Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
  • C08J7/04—Coating
  • C08J7/048—Forming gas barrier coatings
• • 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
  • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
  • B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
  • B05D3/0254—After-treatment
• • 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
• • 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
• • 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
  • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
  • B32B7/04—Interconnection of layers
  • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
• • 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
  • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/18—Manufacture of films or sheets
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
  • C08J7/04—Coating
  • C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
  • C08J7/04—Coating
  • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/20—Oxides; Hydroxides
  • C08K3/22—Oxides; Hydroxides of metals
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/32—Phosphorus-containing compounds
• • 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
  • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
• • 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
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/60—Additives non-macromolecular
  • C09D7/61—Additives non-macromolecular inorganic
• • 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
  • B05D2518/00—Other type of polymers
  • B05D2518/10—Silicon-containing polymers
  • B05D2518/12—Ceramic precursors (polysiloxanes, polysilazanes)
• • 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
• • 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
  • B32B2255/26—Polymeric coating
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/20—Oxides; Hydroxides
  • C08K3/22—Oxides; Hydroxides of metals
  • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
• • 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
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E10/00—Energy generation through renewable energy sources
  • Y02E10/50—Photovoltaic [PV] energy

Definitions

• the present invention relates to a multilayer structure with high gas barrier properties and water vapor barrier properties and high definition, a method for producing the same, and a protective sheet for electronic devices and electronic devices using the same.
• Electronic devices such as electronic equipment equipped with solar cells and display devices require a translucent protective member to protect the surface.
• a protective member for example, a thick glass plate, a protective sheet having an excellent barrier property (oxygen barrier property and water vapor barrier property) having a barrier layer on a resin base material, and the like are sometimes used.
• Patent Document 1 discloses that a coating liquid containing an aluminum-containing compound and a phosphorus compound is applied onto a substrate (X), followed by drying and heat treatment to obtain a reaction product. is provided with a layer (Y) containing It is described that it has excellent barrier properties and can maintain its performance even after a dump heat test.
• protective sheets such as electronic devices may require a higher level of definition, and the multilayer structures used in conventional electronic devices may not have sufficient definition. .
• the high barrier properties of the multilayer structures used in conventional electronic devices are useful as protective sheets for electronic devices and the like, and there is a demand for multilayer structures having high definition while maintaining such performance.
• the present inventors conducted repeated studies using a substrate with high image clarity as the substrate (X), but it was difficult to achieve high definition. rice field. As a result of intensive studies by the present inventors, it was found that there is a relationship between the coating speed of the coating liquid applied when forming the layer (Y) and the definition of the resulting multilayer structure, and the present invention has been realized. reached.
• the present invention has been made based on the circumstances as described above, and an object of the present invention is to provide a multilayer structure having high barrier properties and definition, a method for producing the same, a protective sheet for electronic devices using the same, and an electronic device. to provide the device.
• the object is [1] a multilayer structure comprising a substrate (X) and a layer (Y), wherein the layer (Y) is a metal oxide (A) containing aluminum atoms (hereinafter simply may be abbreviated as “metal oxide (A)”) and an inorganic phosphorus compound (BI), the substrate (X) and the layer (Y) are adjacent to each other, A multilayer structure having an image clarity of 90% or more at an optical comb width of 0.25 mm, measured according to ISO17221:2014; [2] The multilayer structure of [1], which has a haze value of 3% or less as measured according to JIS K7105:1981; [3] of [1] or [2], which has a water vapor transmission rate of 1 ⁇ 10 ⁇ 2 g/m 2 day or less at 40° C.
• metal oxide (A) a metal oxide containing aluminum atoms
• BI inorganic phosphorus compound
• a protective sheet for an electronic device comprising the multilayer structure of any one of [1] to [9];
• the protective sheet of [11] which is a protective sheet for protecting the surface of a photoelectric conversion device, an information display device, or a lighting device;
• the present invention it is possible to provide a multilayer structure having high barrier properties and definition, a method for producing the same, and a protective sheet for an electronic device and an electronic device using the same.
• carrier property mainly means both oxygen barrier property and water vapor barrier property
• gas barrier property mainly means oxygen barrier property
• the multilayer structure of the present invention is a multilayer structure comprising a substrate (X) and a layer (Y), wherein the layer (Y) is a reaction product of a metal oxide (A) and an inorganic phosphorus compound (BI). (D), wherein the substrate (X) and layer (Y) are adjacent, and the image clarity of the multilayer structure at an optical comb width of 0.25 mm, measured according to ISO 17221:2014 is 90% or more.
• the term “adjacent” means that they are laminated in a very close manner, and specifically, they are directly laminated or another layer such as an adhesive layer (for example, a thickness of 10 ⁇ m or less It means that it is laminated via the adhesive layer).
• the distance between the substrate (X) and the layer (Y) may be 0 ⁇ m or more and 10 ⁇ m or less, or 0 ⁇ m or more and 1 ⁇ m or less. 0 ⁇ m or more and 0.1 ⁇ m or less, or 0 ⁇ m or more and 0.03 ⁇ m or less.
• one layer of the substrate (X) may be adjacent to the layer (Y), and the other substrates (X) are the layers ( It may or may not be adjacent to Y).
• one layer (Y) may be adjacent to the substrate (X), and the other layers (Y) may be adjacent to the substrate (X). may or may not be adjacent to That is, at least one set of base material (X) and layer (Y) should be adjacent to each other.
• the multilayer structure of the present invention has an image clarity of 90% or more, it is excellent in definition when used as a protective sheet for electronic devices, for example.
• the image clarity of the multilayer structure of the present invention is preferably 91% or higher, more preferably 92% or higher, still more preferably 93% or higher, and even more preferably 94% or higher or 95% or higher in some cases.
• the image clarity of the multilayer structure of the present invention may be 100% or less, or may be 99%, 98%, 97% or 96% or less.
• thickness means the average value (average thickness) of measured values at any five locations.
• the material of the substrate (X) is not particularly limited, but it preferably contains a thermoplastic resin from the viewpoint of having high image clarity. Although the form of the base material (X) is not particularly limited, it is preferably a layered form such as a film or sheet.
• the substrate (X) preferably contains a thermoplastic resin film or a thermoplastic resin film laminated with an inorganic deposition layer (X′), and more preferably contains a thermoplastic resin film, and is a thermoplastic resin film. is more preferred.
• Thermoplastic resins used for the substrate (X) include, for example, polyolefin resins such as polyethylene and polypropylene; polyethylene terephthalate (PET), polyethylene-2,6-naphthalate, polybutylene terephthalate, and copolymers thereof; Polyamide resins such as nylon-6, nylon-66, and nylon-12; hydroxyl group-containing polymers such as polyvinyl alcohol and ethylene-vinyl alcohol copolymer; polystyrene; poly(meth)acrylic acid ester; polyacrylonitrile; polyvinyl acetate; polycarbonate; polyarylate; regenerated cellulose; polyimide;
• the thermoplastic resin used for the substrate (X) is preferably at least one selected from the group consisting of polyethylene, polypropylene, polyethylene terephthalate, nylon-6, and nylon-66, and polyethylene terephthalate is preferred from the viewpoint of excellent image clarity. more preferred.
• the base material (X) may contain inorganic fine particles or organic fine particles in order to impart lubricity and anti-blocking properties. From the viewpoint of enhancing the image clarity of the substrate (X), when inorganic fine particles or organic fine particles are contained, it is preferable that the surface layer described later contains these. That is, from the viewpoint of image clarity, it may be preferable that the portion of the substrate (X) other than the surface layer does not contain inorganic fine particles or organic fine particles.
