was obtained. Further, similarly, a coating solution (V3) and a coating of a copolymer obtained by copolymerizing VPA and methacrylic acid (hereinafter sometimes abbreviated as “MA”) at a molar ratio of 2/1 and 1/1, respectively. A liquid (V4) was obtained.
- Example 1 As a base material, a stretched polyethylene terephthalate film (manufactured by Toray Industries, Inc., “Lumirror P60” (trade name), thickness 12 ⁇ m, hereinafter sometimes abbreviated as “PET”) was prepared. On the substrate (PET), the coating liquid (U1) was applied by a bar coater so that the thickness after drying was 0.5 ⁇ m, and dried at 110 ° C. for 5 minutes. Next, heat treatment was performed at 180 ° C. for 1 minute to obtain a structure (A1) having a structure of layer (Y1) (0.5 ⁇ m) / PET (12 ⁇ m).
- the coating liquid (V1) is applied on the layer (Y1) of the structure (A1) by a bar coater so that the thickness after drying is 0.3 ⁇ m, and dried at 110 ° C. for 5 minutes,
- a multilayer structure (B1) of the present invention having a structure of (Z1) (0.3 ⁇ m) / layer (Y1) (0.5 ⁇ m) / PET (12 ⁇ m) was obtained.
- the moisture permeability (water vapor transmission rate: WVTR) of the obtained multilayer structure (B1) was measured using a water vapor transmission amount measuring device ("MOCON PERMATRAN 3/33" manufactured by Modern Control). Specifically, the multilayer structure is set so that the layer (Z1) faces the water vapor supply side and the PET layer faces the carrier gas side, the temperature is 40 ° C., the water vapor supply side humidity is 90% RH, the carrier gas side
- the moisture permeability (unit: g / (m 2 ⁇ day)) was measured under the condition of 0% RH.
- the moisture permeability of the multilayer structure (B1) was 0.2 g / (m 2 ⁇ day).
- Examples 2 to 3 A multilayer structure was obtained by the same method as in Example 1 except that the thickness of the layer (Z) was changed according to Table 1.
- Examples 4 to 6 A multilayer structure was obtained in the same manner as in Example 1 except that the coating liquid (V) used was changed according to Table 1.
- Example 7 to 9 A multilayer structure was obtained in the same manner as in Example 1 except that the heat treatment conditions were changed according to Table 1.
- Example 10 to 12 A multilayer structure was obtained in the same manner as in Example 1 except that the coating liquid (U) used was changed according to Table 1.
- Example 13 A multilayer structure was obtained by the same method as in Example 1 except that the heat treatment step was performed after the formation of the layer (Z).
- Example 14 A multilayer structure was obtained by the same method as in Example 1 except that the layer (Y) and the layer (Z) were laminated on both surfaces of the substrate.
- the moisture permeability of the obtained multilayer structure was measured in the same manner as in Example 1 and found to be 0.1 g / (m 2 ⁇ day) or less.
- Example 15 A multilayer structure is obtained by the same method as in Example 1 except that the base material is a stretched nylon film (“Emblem ONBC” (trade name), unit thickness 15 ⁇ m, sometimes abbreviated as “ONY”) manufactured by Unitika Ltd. Got the body.
- Emblem ONBC stretched nylon film
- ONY unit thickness 15 ⁇ m
- Example 16 A multilayer structure was obtained by the same method as in Example 1 except that the layer (Y) was formed after the formation of the layer (Z).
- Example 17 A multilayer structure was obtained by the same method as in Example 1 except that the layer (Y) was an aluminum deposited layer having a thickness of 0.03 ⁇ m. The aluminum layer was formed by a vacuum evaporation method.
- Example 18 A multilayer structure was obtained in the same manner as in Example 1 except that the layer (Y) was an aluminum oxide vapor deposition layer having a thickness of 0.03 ⁇ m.
- the aluminum oxide layer was formed by a vacuum evaporation method.
- Example 19 A multilayer structure was obtained by the same method as in Example 1 except that the layer (Y) was a layer (Y) ′ which was a deposited layer of silicon oxide having a thickness of 0.03 ⁇ m. The silicon oxide layer was formed by a vacuum evaporation method.
- Comparative Example 21 A multilayer structure was obtained in the same manner as in Example 1 except that the layer (Z) was formed on PET. That is, in Comparative Example 20, a multilayer structure of Comparative Example 20 having a structure of layer (Y1) (0.5 ⁇ m) / PET (12 ⁇ m) / layer (Z1) (0.3 ⁇ m) was produced.
- Comparative Example 23 In Comparative Example 20, the layer (Z) was not formed, that is, only the base material (PET) was used as Comparative Example 23.
- the multilayer structures of the examples were able to maintain gas barrier properties at a high level even when subjected to strong stretching stress.
- the multilayer structure of the example showed a good appearance.
- Example 19 a vertical bag-filled sealing bag was produced using the multilayer structure of the present invention.
- a multilayer structure (B1) was produced by the same method as in Example 1.
- a two-component adhesive manufactured by Mitsui Takeda Chemical Co., Ltd., A-520 (trade name) and A-50 (trade name)
- this and a stretched nylon film ONY described above
- the laminated nylon film of the laminate was coated with a two-component adhesive (Mitsui Takeda Chemical Co., Ltd., A-520 (trade name) and A-50 (trade name)) and dried.
- the multilayer structure (C19) is cut into a width of 400 mm and supplied to a vertical bag making and filling packaging machine (manufactured by ORIHIRO Co., Ltd.). 470 mm).
- a vertical bag making and filling packaging machine manufactured by ORIHIRO Co., Ltd.
- 2 kg of water was filled into a vertical bag-filling sealing bag made of a multilayer structure (C19) using a bag-filling and packaging machine.
- the processability of the multilayer structure (C19) in the bag making and filling machine was good, and no defects such as wrinkles and streaks were found in the appearance of the obtained vertical bag filling and sealing bag.
- Example 20 a vacuum packaging bag was produced using the multilayer structure of the present invention.
- a multilayer structure (B1) was produced by the same method as in Example 1.
- a two-component adhesive manufactured by Mitsui Takeda Chemical Co., Ltd., A-520 (trade name) and A-50 (trade name)
- A-520 (trade name) and A-50 (trade name) is coated on a stretched nylon film (ONY described above) and dried.
- a two-component adhesive (A-520 (trade name) and A-50 (trade name) manufactured by Mitsui Takeda Chemical Co., Ltd.) is coated on the laminated multilayer structure (B1) and dried.
- Example 21 a pouch with a spout was produced using the multilayer structure of the present invention.
- a multilayer structure (C21) having a structure of PET / layer (Y1) / layer (Z1) / adhesive / ONY / adhesive / CPP70 was obtained in the same manner as in Example 19.
- the two multilayer structures (C21) are overlaid so that the CPP 70 is on the inside, the periphery is heat-sealed, and further, made of polypropylene.
- a spout was attached by heat sealing. In this way, a flat pouch-type pouch with a spout could be produced without problems.
- Example 22 a laminated tube container was produced using the multilayer structure of the present invention.
- a multilayer structure (B1) was produced by the same method as in Example 1.