• inorganic fine particles include gold, silver, copper, platinum, palladium, rhenium, vanadium, osmium, cobalt, iron, zinc, ruthenium, praseodymium, chromium, nickel, aluminum, tin, zinc, titanium, tantalum, zirconium, and antimony.
• metals such as indium, yttrium and lanthanum
• metal oxides such as zinc oxide, titanium oxide, cesium oxide, antimony oxide, tin oxide, indium tin oxide, yttrium oxide, lanthanum oxide, zirconium oxide, aluminum oxide and silicon oxide , lithium fluoride, magnesium fluoride, aluminum fluoride, cryolite and other metal fluorides, calcium phosphate and other metal phosphates, calcium carbonate and other carbonates, barium sulfate and other sulfates, and other talc and kaolin. can be used.
• organic fine particles examples include silicone-based compounds, crosslinked fine particles such as crosslinked styrene, crosslinked acryl, and crosslinked melamine, as well as those that are incompatible with the thermoplastic resin that constitutes the base material (X), but are finely dispersed to form a sea-island structure.
• the thermoplastic resin to be formed can also be used as fine particles.
• the average particle size of the fine particles (inorganic fine particles and organic fine particles) used is preferably 0.001 to 5 ⁇ m.
• the substrate (X) may be a stretched film or an unstretched film.
• a stretched film, particularly a biaxially stretched film, is preferred because the processability (printing, lamination, etc.) of the obtained 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.
• the thickness of one layer of the substrate (X) is preferably 5 ⁇ m or more and 200 ⁇ m or less, more preferably 7 ⁇ m or more and 150 ⁇ m or less, and even more preferably 10 ⁇ m or more and 100 ⁇ m or less.
• the thickness of each layer of the substrate (X) is 5 ⁇ m or more, the mechanical strength and workability tend to be excellent. Further, when the thickness of each layer of the substrate (X) is 200 ⁇ m or less, the obtained multilayer structure tends to be excellent in flexibility.
• the substrate (X) preferably has high image clarity.
• the image clarity of the substrate (X) may be 99% or less, 97% or less, 96% or less, or 95% or less from the viewpoint of production cost.
• the image clarity of the substrate (X) is 90% or more, it becomes easier to adjust the image clarity of the obtained multilayer structure to 90% or more.
• the layers other than the surface layer described later do not contain additives (components other than thermoplastic resins), or if they contain them, they are contained in small amounts. For example, providing a surface layer that
• the substrate (X) preferably has a surface layer from the viewpoint of imparting various functions and improving the image clarity of the substrate (X).
• the surface layer is a layer provided on the surface of the substrate (X), and may be provided on one side or both sides of the substrate (X).
• the substrate (X) may have a resin substrate layer and a surface layer laminated on one side or both sides of the resin substrate layer.
• the resin substrate layer may be a layer of the thermoplastic resin described above as the thermoplastic resin used for the substrate (X).
• the resin substrate layer may be a PET layer.
• Another layer such as an inorganic deposition layer (X') may be present between the resin substrate layer and the surface layer. It is preferable that the resin substrate layer and the surface layer are directly laminated. Even when the surface layer contains a resin as a main component, the resin base layer and the surface layer can be distinguished from each other by the difference in composition constituting each layer.
• the surface layer is not particularly limited as long as it has adhesiveness to the resin base layer and the like, but it is preferable that the main component is a thermoplastic resin.
• “contained as a main component” means that the content is more than 50% by mass.
• Polyester-based resins, polycarbonate-based resins, epoxy-based resins, alkyd-based resins, acrylic-based resins, urea-based resins, urethane-based resins, and the like can be suitably used as the thermoplastic resins.
• two or more different thermoplastic resins such as polyester resin and urethane resin, polyester resin and acrylic resin, or urethane resin and acrylic resin, may be used in combination. Among them, at least one selected from the group consisting of polyester resins, acrylic resins and urethane resins is preferable, and polyester resins are more preferable.
• the surface layer it is preferable for the surface layer to contain various cross-linking agents from the viewpoint of improving the heat-resistant adhesion and at the same time dramatically improving the moisture-resistant adhesion.
• various cross-linking agents from the viewpoint of improving the heat-resistant adhesion and at the same time dramatically improving the moisture-resistant adhesion.
• the surface layer further contains a cross-linking agent.
• the thermoplastic resin and the cross-linking agent that constitute the surface layer can be used by mixing them at any ratio, but the cross-linking agent is 0.2 to 20 parts by mass with respect to 100 parts by mass of the thermoplastic resin. , more preferably 0.5 to 15 parts by mass, and still more preferably 1 to 10 parts by mass.
• the surface layer may contain the aforementioned inorganic fine particles or organic fine particles in order to impart slipperiness and anti-blocking properties.
• the heat shrinkage rate in the MD direction when the base material (X) is heated at 210° C. for 1 minute is preferably 2.90% or less, more preferably 2.80% or less, from the viewpoint of further enhancing steam barrier properties and image clarity. more preferred.
• the heat shrinkage rate of the base material (X) in the MD direction may be 0.5% or more, but in some cases it is preferably 2.10% or more from the viewpoint of further improving the water vapor barrier properties.
• the thermal shrinkage rate of the substrate (X) is the thermal shrinkage rate of the substrate (X) used as a raw material for the multilayer structure (the substrate (X) before forming the layer (Y) described later). good.
• a commercially available product can be used as the base material (X).
• Commercially available products with high image clarity include, for example, Lumirror (registered trademark) U403, U483, A48, and XW731C manufactured by Toray Industries, Inc., RH210 manufactured by HYOSUNG, Diafoil (registered trademark) T600 manufactured by Mitsubishi Chemical Corporation, and Toyobo Co., Ltd.
• the base material (X) is preferably surface-treated from the viewpoint of the coatability of the coating liquid (S) described below and the barrier properties of the obtained multilayer structure.
• the surface treatment can be performed by a known method such as UV ozone treatment, high-concentration ozone water treatment, excimer ozone treatment, corona treatment, oxygen plasma treatment, or AP plasma treatment.
• the thermoplastic resin film laminated with the inorganic deposition layer (X') used as the base material (X) is usually a film having barrier properties against oxygen and water vapor, and is a film having transparency.
• a thermoplastic resin film having an inorganic vapor deposition layer (X') laminated on one side thereof is used as the substrate (X)
• the later-described layer (Y) is laminated on the inorganic vapor deposition layer (X') side.
• the thermoplastic resin film used for the thermoplastic resin film laminated with the inorganic deposition layer (X') the thermoplastic resin films exemplified as the substrate (X) described above can be used.
• the inorganic deposition layer (X') can be formed by depositing an inorganic material.
• inorganic substances include metal oxides (eg, silicon oxide, aluminum oxide), metal nitrides (eg, silicon nitride), and metal oxynitrides (eg, silicon oxynitride).
• metal oxides eg, silicon oxide, aluminum oxide
• metal nitrides eg, silicon nitride
• metal oxynitrides eg, silicon oxynitride
• an inorganic deposited layer (X') formed of aluminum oxide, silicon oxide, magnesium oxide, or silicon nitride is preferable from the viewpoint of excellent transparency.
• the substrate (X) does not contain the inorganic deposition layer (X') from the viewpoint of image clarity.
• the method for forming the inorganic vapor deposition layer (X′) is not particularly limited, and physical vapor deposition methods such as vacuum vapor deposition (e.g., resistance heating vapor deposition, electron beam vapor deposition, molecular beam epitaxy, etc.), sputtering methods, ion plating methods, etc. Growth method; thermal chemical vapor deposition method (e.g., catalytic chemical vapor deposition method), photochemical vapor deposition method, plasma chemical vapor deposition method (e.g., capacitively coupled plasma, inductively coupled plasma, surface wave plasma, electron cyclotron resonance , dual magnetron, atomic layer deposition, etc.), chemical vapor deposition such as metal-organic vapor deposition.