- each of two unstretched polypropylene films (manufactured by Tosero Co., Ltd., RXC-21 (trade name), thickness 100 ⁇ m, hereinafter sometimes abbreviated as “CPP100”) is a two-component adhesive ( A product prepared by coating and drying A-520 (trade name) and A-50 (trade name) manufactured by Mitsui Takeda Chemical Co., Ltd. was prepared and laminated with the multilayer structure (B1).
- a multilayer structure (C22) having a structure of CPP100 / adhesive / layer (Z1) / layer (Y1) / PET / adhesive / CPP100 was obtained.
- a cylindrical body was manufactured by heat-sealing the overlapped portions.
- the cylindrical body was attached to a mandrel for forming a tube container, and a frustoconical shoulder portion and a leading end portion thereof were produced at one end of the cylindrical body.
- the shoulder and the tip were formed by compression molding polypropylene resin.
- a polypropylene resin cap was attached to the tip.
- the other open end of the cylindrical body was heat sealed.
- Example 23 an infusion bag was produced using the multilayer structure of the present invention.
- a multilayer structure (C23) having a structure of PET / layer (Y1) / layer (Z1) / adhesive / ONY / adhesive / CPP70 was obtained in the same manner as in Example 19.
- the two multilayer structures (C23) are overlaid so that the CPP 70 is on the inside, the periphery is heat-sealed, and further made of polypropylene. A spout was attached by heat sealing. In this way, an infusion bag could be produced without problems.
- Example 24 a container lid was produced using the multilayer structure of the present invention.
- a multilayer structure (C24) having a structure of PET / layer (Y1) / layer (Z1) / adhesive / ONY / adhesive / CPP70 was obtained by the same method as in Example 19.
- the multilayer structure (C24) was cut into a circle having a diameter of 88 mm as a container lid.
- a cylindrical container (high reflex HR78-84 manufactured by Toyo Seikan Co., Ltd.) having a diameter of 78 mm, a flange width of 6.5 mm, and a height of 30 mm and comprising three layers of polyolefin layer / steel layer / polyolefin layer Got ready.
- the container was almost completely filled with water, and a container lid made of a multilayer structure (C24) was heat sealed to the flange portion. In this way, a lidded container using the container lid material could be produced without problems.
- Example 25 a paper container was produced using the multilayer structure of the present invention.
- a multilayer structure (B1) was produced by the same method as in Example 1.
- an adhesive is applied to both sides of a 400 g / m 2 paperboard, and a polypropylene resin (hereinafter sometimes abbreviated as “PP”) is extrusion laminated on both sides, thereby forming a PP layer on both sides of the paperboard. (Thickness 20 ⁇ m each) was formed.
- PP polypropylene resin
- an adhesive is applied to the surface of one PP layer, the multilayer structure (B1) is laminated thereon, an adhesive is further applied to the surface of the multilayer structure (B1), and an unstretched polypropylene film (described above) CPP70).
- a multilayer structure (C25) having a configuration of PP / paperboard / PP / adhesive / layer (Z1) / layer (Y1) / PET / adhesive / CPP70 was produced.
- an anchor coating agent was used as necessary.
- a brick-type paper container could be produced without problems.
- Example 26 a vacuum thermal insulator was produced using the multilayer structure of the present invention.
- a multilayer structure (C26) having a configuration of ONY / adhesive / layer (Z1) / layer (Y1) / PET / adhesive / CPP70 was obtained in the same manner as in Example 20.
- the two multilayer structures (C26) are overlaid so that the CPP 70 is inside, and the three sides of the rectangle are heat sealed.
- a bag was formed.
- a heat insulating core material was filled from the opening of the bag, and the bag was sealed using a vacuum packaging machine (VAC-STAR 2500 type manufactured by Frimark GmbH) at a temperature of 20 ° C. and an internal pressure of 10 Pa.
- VAC-STAR 2500 type manufactured by Frimark GmbH a vacuum packaging machine
- the silica fine powder dried for 4 hours in 120 degreeC atmosphere was used for the heat insulating core material.
- Example 27 a solar cell module was produced using the multilayer structure of the present invention.
- a multilayer structure (B1) was produced by the same method as in Example 1.
- an amorphous silicon solar battery cell placed on a 10 cm square tempered glass is sandwiched with an ethylene-vinyl acetate copolymer having a thickness of 450 ⁇ m, and a layer (Z1) of the multilayer structure (B1) is formed thereon.
- a solar cell module was fabricated by bonding so as to face each other. The bonding was performed by performing vacuum drawing at 150 ° C. for 3 minutes and then performing pressure bonding for 9 minutes.
- the solar cell module produced in this way operated well and showed good electrical output characteristics over a long period of time.
- the multilayer structure of the present invention has excellent gas barrier properties and a good appearance. Further, even when subjected to physical stress such as deformation and impact, the gas barrier property can be maintained at a high level. Therefore, the multilayer structure of the present invention can be preferably used as a packaging material for foods, medicines, medical equipment, industrial materials, clothing and the like.
- LCD substrate films In addition to packaging materials, LCD substrate films, organic EL substrate films, electronic paper substrate films, electronic device sealing films, PDP films and other display members, LED films, IC tag films , Solar cell modules, solar cell back sheets, solar cell members such as solar cell protective films, and other electronic device-related members; optical communication members, electronic device flexible films, fuel cell membranes, fuel cell sealing films Examples thereof include substrate films of various functional films.