• vacuum vapor deposition e.g., resistance heating vapor deposition, electron beam vapor deposition, molecular beam epitaxy, etc.
• sputtering methods ion plating methods, etc. Growth method
• thermal chemical vapor deposition method e.g
• the thickness of the inorganic vapor deposition layer (X′) varies depending on the type of components constituting the inorganic vapor deposition layer, but is preferably 0.002 to 0.5 ⁇ m, more preferably 0.005 to 0.2 ⁇ m, and 0.01 to 0.01 ⁇ m. 0.1 ⁇ m is more preferred. The thickness may be selected within this range so that the multilayer structure has good barrier properties and mechanical properties.
• the thickness of the inorganic vapor deposition layer (X') is 0.002 ⁇ m or more, the barrier property of the inorganic vapor deposition layer (X') against oxygen and water vapor tends to be improved. Further, when the thickness of the inorganic vapor deposition layer (X') is 0.5 ⁇ m or less, the barrier property of the inorganic vapor deposition layer (X') after bending tends to be maintained.
• each substrate (X) may be the same or different.
• the number of layers of the substrate (X) may be one layer, or two or more layers.
• the number of layers of the substrate (X) is, for example, 1 to 3 layers, preferably 1 to 2 layers, more preferably 1 layer.
• Layer (Y) comprises reaction product (D) of metal oxide (A) and inorganic phosphorus compound (BI).
• the layer (Y) functions as a barrier layer, the provision of the layer (Y) in the multilayer structure of the present invention tends to improve barrier properties. Further, by forming the layer (Y) by an appropriate method, the image clarity of the multilayer structure can be made 90% or more.
• Metal oxide containing aluminum atom (A) The metal atoms constituting the metal oxide (A) (they may be collectively referred to as "metal atoms (M)”) are usually at least one selected from metal atoms belonging to groups 2 to 14 of the periodic table. A species of metal atoms, including at least aluminum atoms.
• the metal atom (M) is preferably an aluminum atom alone, but may contain an aluminum atom and other metal atoms. In addition, you may mix and use 2 or more types of metal oxides (A) as a metal oxide (A).
• Metal atoms other than aluminum atoms include, for example, metals of group 2 of the periodic table such as magnesium and calcium; metals of group 12 of the periodic table such as zinc; metals of group 13 of the periodic table; metals of group 13 of the periodic table such as silicon; group metals; transition metals such as titanium and zirconium; Although silicon is sometimes classified as a semimetal, silicon is included in metals in this specification.
• the metal atom (M) that can be used in combination with aluminum is preferably at least one selected from the group consisting of titanium and zirconium from the viewpoint of excellent handleability and gas barrier properties of the resulting multilayer structure.
• the proportion of aluminum atoms in the metal atoms (M) is preferably 50 mol% or more, more preferably 70 mol% or more, still more preferably 90 mol% or more, and even if it is 95 mol% or more, substantially only aluminum atoms may consist of
• Examples of the metal oxide (A) include metal oxides produced by methods such as a liquid phase synthesis method, a gas phase synthesis method, and a solid pulverization method.
• the metal oxide (A) is a hydrolytic condensate of a compound (E) containing a metal atom (M) to which a hydrolyzable characteristic group is bonded (hereinafter sometimes abbreviated as "compound (E)").
• the characteristic group include a halogen atom, NO 3 , an alkoxy group having 1 to 9 carbon atoms which may have a substituent, and an aryloxy group having 6 to 9 carbon atoms which may have a substituent.
• a hydrolytic condensate of compound (E) can be substantially regarded as metal oxide (A). Therefore, in this specification, the hydrolytic condensate of compound (E) may be referred to as "metal oxide (A)".
• metal oxide (A) can be read as “hydrolysis condensate of compound (E)"
• hydrolysis condensate of compound (E) can be read as "metal oxidation It can also be read as “thing (A)”.
• the compound (E) contains a compound (Ea) containing an aluminum atom, which will be described later, because the reaction with the inorganic phosphorus compound (BI) can be easily controlled and the resulting multilayer structure has excellent gas barrier properties.
• Examples of the compound (Ea) include aluminum chloride, aluminum nitrate, aluminum acetate, tris(2,4-pentanedionato)aluminum, trimethoxyaluminum, triethoxyaluminum, tri-n-propoxyaluminum, triisopropoxyaluminum, tri-n-butoxyaluminum, tri-sec-butoxyaluminum, tri-tert-butoxyaluminum and the like, among which triisopropoxyaluminum and tri-sec-butoxyaluminum are preferred.
• two or more compounds (Ea) may be used in combination.
• the compound (E) may contain a compound (Eb) containing a metal atom (M) other than aluminum.
• the compound (Eb) include tetrakis(2,4-pentanedionato)titanium, tetramethoxytitanium, tetraethoxytitanium, tetraisopropoxytitanium, tetra-n-butoxytitanium, tetrakis(2-ethylhexoxy)titanium, and the like.
• Titanium compounds such as tetrakis(2,4-pentanedionato)zirconium, tetra-n-propoxyzirconium, tetra-n-butoxyzirconium, and the like. These may be used individually by 1 type, or may use 2 or more types of compounds (Eb) together.
• the ratio of the compound (Ea) to the compound (E) is not particularly limited, and is preferably 80 mol% or more, more preferably 90 mol% or more, further preferably 95 mol% or more, and may be 100 mol%. .
• a compound in which the ratio of [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 defined as a metal shall be included in oxide (A).
• the oxygen atom (O) bonded only to the metal atom (M) is the oxygen atom (O) in the structure represented by MOM, and the structure represented by MOH Oxygen atoms bonded to metal atoms (M) and hydrogen atoms (H) such as oxygen atoms (O) in are excluded.
• the ratio in the metal oxide (A) is preferably 0.9 or higher, more preferably 1.0 or higher, and even more preferably 1.1 or higher. Although the upper limit of this ratio is not particularly limited, it is usually represented by n/2, where n is the valence of the metal atom (M).
• compound (E) In order for the hydrolytic condensation to occur, it is important that compound (E) has a hydrolyzable characteristic group. If these groups are not bonded, the hydrolytic condensation reaction does not occur or becomes extremely slow, making it difficult to prepare the desired metal oxide (A).
• a hydrolytic condensate of compound (E) may be produced from a specific raw material by, for example, a method employed in a known sol-gel method.
• the raw materials include compound (E), a partial hydrolyzate of compound (E), a complete hydrolyzate of compound (E), a compound obtained by partially hydrolyzing and condensing compound (E), and compound (E ) can be used at least one selected from the group consisting of compounds obtained by condensing a part of the complete hydrolyzate.
• the metal oxide (A) to be mixed with the inorganic phosphorus compound (BI)-containing material contains substantially phosphorus atoms. It is preferable not to contain
• the inorganic phosphorus compound (BI) contains sites capable of reacting with the metal oxide (A), and typically contains a plurality of such sites, preferably 2 to 20 sites.
• sites include functional groups (e.g., hydroxyl groups) present on the surface of the metal oxide (A) and sites capable of condensation reactions, e.g., halogen atoms directly bonded to phosphorus atoms, phosphorus atoms directly bonded to An oxygen atom etc. are mentioned.
• Functional groups (eg, hydroxyl groups) present on the surface of the metal oxide (A) are usually bonded to metal atoms (M) constituting the metal oxide (A).
• inorganic phosphorus compounds include phosphoric acid, diphosphoric acid, triphosphoric acid, polyphosphoric acid in which four or more molecules of phosphoric acid are condensed, phosphorous acid, phosphonic acid, phosphonous acid, phosphinic acid, and phosphine.
• Phosphorus oxoacids such as acids, salts thereof (e.g., sodium phosphate), and derivatives thereof (e.g., halides (e.g., phosphoryl chloride), dehydrates (e.g., diphosphorus pentoxide)), etc. be done.
• the inorganic phosphorus compounds (BI) may be used singly or in combination of two or more.
• the coating liquid (S) described later it is possible to use phosphoric acid alone or to use phosphoric acid in combination with other inorganic phosphorus compounds.
• reaction product (D) The reaction product (D) is obtained by reacting the metal oxide (A) with the inorganic phosphorus compound (BI).
• the reaction product (D) also includes compounds produced by reacting the metal oxide (A), the inorganic phosphorus compound (BI), and other compounds.
• the maximum absorption wave number in the region of 800-1400 cm -1 is preferably in the range of 1080-1130 cm -1 .
• the metal atom (M) derived from the metal oxide (A) and the inorganic phosphorus compound ( BI) and a phosphorus atom (P) originating from BI) form a bond represented by M--O--P via an oxygen atom (O).
• a characteristic absorption band derived from the bond is generated in the infrared absorption spectrum of the reaction product (D).
• the obtained multilayer structure When the characteristic absorption band based on MOP bonds is found in the region of 1080 to 1130 cm ⁇ 1 , the obtained multilayer structure exhibits excellent gas barrier properties. In particular, when the characteristic absorption band is the strongest absorption in the region of 800 to 1400 cm ⁇ 1 where absorption derived from bonding between various atoms and oxygen atoms is generally observed, the obtained multilayer structure further Exhibits excellent gas barrier properties.
• the compound (E) or a metal compound such as a metal salt and the inorganic phosphorus compound (BI) are mixed in advance and then hydrolytically condensed, the metal atoms derived from the metal compound and the inorganic phosphorus compound (BI ) are almost uniformly mixed and reacted to obtain a complex.
• the maximum absorption wave number in the region of 800 to 1400 cm ⁇ 1 is outside the range of 1080 to 1130 cm ⁇ 1 .
• the half width of the maximum absorption band in the region of 800 to 1400 cm ⁇ 1 is preferably 200 cm ⁇ 1 or less, and 150 cm ⁇ 1 or less from the viewpoint of the gas barrier properties of the resulting multilayer structure. It is more preferably 100 cm ⁇ 1 or less, and particularly preferably 50 cm ⁇ 1 or less.
• the infrared absorption spectrum of the layer (Y) can be measured by an attenuated total reflection method using a Fourier transform infrared spectrophotometer (Spectrum One manufactured by PerkinElmer Co., Ltd.) with a measurement range of 800 to 1400 cm ⁇ 1 .
• a Fourier transform infrared spectrophotometer Spectrum One manufactured by PerkinElmer Co., Ltd.
• reflection measurements such as the reflection absorption method, external reflection method, and attenuated total reflection method
• transmission measurements such as the Nujol method and the tablet method after scraping the layer (Y) from the multilayer structure. , but is not limited to these.
• the layer (Y) may partially contain the metal oxide (A) and/or the inorganic phosphorus compound (BI) that are not involved in the reaction.
• the molar ratio of the metal atoms derived from the metal oxide (A) and the phosphorus atoms derived from the inorganic phosphorus compound (BI) is [metal atoms derived from the metal oxide (A)]:[ Phosphorus atom derived from inorganic phosphorus compound (BI)] is preferably in the range of 1.0:1.0 to 3.6:1.0, preferably 1.1:1.0 to 3.0:1. It is more preferably in the range of 0. Within this range, excellent gas barrier performance is obtained.
• the molar ratio in the layer (Y) can be adjusted by adjusting the mixing ratio of the metal oxide (A) and the inorganic phosphorus compound (BI) in the coating liquid (S) for forming the layer (Y).
• the molar ratio in layer (Y) is usually the same as in coating liquid (S).
• the thickness of the layer (Y) (when the multilayer structure has two or more layers (Y), the total thickness of each layer (Y)) is preferably 0.05 to 4.0 ⁇ m, more preferably 0.1 to 2 0 ⁇ m is more preferred. By making the layer (Y) thinner, it is possible to suppress the dimensional change of the multilayer structure during processing such as printing and lamination. Moreover, since the flexibility of the multilayer structure is increased, its mechanical properties can be brought closer to those of the base material itself. From the viewpoint of gas barrier properties, the thickness of each layer (Y) is preferably 0.05 ⁇ m or more, more preferably 0.1 ⁇ m or more. The thickness of each layer (Y) is preferably 2.0 ⁇ m or less, more preferably 1.0 ⁇ m or less.
• the thickness of the layer (Y) can be controlled by the concentration of the coating liquid (S) used for forming the layer (Y), which will be described later, or the coating method thereof.
• the thickness of layer (Y) can be measured by observing the cross section of the multilayer structure with a scanning electron microscope or a transmission electron microscope.
• the number of layers (Y) may be one or two or more. Having two or more layers (Y) tends to improve barrier properties.
• the number of layers of the layer (Y) may be two layers. In the case of having two or more layers (Y), it is preferable that the layers (Y) are arranged on both sides of each substrate (X). In the case of having two or more layers (Y), the lamination method is not particularly limited. You may bond together using the adhesive layer (I) mentioned later.
• the layer (Y) may further contain other components in addition to the components described above (metal oxide (A), inorganic phosphorus compound (BI), and reaction product (D) thereof).
• Other components that can be contained in the layer (Y) include, for example, a polymer having at least one functional group selected from the group consisting of a carbonyl group, a hydroxyl group, a carboxyl group, a carboxylic acid anhydride group, and a salt of a carboxyl group.
• polymer (F) (hereinafter sometimes abbreviated as "polymer (F)"), organic phosphorus compound (BO), cross-linking agent-containing resin composition (V), carbonate, hydrochloride, nitrate, hydrogen carbonate, sulfuric acid salts, inorganic acid metal salts such as hydrogen sulfates and borates, organic acid metal salts such as oxalates, acetates, tartrates and stearates, cyclopentadienyl metal complexes (e.g.
• the content of the other component in the layer (Y) in the multilayer structure is preferably 50% by mass or less, more preferably 20% by mass or less, even more preferably 10% by mass or less, and particularly preferably 5% by mass or less, It may be 4% by mass or less, 3% by mass or less, 2% by mass or less, 1% by mass or less, or 0% by mass (excluding other components). From the viewpoint that the multilayer structure of the present invention has higher definition, it is preferable that the content of other components is small.
• Polymer (F) has at least one functional group selected from the group consisting of carbonyl groups, hydroxyl groups, carboxyl groups, carboxylic acid anhydride groups, and salts of carboxyl groups.
• Polymer (F) is preferably a polymer having at least one functional group selected from the group consisting of hydroxyl groups and carboxyl groups.
• polymer (F) examples include polyethylene glycol; polyvinyl alcohol, modified polyvinyl alcohol containing 1 to 50 mol% of an ⁇ -olefin unit having 4 or less carbon atoms, polyvinyl alcohol-based polymers such as polyvinyl acetal (polyvinyl butyral, etc.); Polysaccharides such as cellulose and starch; (meth)acrylic acid polymers such as polyhydroxyethyl (meth)acrylate, poly(meth)acrylic acid, and ethylene-acrylic acid copolymers; ethylene-maleic anhydride copolymers Examples include hydrolysates, hydrolysates of styrene-maleic anhydride copolymers, and hydrolysates of isobutylene-maleic anhydride alternating copolymers, and other maleic acid polymers. Among them, polyethylene glycol or polyvinyl alcohol polymer is preferable.