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Abstract
Description
AlX1 mR1 (3-m) (II)
[式(II)中、X1は、F、Cl、Br、I、R2O-、R3C(=O)O-、(R4C(=O))2CH-およびNO3からなる群より選ばれる。R1、R2、R3およびR4はそれぞれ、アルキル基、アラルキル基、アリール基およびアルケニル基からなる群より選ばれる。式(II)において、複数のX1が存在する場合には、それらのX1は互いに同一であってもよいし異なっていてもよい。式(II)において、複数のR1が存在する場合には、それらのR1は互いに同一であってもよいし異なっていてもよい。式(II)において、複数のR2が存在する場合には、それらのR2は互いに同一であってもよいし異なっていてもよい。式(II)において、複数のR3が存在する場合には、それらのR3は互いに同一であってもよいし異なっていてもよい。式(II)において、複数のR4が存在する場合には、それらのR4は互いに同一であってもよいし異なっていてもよい。mは1~3の整数を表す。]
前記基材(X)上に前記コーティング液(U)を塗布することによって、前記基材(X)上に前記層(YA)の前駆体層を形成する工程(II)と、
前記層(YA)の前駆体層を110℃以上の温度で熱処理して前記層(YA)を形成する工程(III)とをさらに含んでもよい。前記少なくとも1種の化合物が前記リン化合物(B)を含んでもよい。前記コーティング液(U)において、前記金属酸化物(A)を構成する金属原子(M)のモル数NMと、前記リン化合物(B)に含まれるリン原子のモル数NPとが、1.0≦(前記モル数NM)/(前記モル数NP)≦3.6の関係を満たしてもよい。
本発明の多層構造体は、基材(X)、層(Y)および層(Z)をそれぞれ1層以上有する多層構造体であって、層(Y)はアルミニウム原子を含み、層(Z)はリン原子を複数有する重合体(E)を含み、前記重合体(E)は、ビニルホスホン酸類を含む少なくとも1種の単量体の重合体であり、少なくとも1組の層(Y)と層(Z)とが隣接して積層されている。このような多層構造体は、多層構造体を製造するための本発明の方法によって得られる。
本発明の多層構造体が有する層(Y)は、少なくともアルミニウムを含む金属酸化物(A)とリン化合物(B)とが反応してなる反応生成物(R)を含む層(YA)であってもよい。あるいは、層(Y)は、アルミニウムの蒸着層である層(以下では、「層(YB)」という場合がある)または酸化アルミニウムの蒸着層(以下では、「層(YC)という場合がある)であってもよい。以下、順に説明する。
本発明の多層構造体が有する層(Y)が前記層(YA)である場合には、層(YA)の赤外線吸収スペクトルにおいて、800~1400cm-1の範囲における赤外線吸収が最大となる波数(n1)が1080~1130cm-1の範囲にあってもよい。
金属酸化物(A)を構成する金属原子(それらを総称して「金属原子(M)」という場合がある)としては、原子価が2価以上(たとえば、2~4価や3~4価)の金属原子を挙げることができ、具体的には、例えば、マグネシウム、カルシウムなどの周期表第2族の金属;亜鉛などの周期表第12族の金属;アルミニウムなどの周期表第13族の金属;ケイ素などの周期表第14族の金属;チタン、ジルコニウムなどの遷移金属などを挙げることができる。なお、ケイ素は半金属に分類される場合があるが、本明細書ではケイ素を金属に含めるものとする。金属酸化物(A)を構成する金属原子(M)は1種類であってもよいし、2種類以上であってもよいが、アルミニウムを少なくとも含む必要がある。アルミニウムと併用されうる金属原子(M)としては、金属酸化物(A)を製造するための取り扱いの容易さや得られる多層構造体のガスバリア性が優れることから、チタンおよびジルコニウムからなる群より選ばれる少なくとも1種であることが好ましい。
AlX1 mR1 (3-m) (II)
[式(II)中、X1は、F、Cl、Br、I、R2O-、R3C(=O)O-、(R4C(=O))2CH-およびNO3からなる群より選ばれる。R1、R2、R3およびR4はそれぞれ、アルキル基、アラルキル基、アリール基およびアルケニル基からなる群より選ばれる。式(II)において、複数のX1が存在する場合には、それらのX1は互いに同一であってもよいし異なっていてもよい。式(II)において、複数のR1が存在する場合には、それらのR1は互いに同一であってもよいし異なっていてもよい。式(II)において、複数のR2が存在する場合には、それらのR2は互いに同一であってもよいし異なっていてもよい。式(II)において、複数のR3が存在する場合には、それらのR3は互いに同一であってもよいし異なっていてもよい。式(II)において、複数のR4が存在する場合には、それらのR4は互いに同一であってもよいし異なっていてもよい。mは1~3の整数を表す。]
M1X1 mR1 (n-m) (III)
[式中、M1はTiまたはZrを表す。X1は、F、Cl、Br、I、R2O-、R3C(=O)O-、(R4C(=O))2CH-およびNO3からなる群より選ばれる。R1、R2、R3およびR4はそれぞれ、アルキル基、アラルキル基、アリール基およびアルケニル基からなる群より選ばれる。式(III)において、複数のX1が存在する場合には、それらのX1は互いに同一であってもよいし異なっていてもよい。式(III)において、複数のR1が存在する場合には、それらのR1は互いに同一であってもよいし異なっていてもよい。式(III)において、複数のR2が存在する場合には、それらのR2は互いに同一であってもよいし異なっていてもよい。式(III)において、複数のR3が存在する場合には、それらのR3は互いに同一であってもよいし異なっていてもよい。式(III)において、複数のR4が存在する場合には、それらのR4は互いに同一であってもよいし異なっていてもよい。nは、M1の原子価に等しい。mは1~nの整数を表す。]
リン化合物(B)は、金属酸化物(A)と反応可能な部位を含有し、典型的には、そのような部位を複数含有する。好ましい一例では、リン化合物(B)は、そのような部位(原子団または官能基)を2~20個含有する。そのような部位の例には、金属酸化物(A)の表面に存在する官能基(たとえば水酸基)と反応可能な部位が含まれる。たとえば、そのような部位の例には、リン原子に直接結合したハロゲン原子や、リン原子に直接結合した酸素原子が含まれる。それらのハロゲン原子や酸素原子は、金属酸化物(A)の表面に存在する水酸基と縮合反応(加水分解縮合反応)を起こすことができる。金属酸化物(A)の表面に存在する官能基(たとえば水酸基)は、通常、金属酸化物(A)を構成する金属原子(M)に結合している。
反応生成物(R)には、金属酸化物(A)およびリン化合物(B)のみが反応することによって生成される反応生成物が含まれる。また、反応生成物(R)には、金属酸化物(A)とリン化合物(B)とさらに他の化合物とが反応することによって生成される反応生成物も含まれる。反応生成物(R)は、後述する製造方法で説明する方法によって形成できる。