• the polymer (F) may be a homopolymer of a monomer having a polymerizable group, a copolymer of two or more monomers, a carbonyl group, a hydroxyl group, a carboxyl It may be a copolymer of a monomer having at least one functional group selected from the group consisting of a group consisting of a group, a carboxylic anhydride group and a salt of a carboxyl group and a monomer having no such group.
• a polymer (F) you may mix and use 2 or more types of polymers (F).
• the weight average molecular weight of the polymer (F) is preferably 5000 or more, more preferably 8000 or more, in order to obtain a multilayer structure having better gas barrier properties and mechanical strength. More preferably, 10,000 or more is even more preferable.
• the upper limit of the weight average molecular weight of the polymer (F) is not particularly limited, and is, for example, 1,500,000 or less.
• the content of the polymer (F) in the layer (Y) is preferably less than 50% by mass, more preferably 20% by mass or less, based on the mass of the layer (Y). It is preferably 10% by mass or less, more preferably 0% by mass. Polymer (F) may or may not have reacted with the components in layer (Y).
• Organic phosphorus compound (BO) is preferably a polymer (BOa) having a plurality of phosphorus atoms or an organic phosphorus compound (BOb) described below.
• the functional group containing a phosphorus atom possessed by the polymer (BOa) includes, for example, a phosphoric acid group, a phosphorous acid group, a phosphonic acid group, a phosphonous acid group, a phosphinic acid group, a phosphinic acid group, and derivatives thereof.
• functional groups e.g., salts, (partial) ester compounds, halides (e.g., chlorides), dehydrates), etc., among which phosphate groups and phosphonic acid groups are preferred, and phosphonic acid groups are more preferred.
• Examples of the polymer (BOa) include 6-[(2-phosphonoacetyl)oxy]hexyl acrylate, 2-phosphonooxyethyl methacrylate, phosphonomethyl methacrylate, 11-phosphonoundecyl methacrylate, methacrylic acid 1 , Polymers of phosphono (meth) acrylic acid esters such as 1-diphosphonoethyl; Polymers; polymers of vinylphosphinic acids such as vinylphosphinic acid and 4-vinylbenzylphosphinic acid; and starch phosphates.
• the polymer (BOa) may be a homopolymer of a monomer having a functional group containing at least one phosphorus atom, or may be a copolymer of two or more monomers. Further, as the polymer (BOa), two or more types of polymers composed of a single monomer may be used in combination. Among them, phosphono(meth)acrylic acid ester polymers and vinylphosphonic acid polymers are preferred, vinylphosphonic acid polymers are more preferred, and polyvinylphosphonic acid is even more preferred.
• the polymer (BOa) can also be obtained by homopolymerizing or copolymerizing a vinylphosphonic acid derivative such as a vinylphosphonic acid halide or a vinylphosphonic acid ester, followed by hydrolysis.
• the polymer (BOa) may also be a copolymer of a monomer having a functional group containing at least one phosphorus atom and another vinyl monomer.
• Other vinyl monomers that can be copolymerized with a monomer having a functional group containing a phosphorus atom include, for example, (meth)acrylic acid, (meth)acrylates, acrylonitrile, methacrylonitrile, styrene, nuclear substitution styrenes, alkyl vinyl ethers, alkyl vinyl esters, perfluoroalkyl vinyl ethers, perfluoroalkyl vinyl esters, maleic acid, maleic anhydride, fumaric acid, itaconic acid, maleimide, phenylmaleimide, etc.; ) Acrylic esters, acrylonitrile, styrene, maleimide and phenylmaleimide are preferred.
• the proportion of structural units derived from a monomer having a functional group containing a phosphorus atom in the total structural units of the polymer (BOa) is 10 mol% or more. is preferably 40 mol% or more, more preferably 70 mol% or more, particularly preferably 90 mol% or more, and may be 100 mol%.
• the molecular weight of the polymer (BOa) is not particularly limited, but the number average molecular weight is preferably in the range of 1,000 to 100,000. When the number average molecular weight is in this range, the effect of improving the bending resistance of the multilayer structure of the present invention and the viscosity stability of the coating liquid (S) when using the coating liquid (S) described later are increased. level can be compatible.
• the ratio WBOa/WBI of the mass WBOa of the polymer (BOa) to the mass WBI of the inorganic phosphorus compound (BI) in the layer (Y) is 0. 01/99.99 ⁇ WBOa/WBI ⁇ 6.00/94.00, and from the viewpoint of excellent barrier performance, 0.10/99.90 ⁇ WBOa/WBI ⁇ 4.50/95. 50, more preferably 0.20/99.80 ⁇ WBOa/WBI ⁇ 4.00/96.00, more preferably 0.50/99.50 ⁇ WBOa/WBI ⁇ Those satisfying the relationship 3.50/96.50 are particularly preferred.
• the inorganic phosphorus compound (BI) and/or the organic phosphorus compound (BOa) react in the layer (Y), the inorganic phosphorus compound (BI) and/or the organic phosphorus compound constituting the reaction product (D) Part of the compound (BOa) is considered an inorganic phosphorus compound (BI) and/or an organic phosphorus compound (BOa).
• the mass of the inorganic phosphorus compound (BI) and/or the organic phosphorus compound (BOa) used to form the reaction product (D) (the inorganic phosphorus compound (BI) and/or the organic phosphorus compound (BOa before the reaction) )) is included in the mass of inorganic phosphorus compound (BI) and/or organic phosphorus compound (BOa) in layer (Y).
• Organic phosphorus compound (BOb) In the organic phosphorus compound (BOb), a phosphorus atom to which at least one hydroxyl group is bonded and a polar group are bonded via an alkylene chain or polyoxyalkylene chain having 3 to 20 carbon atoms.
• the organic phosphorus compound (BOb) has a lower surface free energy than the metal oxide (A), the inorganic phosphorus compound (BI), and their reaction products (D), and in the process of forming the precursor of the layer (Y) Segregate on the surface side.
• Organic phosphorus compounds include, for example, 3-hydroxypropylphosphonic acid, 4-hydroxybutylphosphonic acid, 5-hydroxypentylphosphonic acid, 6-hydroxyhexylphosphonic acid, 7-hydroxyhepcylphosphonic acid, 8-hydroxy octylphosphonic acid, 9-hydroxynonylphosphonic acid, 10-hydroxydecylphosphonic acid, 11-hydroxyundecylphosphonic acid, 12-hydroxydodecylphosphonic acid, 13-hydroxydotridecylphosphonic acid, 14-hydroxytetradecylphosphonic acid, 15-hydroxypentadecylphosphonic acid, 16-hydroxyhexadecylphosphonic acid, 17-hydroxyheptadecylphosphonic acid, 18-hydroxyoctadecylphosphonic acid, 19-hydroxynonadecylphosphonic acid, 20-hydroxyicosylphosphonic acid, 3-hydroxy propyl dihydrogen phosphate, 4-hydroxybutyl dihydrogen phosphate, 5-
• the ratio MBOb between the number of moles MBOb of the organic phosphorus compound (BOb) and the number of moles MBI of the inorganic phosphorus compound (BI) in the layer (Y) /MBI preferably satisfies the relationship of 1.0 ⁇ 10 -4 ⁇ MBOb/MBI ⁇ 2.0 ⁇ 10 -2 , and 3.5 ⁇ 10 -4 ⁇ MBOb/MBI ⁇ 1.0 ⁇ 10 -2 Those satisfying the relationship are more preferable, and those satisfying the relationship 5.0 ⁇ 10 ⁇ 4 ⁇ MBOb/MBI ⁇ 6.0 ⁇ 10 ⁇ 3 are even more preferable.