層(YA)において、金属酸化物(A)を構成する金属原子のモル数NMとリン化合物(B)に由来するリン原子のモル数NPとが、1.0≦(モル数NM)/(モル数NP)≦3.6の関係を満たすことが好ましく、1.1≦(モル数NM)/(モル数NP)≦3.0の関係を満たすことがより好ましい。(モル数NM)/(モル数NP)の値が3.6を超えると、金属酸化物(A)がリン化合物(B)に対して過剰となり、金属酸化物(A)の粒子同士の結合が不充分となり、また、金属酸化物(A)の表面に存在する水酸基の量が多くなるため、ガスバリア性とその安定性が低下する傾向がある。一方、(モル数NM)/(モル数NP)の値が1.0未満であると、リン化合物(B)が金属酸化物(A)に対して過剰となり、金属酸化物(A)との結合に関与しない余剰なリン化合物(B)が多くなり、また、リン化合物(B)由来の水酸基の量が多くなりやすく、やはりガスバリア性とその安定性が低下する傾向がある。
本発明の多層構造体が有する層(YA)は、特定の重合体(C)をさらに含んでもよい。重合体(C)は、水酸基、カルボキシル基、カルボン酸無水物基、およびカルボキシル基の塩からなる群より選ばれる少なくとも1種の官能基(f)を有する重合体である。多層構造体が有する層(YA)において重合体(C)は、それが有する官能基(f)によって金属酸化物(A)の粒子およびリン化合物(B)に由来するリン原子の一方または両方と直接的にまたは間接的に結合していてもよい。また多層構造体が有する層(YA)において反応生成物(R)は、重合体(C)が金属酸化物(A)やリン化合物(B)と反応するなどして生じる重合体(C)部分を有していてもよい。なお、本明細書において、リン化合物(B)としての要件を満たす重合体であって官能基(f)を含む重合体は、重合体(C)には含めずにリン化合物(B)として扱う。
本発明の多層構造体が有する層(YA)の厚さ(多層構造体が2層以上の層(YA)を有する場合には各層(YA)の厚さの合計)は、4.0μm以下であることが好ましく、2.0μm以下であることがより好ましく、1.0μm以下であることがさらに好ましく、0.9μm以下であってもよい。層(YA)を薄くすることによって、印刷、ラミネートなどの加工時における多層構造体の寸法変化を低く抑えることができ、さらに多層構造体の柔軟性が増し、その力学的特性を、基材自体の力学的特性に近づけることができる。
本発明の多層構造体が有する層(Y)は、アルミニウムの蒸着層である層(YB)または酸化アルミニウムの蒸着層である層(YC)であってもよい。これらの蒸着層は、後述する無機蒸着層と同様の方法により製造することができる。
本発明の多層構造体が有する層(Z)は、リン原子を複数有する重合体(E)を含む。層(Z)を層(Y)に隣接して形成することで、本発明の多層構造体の耐屈曲性を大幅に向上することができる。
重合体(E)は、高分子中に複数のリン原子を有している。一例では、当該リン原子は酸性基またはその誘導体に含まれる。リン原子を含む酸性基の例には、リン酸基、ポリリン酸基、亜リン酸基、ホスホン酸基が含まれる。重合体(E)が有する複数のリン原子のうち、少なくとも1つのリン原子は、金属酸化物(A)と反応可能な部位を含有する。好ましい一例では、重合体(E)は、そのようなリン原子を10~1000個程度含有する。金属酸化物(A)と反応可能なリン原子に関する部位の例には、リン化合物(B)に対して記載した構造の部位を挙げることができる。
(a)置換基を有するホスホン酸、置換基を有するホスフィン酸、またはこれらのエステルである。
(b)分子中のリン原子(ホスホン酸基、ホスフィン酸基またはそれらのエステル中のリン原子)に置換基の炭素鎖がリン-炭素結合を介して結合している。炭素鎖中に炭素-炭素二重結合が存在する。炭素鎖の一部は、炭素環を構成していてもよい。
(c)分子中のリン原子(ホスホン酸基、ホスフィン酸基またはそれらのエステル中のリン原子)には、少なくとも1つの水酸基が結合している。
層(Z)の1層当たりの厚さは、本発明の多層構造体の耐屈曲性がより良好になる観点から、0.005μm以上であることが好ましい。層(Z)の厚さの上限は特に限定されないが、1.0μm以上では耐屈曲性の改善効果は飽和に達するため、層(Z)の厚さの上限を1.0μmとすることが経済的に好ましい。層(Z)の厚さは、層(Z)の形成に用いられる後述するコーティング液(V)の濃度や、その塗布方法によって制御することができる。
本発明の多層構造体が有する基材(X)の材質に特に制限はなく、様々な材質からなる基材を用いることができる。基材(X)の材質としては、例えば、熱可塑性樹脂、熱硬化性樹脂などの樹脂;布帛、紙類などの繊維集合体;木材;ガラス;金属;金属酸化物などが挙げられる。なお、基材は複数の材質からなる複合構成または多層構成のものであってもよい。
本発明の多層構造体において、層(Y)および/または層(Z)は、基材(X)と直接接触するように積層されていてもよいが、基材(X)と層(Y)および/または層(Z)との間に配置された接着層(H)を介して層(Y)および/または層(Z)が基材(X)に積層されていてもよい。この構成によれば、基材(X)と層(Y)および/または層(Z)との接着性を高めることができる場合がある。接着層(H)は、接着性樹脂で形成してもよい。接着性樹脂からなる接着層(H)は、基材(X)の表面を公知のアンカーコーティング剤で処理するか、基材(X)の表面に公知の接着剤を塗布することによって形成できる。当該接着剤としては、ポリイソシアネート成分とポリオール成分とを混合し反応させる二液反応型ポリウレタン系接着剤が好ましい。また、アンカーコーティング剤や接着剤に、公知のシランカップリング剤などの少量の添加剤を加えることによって、さらに接着性を高めることができる場合がある。シランカップリング剤の好適な例としては、イソシアネート基、エポキシ基、アミノ基、ウレイド基、メルカプト基などの反応性基を有するシランカップリング剤を挙げることができる。基材(X)と層(Y)および/または層(Z)とを接着層(H)を介して強く接着することによって、本発明の多層構造体に対して印刷やラミネートなどの加工を施す際に、ガスバリア性や外観の悪化をより効果的に抑制することができる。
本発明の多層構造体(積層体)は、基材(X)、層(Y)および層(Z)のみによって構成されてもよいし、基材(X)、層(Y)、層(Z)および接着層(H)のみによって構成されていてもよい。本発明の多層構造体は、複数の層(Y)および/または複数の層(Z)を含んでもよい。また、本発明の多層構造体は、基材(X)、層(Y)、層(Z)および接着層(H)以外の他の部材(例えば熱可塑性樹脂フィルム層、紙層、無機蒸着層などの他の層など)をさらに含んでもよい。そのような他の部材(他の層など)を有する本発明の多層構造体は、たとえば、基材(X)に直接または接着層(H)を介して層(Y)および層(Z)を積層させた後に、さらに当該他の部材(他の層など)を直接または接着層を介して接着または形成することによって製造できる。このような他の部材(他の層など)を多層構造体に含ませることによって、多層構造体の特性を向上させたり、新たな特性を付与したりすることができる。例えば、本発明の多層構造体にヒートシール性を付与したり、バリア性や力学的物性をさらに向上させたりすることができる。
(1)層(YZ)/ポリエステル層、
(2)層(YZ)/ポリエステル層/層(YZ)、
(3)層(YZ)/ポリアミド層、
(4)層(YZ)/ポリアミド層/層(YZ)、
(5)層(YZ)/ポリオレフィン層、
(6)層(YZ)/ポリオレフィン層/層(YZ)、
(7)層(YZ)/水酸基含有ポリマー層、
(8)層(YZ)/水酸基含有ポリマー層/層(YZ)、
(9)層(YZ)/紙層、
(10)層(YZ)/紙層/層(YZ)、
(11)層(YZ)/無機蒸着層/ポリエステル層、
(12)無機蒸着層/層(YZ)/ポリエステル層、
(13)層(YZ)/無機蒸着層/ポリアミド層、
(14)無機蒸着層/層(YZ)/ポリアミド層、
(15)層(YZ)/無機蒸着層/ポリオレフィン層、
(16)無機蒸着層/層(YZ)/ポリオレフィン層、
(17)層(YZ)/無機蒸着層/水酸基含有ポリマー層、
(18)無機蒸着層/層(YZ)/水酸基含有ポリマー層、
(19)層(YZ)/ポリエステル層/ポリアミド層/ポリオレフィン層、
(20)層(YZ)/ポリエステル層/層(YZ)/ポリアミド層/ポリオレフィン層、
(21)ポリエステル層/層(YZ)/ポリアミド層/ポリオレフィン層、
(22)層(YZ)/ポリアミド層/ポリエステル層/ポリオレフィン層、
(23)層(YZ)/ポリアミド層/層(YZ)/ポリエステル層/ポリオレフィン層、
(24)ポリアミド層/層(YZ)/ポリエステル層/ポリオレフィン層、
(25)層(YZ)/ポリオレフィン層/ポリアミド層/ポリオレフィン層、
(26)層(YZ)/ポリオレフィン層/層(YZ)/ポリアミド層/ポリオレフィン層、
(27)ポリオレフィン層/層(YZ)/ポリアミド層/ポリオレフィン層、
(28)層(YZ)/ポリオレフィン層/ポリオレフィン層、
(29)層(YZ)/ポリオレフィン層/層(YZ)/ポリオレフィン層、
(30)ポリオレフィン層/層(YZ)/ポリオレフィン層、
(31)層(YZ)/ポリエステル層/ポリオレフィン層、
(32)層(YZ)/ポリエステル層/層(YZ)/ポリオレフィン層、
(33)ポリエステル層/層(YZ)/ポリオレフィン層、
(34)層(YZ)/ポリアミド層/ポリオレフィン層、
(35)層(YZ)/ポリアミド層/層(YZ)/ポリオレフィン層、
(36)ポリアミド層/層(YZ)/ポリオレフィン層、
(37)層(YZ)/ポリエステル層/紙層、
(38)層(YZ)/ポリアミド層/紙層、
(39)層(YZ)/ポリオレフィン層/紙層、
(40)ポリオレフィン層/紙層/ポリオレフィン層/層(YZ)/ポリエステル層/ポリオレフィン層、
(41)ポリオレフィン層/紙層/ポリオレフィン層/層(YZ)/ポリアミド層/ポリオレフィン層、
(42)ポリオレフィン層/紙層/ポリオレフィン層/層(YZ)/ポリオレフィン層、
(43)紙層/ポリオレフィン層/層(YZ)/ポリエステル層/ポリオレフィン層、
(44)ポリオレフィン層/紙層/層(YZ)/ポリオレフィン層、
(45)紙層/層(YZ)/ポリエステル層/ポリオレフィン層、
(46)紙層/層(YZ)/ポリオレフィン層、
(47)層(YZ)/紙層/ポリオレフィン層、
(48)層(YZ)/ポリエステル層/紙層/ポリオレフィン層、
(49)ポリオレフィン層/紙層/ポリオレフィン層/層(YZ)/ポリオレフィン層/水酸基含有ポリマー層、
(50)ポリオレフィン層/紙層/ポリオレフィン層/層(YZ)/ポリオレフィン層/ポリアミド層、
(51)ポリオレフィン層/紙層/ポリオレフィン層/層(YZ)/ポリオレフィン層/ポリエステル層。
(性能1)20℃、85%RHの条件下における酸素透過度が2ml/(m2・day・atm)以下である。
(性能2)
23℃、50%RHの条件下で、5%延伸した状態で5分間保持した後の20℃、85%RHの条件下における酸素透過度が、4ml/(m2・day・atm)以下である。
本発明の多層構造体は、ガスバリア性に優れ、変形や衝撃などの物理的ストレスを受けた際にも、ガスバリア性を高いレベルで維持することができる。また、本発明によれば、外観に優れる多層構造体を得ることができる。そのため、本発明の多層構造体は、様々な用途に適用できる。たとえば、本発明の多層構造体を備えた製品は、当該多層構造体を包装材料として、または太陽電池、ディスプレイもしくは照明装置である電子デバイスの部材として含む製品であってもよい。包装材料は、成形品であってもよく、袋の形状を有していてもよい。電子デバイスの部材は、たとえば、電子デバイス本体を表面を保護する保護シートである。また、本発明の多層構造体は、ガスバリア性に加えて、水蒸気に対するバリア性を有することもでき、その場合には、変形や衝撃などの物理的ストレスを受けた際にも、その水蒸気バリア性を高いレベルで維持することができる。特に、太陽電池部材やディスプレイ部材などの製品に使用する場合には、この特性が製品の耐久性に大きく寄与する場合がある。
以下、本発明の多層構造体の製造方法について説明する。この方法によれば、本発明の多層構造体を容易に製造できる。本発明の多層構造体の製造方法に用いられる材料、および多層構造体の構成などは、上述したものと同様であるので、重複する部分については説明を省略する場合がある。たとえば、基材(X)、層(Y)、層(Z)、金属酸化物(A)、リン化合物(B)、重合体(C)および重合体(E)に対して、本発明の多層構造体の説明における記載を適用することが可能である。なお、この製造方法について説明した事項については、本発明の多層構造体に適用できる。また、本発明の多層構造体について説明した事項については、本発明の製造方法に適用できる。
工程(I)で用いられる、金属酸化物(A)と反応可能な部位を含有する少なくとも1種の化合物を、以下では、「少なくとも1種の化合物(Z)」という場合がある。工程(I)では、金属酸化物(A)と、少なくとも1種の化合物(Z)と、溶媒とを少なくとも混合する。1つの観点では、工程(I)では、金属酸化物(A)と、少なくとも1種の化合物(Z)とを含む原料を、溶媒中で反応させる。当該原料は、金属酸化物(A)および少なくとも1種の化合物(Z)の他に、他の化合物を含んでもよい。典型的には、金属酸化物(A)は粒子の形態で混合される。
工程(a):金属酸化物(A)を含む液体(S)を調製する工程。
工程(b):リン化合物(B)を含む溶液(T)を調製する工程。
工程(c):上記工程(a)および(b)で得られた液体(S)と溶液(T)とを混合する工程。
工程(II)では、基材(X)上にコーティング液(U)を塗布することによって、基材(X)上に層(YA)の前駆体層を形成する。コーティング液(U)は、基材(X)の少なくとも一方の面の上に直接塗布してもよい。また、コーティング液(U)を塗布する前に、基材(X)の表面を公知のアンカーコーティング剤で処理したり、基材(X)の表面に公知の接着剤を塗布したりするなどして、基材(X)の表面に接着層(H)を形成しておいてもよい。また、後述する工程(IV)によって基材(X)上に予め形成された層(Z)上に、コーティング液(U)を塗布することによって、層(Z)上に層(YA)の前駆体層を形成することもできる。
工程(III)では、工程(II)で形成された前駆体層(層(YA)の前駆体層)を、110℃以上の温度で熱処理することによって層(YA)を形成する。
工程(IV)では、リン原子を複数有する重合体(E)を含むコーティング液(V)を塗布することによって、基材(X)上(または層(Y)上)に層(Z)を形成する。通常、コーティング液(V)は、重合体(E)が溶媒に溶解された溶液である。
実施例で形成される層(YA)の赤外線吸収スペクトルは、以下の方法で測定した。
得られた多層構造体の外観を、目視によって下記のように評価した。
A:無色透明で均一であり、極めて良好な外観であった。
B:わずかにくもりまたはムラが見られたが、良好な外観であった。
酸素透過度は、酸素透過量測定装置(モダンコントロール社製「MOCON OX-TRAN2/20」)を用いて測定した。具体的には、酸素供給側に層(YZ)(または層(YZ))が向き、キャリアガス側に基材(X)が向くように多層構造体をセットし、温度が20℃、酸素供給側の湿度が85%RH、キャリアガス側の湿度が85%RH、酸素圧が1気圧、キャリアガス圧力が1気圧の条件下で酸素透過度(単位:ml/(m2・day・atm))を測定した。キャリアガスとしては2体積%の水素ガスを含む窒素ガスを使用した。