• the layer (Y) contains an organic phosphorus compound (BOb)
• the atomic ratio of carbon atoms to aluminum atoms (C/Al ratio) in the range from the surface to 5 nm is preferably in the range of 0.1 to 15.0, and in the range of 0.3 to 10.0. is more preferred, and a range of 0.5 to 5.0 is particularly preferred.
• the adhesion between the layer (Y) and the adjacent layer may be improved.
• the layer (Y) containing the resin composition (V) containing a cross-linking agent may have good flex resistance.
• the cross-linking agent-containing resin composition (V) comprises a hydroxyl group-containing resin and a cross-linking agent.
• the hydroxyl group-containing resin include hydroxyl group-containing epoxy resins, hydroxyl group-containing polyester resins, hydroxyl group-containing (meth)acrylic resins, hydroxyl group-containing polyurethane resins, vinyl alcohol resins, polysaccharides, and the like. It preferably contains a saccharide, more preferably contains a vinyl alcohol resin, and further preferably contains a polyvinyl alcohol resin.
• a silicon compound having a glycidyl group, an organic titanium compound, or an organic zirconium compound is preferably used as the cross-linking agent.
• the mass ratio of the hydroxyl group-containing resin to the crosslinking agent (hydroxyl group-containing resin/crosslinking agent) is preferably 2.0 or more and 200 or less, more preferably 9.0 or more and 60 or less.
• the layer (W) containing at least one selected from the group consisting of the polymer (F), the organic phosphorus compound (BO) and the cross-linking agent-containing resin composition (V) is a layer ( It may be directly laminated on the surface of Y) opposite to the substrate (X).
• the layer (W) in the multilayer structure the bending resistance may be improved, or the adhesiveness to the adhesive layer (I′) described later may be improved. From the viewpoint of definition of the multilayer structure, it may be preferable not to include the layer (W).
• layer (W) is preferably directly laminated with layer (Y).
• layer (F) organic phosphorus compound (BO) and cross-linking agent-containing resin composition (V) that can be contained in the layer (W) are as described above.
• the layer (W) may further contain other components, for example, inorganic acid metal salts such as carbonates, hydrochlorides, nitrates, hydrogen carbonates, sulfates, hydrogen sulfates, borates, oxalic acid Organic acid metal salts such as salts, acetates, tartrates and stearates, metal complexes such as cyclopentadienyl metal complexes (e.g. titanocene), cyano metal complexes (e.g. Prussian blue), layered clay compounds, cross-linking agents , polymer compounds other than the polymer (BOa) and the polymer (F), plasticizers, antioxidants, ultraviolet absorbers, flame retardants, and the like.
• inorganic acid metal salts such as carbonates, hydrochlorides, nitrates, hydrogen carbonates, sulfates, hydrogen sulfates, borates, oxalic acid Organic acid metal salts such as salts, acetates, tart
• the content of the other components in the layer (W) is preferably 20% by mass or less, more preferably 10% by mass or less, even more preferably 5% by mass or less, and even if it is 2% by mass or less, it is 1% by mass or less. It may be present or may be 0% by mass (not including other components).
• the thickness thereof 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 (W) is not particularly limited. preferable.
• the multilayer structure of the present invention may have an adhesive layer (I) between the substrate (X) and the layer (Y).
• the adhesive layer (I) By providing the adhesive layer (I), the adhesiveness between the substrate (X) and the layer (Y) can be enhanced in some cases.
• the adhesive layer (I) between the surface layer and the layer (Y). ) is more preferably provided.
• the adhesive constituting the adhesive layer (I) is not particularly limited as long as it has adhesiveness between the substrate (X) and the layer (Y), and examples thereof include polyurethane adhesives and polyester adhesives. be done. By adding a small amount of additive such as a known silane coupling agent to these adhesives, the adhesiveness can be further enhanced in some cases.
• Silane coupling agents include, for example, silane coupling agents having reactive groups such as isocyanate groups, epoxy groups, amino groups, ureido groups, and mercapto groups.
• the polyurethane adhesive As the polyurethane adhesive, a known one can be used, but it is preferable to use a two-liquid polyurethane adhesive in which a polyisocyanate component and a polyol component are mixed and reacted.
• Commercially available products can be used as the two-liquid type polyurethane adhesive, and examples thereof include Takelac (registered trademark) and Takenate (registered trademark) manufactured by Mitsui Chemicals, Inc.
• polyester adhesives can be used, and commercially available products include, for example, Elitel (registered trademark) KT-0507, KT-8701, KT-8803, KT-9204, KA-5034, KA -3556, KA-1449, KA-5071S, KZA-1449S, (manufactured by Unitika Ltd.), Vylonal (registered trademark) MD-1200, Vylonal MD-1480 (manufactured by Toyobo Co., Ltd.), Pesresin A124GP, Pesresin A684G (manufactured by Takamatsu Oil Co., Ltd.) and the like.
• a vinyl alcohol-based resin particularly polyvinyl alcohol
• Addition of a vinyl alcohol-based resin, particularly polyvinyl alcohol, to a polyester-based adhesive may improve adhesion.
• the mass ratio (vinyl alcohol resin/polyester resin) should be 1/99 or more and 50/50 or less while maintaining good adhesion. It is preferable from the viewpoint of exhibiting high peel strength.
• the polyester-based resin is preferably a polyester-based resin having a carboxyl group from the viewpoint of affinity with the vinyl alcohol-based resin.
• it is preferable that the polyester-based resin is an aqueous dispersion. Since the polyester-based resin is an aqueous dispersion, the affinity with the polyvinyl alcohol-based resin tends to be better.
• the thickness of the adhesive layer (I) per layer is preferably 0.001 to 10.0 ⁇ m, more preferably 0.003 to 5.0 ⁇ m, even more preferably 0.005 to 1.0 ⁇ m, further preferably 0.007 to 0.05 ⁇ m. 1 ⁇ m is even more preferable, and 0.01 to 0.03 ⁇ m is particularly preferable.
• the multilayer structure of the present invention comprises a substrate (X), a layer (Y), a layer (W) and an adhesive layer (I) in order to improve various properties (for example, heat sealability, barrier properties, mechanical properties). ) other than the layer (J).
• a multilayer structure of the present invention can be obtained, for example, by laminating a layer (Y) on a substrate (X) (via an adhesive layer (I) as necessary), and further laminating the other layer (J). It can be manufactured by bonding or forming directly or through an adhesive layer (I') described later.
• the other layer (J) include, but are not limited to, an ink layer, a polyolefin layer, a thermoplastic resin layer such as an ethylene-vinyl alcohol copolymer resin layer, and the like.
• examples of the ink layer include a film obtained by drying a liquid in which a polyurethane resin containing a pigment (e.g., titanium dioxide) is dispersed in a solvent.
• a film obtained by drying an ink or a resist for forming an electronic circuit wiring, the main ingredient of which is a polyurethane resin or other resin, may be used.
• coating methods for the ink layer include gravure printing, wire bar, spin coater, die coater, and various other coating methods.
• the thickness of the ink layer is preferably 0.5-10.0 ⁇ m, more preferably 1.0-4.0 ⁇ m.
• polyolefin layer As the outermost layer of the multilayer structure of the present invention, it is possible to impart heat sealability to the multilayer structure and improve the mechanical properties of the multilayer structure.
• Polyolefin is preferably polypropylene or polyethylene from the viewpoint of improving heat sealability and mechanical properties.
• the polyester is preferably polyethylene terephthalate
• the polyamide is preferably nylon-6
• the hydroxyl group-containing polymer is preferably ethylene-vinyl alcohol copolymer.
• the other layer (J) may be a layer formed by extrusion coat lamination.
• the extrusion coat lamination method that can be used in the present invention is not particularly limited, and known methods may be used.
• a typical extrusion coat lamination method a laminated film is produced by feeding a molten thermoplastic resin to a T-die and cooling the thermoplastic resin taken out from a flat slit of the T-die.
• extrusion coat lamination methods include the sandwich lamination method and the tandem lamination method.
• the sandwich lamination method is a method in which a molten thermoplastic resin is extruded onto one base material, and a second base material is supplied from another unwinder (unwinder) and laminated to produce a laminate.
• the tandem lamination method is a method in which two single lamination machines are connected to produce a laminate having a five-layer structure at one time.
• the adhesive layer (I') may be used to enhance adhesion with other members (for example, another layer (J), etc.).
• the adhesive layer (I) may be composed of an adhesive resin.
• the adhesive constituting the adhesive layer (I') those exemplified as the adhesive constituting the adhesive layer (I) can also be used.
• the adhesive resin that enhances the adhesiveness with other members a two-liquid reaction type polyurethane adhesive that mixes and reacts a polyisocyanate component and a polyol component is preferable.
• additive such as a known silane coupling agent to the anchor coating agent or adhesive, it may be possible to further increase the adhesiveness.
• Silane coupling agents include, but are not limited to, silane coupling agents having reactive groups such as isocyanate groups, epoxy groups, amino groups, ureido groups, and mercapto groups. Adhesion with other members makes it possible to more effectively suppress deterioration of gas barrier properties or appearance when the multilayer structure of the present invention is subjected to processing such as printing or lamination. It may be possible to increase the drop strength of protective sheets and electronic devices using.
• the substrate (X) and the layer (Y) are laminated adjacently.
• the substrate (X) and the layer (Y) may be directly laminated or laminated via the adhesive layer (I), but the substrate (X) has a surface layer and the surface
• the substrate (X) and the layer (Y) are preferably laminated via the adhesive layer (I), and the substrate (X) forms the surface layer. If not, the substrate (X) and the layer (Y) are preferably laminated directly.
• the multilayer structure of the present invention is not limited thereto. A plurality of specific examples may be combined.
• "/" means lamination via an adhesive layer or directly.
• Layer (Y)/Substrate (X) (2) Layer (Y)/Base (X)/Layer (Y) (3) Substrate (X)/Layer (Y)/Layer (Y)/Substrate (X) (4) Layer (Y)/Base (X)/Base (X)/Layer (Y) (5) Layer (Y)/Base (X)/Layer (Y)/Base (X) (6) Layer (Y)/Base (X)/Layer (Y)/Base (X)/Layer (Y) in the above examples, the substrate (X) preferably contains a PET layer.
• the multilayer structure may consist of the substrate layer (X) and the layer (Y) alone, or may consist of the substrate layer (X), the layer (Y) and the adhesive layer (I) alone.
• the haze value of the multilayer structure of the present invention measured according to JIS K7105:1981, is preferably 3% or less, more preferably 2.5% or less, and even more preferably 2.0% or less. When the haze value is equal to or less than the upper limit, the definition of the multilayer structure is further enhanced.
• the haze value of the multilayer structure of the present invention may be 0.1% or more, or 0.5% or more.
• the haze value of the multilayer structure can be adjusted by the type and thickness of the substrate (X), the thickness of the layer (Y), and the like.
• the water vapor transmission rate of the multilayer structure of the present invention at 40° C. and 90% RH, measured according to ISO15106-5:2015, is preferably 1 ⁇ 10 ⁇ 2 g/m 2 ⁇ day or less, and is 5.0. ⁇ 10 -3 g/m 2 ⁇ day or less is more preferable, and 3.0 ⁇ 10 -3 g/m 2 ⁇ day or less is even more preferable.
• the water vapor transmission rate of the multilayer structure of the present invention may be 1.0 ⁇ 10 ⁇ 5 g/m 2 ⁇ day or more, or may be 1.0 ⁇ 10 ⁇ 4 g/m 2 ⁇ day or more. good.
• the water vapor transmission rate of the multilayer structure can be adjusted by the type and thickness of the substrate (X), the thickness of the layer (Y), and the like.
• a coating liquid (S) containing a metal oxide (A), an inorganic phosphorus compound (BI), and a solvent is applied to at least one side of the substrate (X).
• a step (I) of forming a precursor layer of the layer (Y) by coating and removing the solvent, and a step of forming the layer (Y) by heat-treating the precursor layer of the layer (Y) ( II), and the coating speed of the coating liquid (S) in step (I) is 0.03 cm/s or more and 2.5 cm/s or less per 1 cm of coating width.
• the coating liquid (S) used in step (I) contains the organic phosphorus compound (BO) or the polymer (F).
• a layer (Y) containing an organic phosphorus compound (BO) or a polymer (F) may be formed, a coating liquid (T) containing an organic phosphorus compound (BO) or a polymer (F) is prepared, and a step (
• an organic phosphorus compound (BO ) or the polymer (F) may be impregnated into the layer (Y), or the layer (W) may be provided on the layer (Y).
• the adhesive layer (I) is provided between the substrate (X) and the layer (Y)
• the production method includes forming the adhesive layer (I) on the substrate (X) before step (I). The step of providing
• step (I) a coating liquid (S) containing a metal oxide (A), an inorganic phosphorus compound (BI), and a solvent is applied to at least one surface side of the substrate (X) in an amount of 0.03 cm per 1 cm of coating width. /s or more and 2.5 cm/s or less, the solvent is removed to form a precursor layer of the layer (Y).
• Application of the coating liquid (S) is usually carried out by applying the coating liquid (S) directly or via the adhesive layer (I) on at least one surface of the substrate (X). That is, the coating liquid (S) may be applied onto the adhesive layer (I) of the substrate (X) provided with the adhesive layer (I).
• the coating speed of the coating liquid (S) is preferably 2.4 cm/s or less, more preferably 2.0 cm/s or less per 1 cm of coating width, from the viewpoint of good image clarity of the resulting multilayer structure.
• the coating speed of the coating liquid (S) is preferably 0.05 cm/s or more per 1 cm of the coating width from the viewpoint of the image clarity, productivity, and coating stability of the multilayer structure to be obtained, and 0.2 cm/s. /s or more is more preferable.
• the coating speed of the coating liquid (S) increases the image clarity of the resulting multilayer structure
• the coating speed is more than 2.5 cm/s per 1 cm of the width of the substrate (X)
• the coating speed is less than 0.03 cm/s per 1 cm of width
• the coating liquid (S) applied to the substrate tends to be repelled from the substrate, and the layer (Y) cannot be properly constructed. presumed to disappear.
• it is essential to control the coating speed with respect to the coating width within the range described above.
• the coating liquid (S) is obtained by mixing the metal oxide (A), inorganic phosphorus compound (BI) and solvent.
• Specific means for adjusting the coating liquid (S) include a method of mixing a dispersion of the metal oxide (A) and a solution containing the inorganic phosphorus compound (BI); A method of adding an inorganic phosphorus compound (BI) and mixing may be mentioned.
• the temperature at which these are mixed is preferably 50° C. or lower, more preferably 30° C. or lower, and even more preferably 20° C. or lower.