21cm×30cmの大きさの多層構造体を作製した。そして、その多層構造体を23℃、50%RHの条件下で24時間以上放置した後、同条件下で長軸方向に5%延伸し、延伸した状態を5分間保持することで、延伸後の多層構造体を得た。酸素透過度は、酸素透過量測定装置(モダンコントロール社製「MOCON OX-TRAN2/20」)を用いて測定した。具体的には、酸素供給側に層(YZ)が向き、キャリアガス側に基材(X)が向くように多層構造体をセットし、温度が20℃、酸素供給側の湿度が85%RH、キャリアガス側の湿度が85%RH、酸素圧が1気圧、キャリアガス圧力が1気圧の条件下で酸素透過度(単位:ml/(m2・day・atm))を測定した。キャリアガスとしては2体積%の水素ガスを含む窒素ガスを使用した。
層(YA)を製造するために使用したコーティング液(U)の製造例を示す。
蒸留水230質量部を撹拌しながら70℃に昇温した。その蒸留水に、アルミニウムイソプロポキシド88質量部を1時間かけて滴下し、液温を徐々に95℃まで上昇させ、発生するイソプロパノールを留出させることによって加水分解縮合を行った。得られた液体に、60質量%の硝酸水溶液4.0質量部を添加し、95℃で3時間撹拌することによって加水分解縮合物の粒子の凝集体を解膠させた後に、固形分濃度がアルミナ換算で10質量%になるように濃縮した。こうして得られた分散液18.66質量部に対して、蒸留水58.19質量部、メタノール19.00質量部、および5質量%のポリビニルアルコール水溶液0.50質量部を加え、均一になるように撹拌することによって、分散液(S1)を得た。また、85質量%のリン酸水溶液3.66質量部を、溶液(T1)として使用した。続いて、分散液(S1)および溶液(T1)をともに15℃に調節した。次に、15℃の液温を維持した状態で、分散液(S1)を攪拌しながら溶液(T1)を滴下してコーティング液(U1)を得た。得られたコーティング液(U1)を15℃に保持したまま、粘度が1500mPa・sになるまで攪拌を続けた。なお、当該コーティング液(U1)における、金属酸化物(A)(アルミナ)を構成する金属原子のモル数(NM)とリン化合物(B)(リン酸)を構成するリン原子のモル数(NP)との比率(モル数(NM)/モル数(NP))は、1.15であった。
攪拌機及び温度計を備えた丸底フラスコ(内容積:50ml)を窒素置換し、溶媒として水2.5gを仕込み、攪拌しながらビニルホスホニックアシッド(以下、「VPA」と略記する場合がある)10g、水2.5g及び2,2’-アゾビス(2-アミジノプロパン)2塩酸塩(以下、「AIBA」と略記する場合がある)25mgの混合溶液を丸底フラスコに滴下した。この時から重合の全過程を通じて微量の窒素ガスを流し続けた。丸底フラスコをオイルバスに漬けて80℃で3時間反応させた後、反応混合物を15gの水で希釈し、セルロース膜(スペクトラム・ラボラトリーズ社製、「Spectra/Por」(商品名))でろ過した。次に、エバポレーターによってろ液の溶媒を留去し、50℃で24時間真空乾燥することによって白色の重合体を得た。この重合体をゲル・パーミエーション・クロマトグラフで、溶媒として1.2wt%のNaCl水溶液を用い重合体濃度0.1wt%で分子量を測定したところ、数平均分子量はポリエチレングリコール換算で約10,000であった。
基材として、延伸ポリエチレンテレフタレートフィルム(東レ株式会社製、「ルミラーP60」(商品名)、厚さ12μm、以下では「PET」と略記することがある)を準備した。その基材(PET)上に、乾燥後の厚さが0.5μmとなるようにバーコータによってコーティング液(U1)を塗布し、110℃で5分間乾燥した。次いで、180℃で1分間の熱処理を施し、層(Y1)(0.5μm)/PET(12μm)という構造を有する構造体(A1)を得た。次いで、構造体(A1)の層(Y1)上に、乾燥後の厚さが0.3μmとなるようにバーコータによってコーティング液(V1)を塗布し、110℃で5分間乾燥することで、層(Z1)(0.3μm)/層(Y1)(0.5μm)/PET(12μm)という構造を有する本発明の多層構造体(B1)を得た。
層(Z)の厚みを表1に従って変更したこと以外は実施例1と同様の方法によって、多層構造体を得た。
使用するコート液(V)を表1に従って変更したこと以外は実施例1と同様の方法によって、多層構造体を得た。
熱処理の条件を表1に従って変更したこと以外は実施例1と同様の方法によって、多層構造体を得た。
使用するコート液(U)を表1に従って変更したこと以外は実施例1と同様の方法によって、多層構造体を得た。
熱処理工程を層(Z)の形成後に実施したこと以外は実施例1と同様の方法によって、多層構造体を得た。
層(Y)および層(Z)を基材の両面に積層したこと以外は実施例1と同様の方法によって、多層構造体を得た。得られた多層構造体の透湿度を、実施例1と同様にして測定したところ0.1g/(m2・day)以下であった。
基材を延伸ナイロンフィルム(ユニチカ株式会社製 「エンブレム ONBC」(商品名)、厚さ15μm、「ONY」と略記することがある)としたこと以外は実施例1と同様の方法によって、多層構造体を得た。
層(Z)の形成後に層(Y)を形成したこと以外は実施例1と同様の方法によって、多層構造体を得た。
層(Y)を厚み0.03μmのアルミニウムの蒸着層としたこと以外は実施例1と同様の方法によって、多層構造体を得た。アルミニウム層は、真空蒸着法で形成した。
層(Y)を厚み0.03μmの酸化アルミニウムの蒸着層としたこと以外は実施例1と同様の方法によって、多層構造体を得た。酸化アルミニウム層は、真空蒸着法で形成した。
実施例1~18において、層(Z)を形成しなかったものを比較例1~18とした。
層(Y)を厚み0.03μmの酸化ケイ素の蒸着層である層(Y)’としたこと以外は実施例1と同様の方法によって、多層構造体を得た。酸化ケイ素層は、真空蒸着法で形成した。
層(Y)を形成しなかったこと以外は実施例1と同様の方法によって、多層構造体を得た。
層(Z)をPET上に形成したこと以外は実施例1と同様の方法によって、多層構造体を得た。すなわち、比較例20では、層(Y1)(0.5μm)/PET(12μm)/層(Z1)(0.3μm)という構造を有する、比較例20の多層構造体を作製した。
比較例19において層(Z)を形成しなかったものを、比較例22とした。
比較例20において層(Z)を形成しなかったもの、すなわち基材(PET)のみを比較例23とした。
実施例19では、本発明の多層構造体を用いて縦製袋充填シール袋を作製した。まず、実施例1と同様の方法によって、多層構造体(B1)を作製した。次に、2液型の接着剤(三井武田ケミカル株式会社製、A-520(商品名)およびA-50(商品名))を多層構造体(B1)上にコートして乾燥したものを準備し、これと延伸ナイロンフィルム(上記したONY)とをラミネートして積層体を得た。続いて、その積層体の延伸ナイロンフィルム上に、2液型の接着剤(三井武田ケミカル株式会社製、A-520(商品名)およびA-50(商品名))をコートして乾燥したものを準備し、これと無延伸ポリプロピレンフィルム(東セロ株式会社製、RXC-21(商品名)、厚さ70μm、以下「CPP70」と略記することがある)とをラミネートした。このようにして、PET/層(Y1)/層(Z1)/接着剤/ONY/接着剤/CPP70という構造を有する多層構造体(C19)を得た。
実施例20では、本発明の多層構造体を用いて真空包装袋を作製した。まず、実施例1と同様の方法によって、多層構造体(B1)を作製した。次に、2液型の接着剤(三井武田ケミカル株式会社製、A-520(商品名)およびA-50(商品名))を延伸ナイロンフィルム(上述したONY)上にコートして乾燥したものを準備し、それと多層構造体(B1)とをラミネートした。次に、ラミネートされた多層構造体(B1)上に、2液型の接着剤(三井武田ケミカル株式会社製、A-520(商品名)およびA-50(商品名))をコートして乾燥したものを準備し、それと無延伸ポリプロピレンフィルム(上述したCPP70)とをラミネートした。このようにして、ONY/接着剤/層(Z1)/層(Y1)/PET/接着剤/CPP70という構成を有する多層構造体(C20)を得た。
実施例21では、本発明の多層構造体を用いてスパウト付パウチを作製した。まず、実施例19と同様の方法によって、PET/層(Y1)/層(Z1)/接着剤/ONY/接着剤/CPP70という構造を有する多層構造体(C21)を得た。次に、多層構造体(C21)を所定の形状に2枚切り出した後、CPP70が内側となるように2枚の多層構造体(C21)を重ね合わせ、周縁をヒートシールし、更に、ポリプロピレン製のスパウトをヒートシールによって取り付けた。このようにして、平パウチ型のスパウト付パウチを問題なく作製できた。
実施例22では、本発明の多層構造体を用いてラミネートチューブ容器を作製した。まず、実施例1と同様の方法によって、多層構造体(B1)を作製した。次に、2枚の無延伸ポリプロピレンフィルム(トーセロ株式会社製、RXC-21(商品名)、厚さ100μm、以下「CPP100」と略記することがある)のそれぞれに、2液型の接着剤(三井武田ケミカル株式会社製、A-520(商品名)およびA-50(商品名))をコートして乾燥したものを準備し、多層構造体(B1)とラミネートした。このようにして、CPP100/接着剤/層(Z1)/層(Y1)/PET/接着剤/CPP100という構造を有する多層構造体(C22)を得た。
実施例23では、本発明の多層構造体を用いて輸液バッグを作製した。まず、実施例19と同様の方法によって、PET/層(Y1)/層(Z1)/接着剤/ONY/接着剤/CPP70という構造を有する多層構造体(C23)を得た。次に、多層構造体(C23)を所定の形状に2枚切り出した後、CPP70が内側となるように2枚の多層構造体(C23)を重ね合わせ、周縁をヒートシールし、更に、ポリプロピレン製のスパウトをヒートシールによって取り付けた。このようにして、輸液バッグを問題なく作製できた。
実施例24では、本発明の多層構造体を用いて容器用蓋材を作製した。まず、実施例19と同様の方法によって、PET/層(Y1)/層(Z1)/接着剤/ONY/接着剤/CPP70という構造を有する多層構造体(C24)を得た。次に、その多層構造体(C24)を、容器用蓋材として、直径88mmの円形に切り出した。また、直径78mm、フランジ幅が6.5mm、高さ30mmで、ポリオレフィン層/スチール層/ポリオレフィン層の3層で構成される円柱状容器(東洋製罐株式会社製ハイレトフレックスHR78-84)を準備した。この容器に水をほぼ満杯に充填し、多層構造体(C24)からなる容器用蓋材を、フランジ部にヒートシールした。このようにして、容器用蓋材を用いた蓋付き容器を問題なく作製できた。
実施例25では、本発明の多層構造体を用いて紙容器を作製した。まず、実施例1と同様の方法によって、多層構造体(B1)を作製した。次に、400g/m2の板紙の両面に接着剤を塗布した後、その両面にポリプロピレン樹脂(以下、「PP」と略記することがある)を押出ラミネートすることによって、板紙の両面にPP層(厚さ各20μm)を形成した。その後、一方のPP層の表面に接着剤を塗布し、その上に多層構造体(B1)をラミネートし、さらに多層構造体(B1)の表面に接着剤を塗布し、無延伸ポリプロピレンフィルム(上述したCPP70)と貼り合わせた。このようにして、PP/板紙/PP/接着剤/層(Z1)/層(Y1)/PET/接着剤/CPP70という構成を有する多層構造体(C25)を作製した。多層構造体(C25)の作製において、必要に応じてアンカーコート剤を用いた。このようにして得た多層構造体(C25)を用いて、ブリック型の紙容器を問題なく作製できた。
実施例26では、本発明の多層構造体を用いて真空断熱体を作製した。まず、実施例20と同様の方法によって、ONY/接着剤/層(Z1)/層(Y1)/PET/接着剤/CPP70という構成を有する多層構造体(C26)を得た。次に、多層構造体(C26)を所定の形状に2枚切り出した後、CPP70が内側となるように2枚の多層構造体(C26)を重ね合わせ、長方形の3辺をヒートシールすることによって袋を形成した。次に、袋の開口部から断熱性の芯材を充填し、真空包装機(Frimark GmbH製VAC-STAR 2500型)を用いて、温度20℃で内部圧力10Paの状態で袋を密封した。このようにして、真空断熱体を問題なく作製できた。なお、断熱性の芯材には、120℃の雰囲気下で4時間乾燥したシリカ微粉末を用いた。
実施例27では、本発明の多層構造体を用いて太陽電池モジュールを作製した。まず、実施例1と同様の方法によって、多層構造体(B1)を作製した。次に、10cm角の強化ガラス上に設置されたアモルファス系のシリコン太陽電池セルを厚さ450μmのエチレン-酢酸ビニル共重合体で挟み込み、その上に多層構造体(B1)の層(Z1)が対面するように貼り合わせることで太陽電池モジュールを作製した。貼り合わせは、150℃にて真空引きを3分間行った後、9分間圧着を行うことによって実施した。このようにして作製された太陽電池モジュールは、良好に作動し、長期に渡って良好な電気出力特性を示した。
Claims (19)
- 基材(X)、層(Y)および層(Z)をそれぞれ1層以上有する多層構造体であって、
前記層(Y)はアルミニウム原子を含み、前記層(Z)はリン原子を複数有する重合体(E)を含み、
前記重合体(E)は、ビニルホスホン酸類を含む少なくとも1種の単量体の重合体であり、
少なくとも1組の前記層(Y)と前記層(Z)とが隣接して積層されている、多層構造体。 - 少なくとも1組の、前記基材(X)、前記層(Y)および前記層(Z)が、前記基材(X)/前記層(Y)/前記層(Z)の順に積層された構造を有する、請求項1に記載の多層構造体。
- 前記層(Y)が反応生成物(R)を含む層(YA)であり、
前記反応生成物(R)は、アルミニウムを含む金属酸化物(A)とリン化合物(B)とが反応してなる反応生成物であり、
前記層(YA)の赤外線吸収スペクトルにおいて800~1400cm-1の範囲における赤外線吸収が最大となる波数(n1)が1080~1130cm-1の範囲にある、請求項1に記載の多層構造体。 - 前記層(YA)の赤外線吸収スペクトルにおいて、前記波数(n1)における吸光度(α1)と、波数(n2)における吸光度(α2)とが、吸光度(α2)/吸光度(α1)≦0.2の関係を満たし、
前記前記波数(n2)は、前記層(YA)の赤外線吸収スペクトルにおいて、2500~4000cm-1の範囲における水酸基の伸縮振動に基づく赤外線吸収が最大となる波数である、請求項4に記載の多層構造体。 - 前記波数(n1)の吸収ピークの半値幅が200cm-1以下である、請求項4に記載の多層構造体。
- 前記金属酸化物(A)は、加水分解可能な特性基が結合した金属原子(M)を含有する化合物(L)の加水分解縮合物であって、
前記化合物(L)が、以下の式(II)で示される少なくとも1種の化合物(L1)を含む、請求項4に記載の多層構造体。
AlX1 mR1 (3-m) (II)
[式(II)中、X1は、F、Cl、Br、I、R2O-、R3C(=O)O-、(R4C(=O))2CH-およびNO3からなる群より選ばれる。R1、R2、R3およびR4はそれぞれ、アルキル基、アラルキル基、アリール基およびアルケニル基からなる群より選ばれる。式(II)において、複数のX1が存在する場合には、それらのX1は互いに同一であってもよいし異なっていてもよい。式(II)において、複数のR1が存在する場合には、それらのR1は互いに同一であってもよいし異なっていてもよい。式(II)において、複数のR2が存在する場合には、それらのR2は互いに同一であってもよいし異なっていてもよい。式(II)において、複数のR3が存在する場合には、それらのR3は互いに同一であってもよいし異なっていてもよい。式(II)において、複数のR4が存在する場合には、それらのR4は互いに同一であってもよいし異なっていてもよい。mは1~3の整数を表す。] - 前記化合物(L1)が、アルミニウムトリイソプロポキシドおよびアルミニウムトリs-ブトキシドから選ばれる少なくとも1種の化合物である、請求項7に記載の多層構造体。
- 前記リン化合物(B)が、リン酸、ポリリン酸、亜リン酸、ホスホン酸およびそれらの誘導体からなる群より選ばれる少なくとも1種の化合物である、請求項4に記載の多層構造体。
- 前記層(YA)において、前記金属酸化物(A)を構成する金属原子(M)のモル数NMと、前記リン化合物(B)に由来するリン原子のモル数NPとが、1.0≦(前記モル数NM)/(前記モル数NP)≦3.6の関係を満たす、請求項4に記載の多層構造体。
- 前記層(Y)が、アルミニウムの蒸着層または酸化アルミニウムの蒸着層である、請求項1に記載の多層構造体。
- 基材(X)が、熱可塑性樹脂フィルム層、紙層および無機蒸着層からなる群より選ばれる少なくとも1種の層を含む、請求項1に記載の多層構造体。
- 20℃、85%RHの条件下における酸素透過度が2ml/(m2・day・atm)以下である、請求項1に記載の多層構造体。
- 23℃、50%RHの条件下で、5%延伸した状態で5分間保持した後の20℃、85%RHの条件下における酸素透過度が、4ml/(m2・day・atm)以下である、請求項1に記載の多層構造体。
- 基材(X)、層(Y)および層(Z)をそれぞれ1層以上有する請求項1に記載の多層構造体の製造方法であって、
前記層(Y)はアルミニウム原子を含み、前記層(Z)はリン原子を複数有する重合体(E)を含み、
前記重合体(E)は、ビニルホスホン酸類を含む少なくとも1種の単量体の重合体であり、
少なくとも1組の前記層(Y)と前記層(Z)とが隣接して積層されており、
前記重合体(E)を含むコーティング液(V)を塗布することによって前記層(Z)を形成する工程(IV)を含む、製造方法。 - 前記層(Y)は、反応生成物(R)を含む層(YA)であり、
前記反応生成物(R)は、アルミニウムを含む金属酸化物(A)とリン化合物(B)とが反応してなる反応生成物であり、
前記金属酸化物(A)と、前記金属酸化物(A)と反応可能な部位を含有する少なくとも1種の化合物と、溶媒とを混合することによって、前記金属酸化物(A)、前記少なくとも1種の化合物および前記溶媒を含むコーティング液(U)を調製する工程(I)と、
前記基材(X)上に前記コーティング液(U)を塗布することによって、前記基材(X)上に前記層(YA)の前駆体層を形成する工程(II)と、
前記層(YA)の前駆体層を110℃以上の温度で熱処理して前記層(YA)を形成する工程(III)とをさらに含み、
前記少なくとも1種の化合物が前記リン化合物(B)を含み、
前記コーティング液(U)において、前記金属酸化物(A)を構成する金属原子(M)のモル数NMと、前記リン化合物(B)に含まれるリン原子のモル数NPとが、1.0≦(前記モル数NM)/(前記モル数NP)≦3.6の関係を満たす、請求項15に記載の製造方法。 - 前記工程(III)の後に前記工程(IV)を実施する、請求項17に記載の製造方法。
- 前記層(Y)が、アルミニウムの蒸着層または酸化アルミニウムの蒸着層である、請求項15に記載の製造方法。
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KR102050710B1 (ko) * | 2015-09-17 | 2019-12-02 | 주식회사 쿠라레 | 다층 구조체 및 그 제조 방법, 그것을 사용한 포장재 및 제품, 및 전자 디바이스의 보호 시트 |
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US11214696B2 (en) | 2016-05-18 | 2022-01-04 | Kuraray Co., Ltd. | Multilayer structure and method for producing same, coating liquid, packaging material, and protective sheet for electronic devices |
US11692106B2 (en) | 2016-05-18 | 2023-07-04 | Kuraray Co., Ltd. | Multilayer structure and method for producing same, coating liquid, packaging material, and protective sheet for electronic devices |
JP2018202809A (ja) * | 2017-06-08 | 2018-12-27 | 株式会社クラレ | 多層構造体、真空包装袋および真空断熱体 |
JP2019034421A (ja) * | 2017-08-10 | 2019-03-07 | 株式会社クラレ | 多層構造体およびその製造方法、それを用いた包装材および製品、ならびに電子デバイスの保護シート |
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US10273379B2 (en) | 2019-04-30 |
EP2955021A4 (en) | 2016-07-13 |
US20150368503A1 (en) | 2015-12-24 |
AU2014215300B2 (en) | 2017-03-30 |
KR20150119010A (ko) | 2015-10-23 |
EP2955021B1 (en) | 2018-03-28 |
JPWO2014122942A1 (ja) | 2017-01-26 |
AU2014215300A1 (en) | 2015-08-20 |
CN105026150B (zh) | 2017-11-24 |
JP6306522B2 (ja) | 2018-04-04 |
CN105026150A (zh) | 2015-11-04 |
EP2955021A1 (en) | 2015-12-16 |
KR102303879B1 (ko) | 2021-09-24 |
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