• the coating liquid (S) may contain other compounds (e.g., organic phosphorus compounds (BO) and polymers (F)), and if necessary, acetic acid, hydrochloric acid, nitric acid, trifluoroacetic acid, and trichloro It may contain at least one acid compound (Q) selected from the group consisting of acetic acid.
• other compounds e.g., organic phosphorus compounds (BO) and polymers (F)
• acetic acid e.g., organic phosphorus compounds (BO) and polymers (F)
• acetic acid e.g., organic phosphorus compounds (BO) and polymers (F)
• acetic acid e.g., organic phosphorus compounds (BO) and polymers (F)
• acetic acid e.g., organic phosphorus compounds (BO) and polymers (F)
• acetic acid e.g., organic phosphorus compounds (BO) and polymers (F)
• acetic acid e.g
• a dispersion liquid of the metal oxide (A) can be obtained, for example, by mixing the compound (E), water, and, if necessary, an acid catalyst or an organic solvent, according to a method employed in a known sol-gel method, to obtain a compound ( It can be prepared by condensation or hydrolytic condensation of E).
• a dispersion of the metal oxide (A) is obtained by condensation or hydrolytic condensation of the compound (E)
• the resulting dispersion may be subjected to a specific treatment (the acid compound (Q) peptization in the presence of, etc.) may be performed.
• the solvent used for preparing the dispersion of the metal oxide (A) is not particularly limited, but alcohols such as methanol, ethanol and isopropanol; water; or mixed solvents thereof are preferred.
• the solvent used for the solution containing the inorganic phosphorus compound (BI) may be appropriately selected according to the type of the inorganic phosphorus compound (BI), and preferably contains water.
• the solvent may contain an organic solvent (for example, alcohols such as methanol) as long as it does not interfere with the dissolution of the inorganic phosphorus compound (BI).
• the solid content concentration of the coating liquid (S) is preferably 1 to 20% by mass, more preferably 2 to 15% by mass, from the viewpoint of the storage stability of the coating liquid and the coatability to the substrate (X), and 3 to 10% by mass is more preferred.
• the solid content concentration can be calculated, for example, by dividing the mass of the solid content remaining after the solvent of the coating liquid (S) is distilled off by the mass of the coating liquid (S) subjected to the treatment.
• the coating liquid (S) preferably has a viscosity of 3000 mPa s or less at the temperature during coating as measured by a Brookfield type rotational viscometer (SB type viscometer: rotor No. 3, rotation speed 60 rpm). , 2500 mPa ⁇ s or less, and more preferably 2000 mPa ⁇ s or less.
• the viscosity of the coating liquid (S) is preferably 50 mPa ⁇ s or more, more preferably 100 mPa ⁇ s or more, and even more preferably 200 mPa ⁇ s or more.
• the molar ratio between aluminum atoms and phosphorus atoms can be calculated by performing a fluorescent X-ray analysis of the dry matter of the coating liquid (S).
• the application of the coating liquid (S) is not particularly limited, and a known method can be adopted.
• coating methods include roll coating, gravure coating, screen printing, reverse coating, kiss coating, die coating, metering bar coating, chamber doctor combined coating, and bar coating.
• the drying method includes, for example, a hot air drying method, a hot roll contact method, an infrared heating method, a microwave heating method, and the like.
• the drying temperature is preferably lower than the flow start temperature of the substrate (X).
• the drying temperature after coating of the coating liquid (S) may be, for example, approximately 60° C. or higher and 180° C. or lower, more preferably 60° C. or higher and lower than 140° C., further preferably 70° C. or higher and lower than 130° C., and 80 °C or higher and lower than 120 °C is particularly preferred.
• the drying time is not particularly limited, but is preferably from 1 second to less than 1 hour, more preferably from 5 seconds to less than 15 minutes, and even more preferably from 5 seconds to less than 300 seconds. In particular, when the drying temperature is 100° C.
• the drying time is preferably 1 second or more and less than 4 minutes, more preferably 5 seconds or more and less than 4 minutes, and further preferably 5 seconds or more and less than 3 minutes. preferable.
• the drying temperature is lower than 100° C. (eg, 60 to 99° C.)
• the drying time is preferably 3 minutes or more and less than 1 hour, more preferably 6 minutes or more and less than 30 minutes, and even more preferably 8 minutes or more and less than 25 minutes.
• the drying treatment conditions for the coating liquid (S) are within the above range, there is a tendency to obtain a multilayer structure having better gas barrier properties. By removing the solvent through the drying, a precursor layer of the layer (Y) is formed.
• the first layer is formed by removing the solvent.
• the coating liquid (S) is applied to the other side of the substrate (X), and then the solvent is removed to form the second layer.
• Precursor layer of second layer (Y) is formed.
• the composition of the coating liquid (S) applied to each surface may be the same or different.
• step (II) the precursor layer of layer (Y) formed in step (I) is heat-treated to form layer (Y).
• a reaction proceeds to produce a reaction product (D).
• the heat treatment temperature is preferably 140° C. or higher, more preferably 170° C. or higher, even more preferably 180° C. or higher, and particularly preferably 190° C. or higher.
• the heat treatment temperature is low, it takes a long time to obtain a sufficient reaction rate, which causes a decrease in productivity.
• the heat treatment temperature varies depending on the type of substrate (X) and the like.
• the heat treatment temperature is preferably 270° C. or lower.
• the heat treatment temperature is preferably 240° C. or lower.
• the heat treatment may be performed in an air atmosphere, a nitrogen atmosphere, an argon atmosphere, or the like.
• the heat treatment time is preferably 1 second to 1 hour, more preferably 1 second to 15 minutes, even more preferably 5 to 300 seconds.
• the step (II) preferably includes a first heat treatment step (II-1) and a second heat treatment step (II-2).
• the temperature of the second stage heat treatment (hereinafter referred to as the second heat treatment) is preferably higher than the temperature of the first stage heat treatment (hereinafter referred to as the first heat treatment), and the temperature of the first heat treatment It is more preferably 15° C. or higher, more preferably 20° C. or higher, and particularly preferably 30° C. or higher.
• the heat treatment temperature in step (II) should be higher than the drying temperature in step (I) in order to obtain a multilayer structure having good properties. is preferably 30° C. or higher, more preferably 50° C. or higher, even more preferably 55° C. or higher, and particularly preferably 60° C. or higher.
• the temperature of the first heat treatment is preferably 140° C. or higher and lower than 200° C.
• the temperature of the second heat treatment is preferably 180° C. or higher and 270° C. or lower.
• the temperature of the second heat treatment is higher than the temperature of the first heat treatment, more preferably 15° C. or more, and even more preferably 25° C. or more.
• the heat treatment time is preferably 0.1 seconds to 10 minutes, more preferably 0.5 seconds to 15 minutes, and even more preferably 1 second to 3 minutes.
• the heat treatment time is preferably 1 second to 15 minutes, more preferably 5 seconds to 10 minutes, even more preferably 10 seconds to 5 minutes.
• Step (III) In the method for producing a multilayer structure of the present invention, when the organophosphorus compound (BO), the polymer (F) and/or other components are used, the organophosphorus compound (BO), the polymer (F) and/or the other components And the coating liquid (T) obtained by mixing the solvent, the precursor layer of the layer (Y) obtained in step (I), the layer (Y) obtained in step (II) or step (II-1) It may have a step (III) of coating on the precursor layer of the subsequent layer (Y) and undergoing a drying treatment.
• step (III) is performed after step (II-1), step (II-2) is preferably performed after the drying treatment of step (III).
• the coating amount of the coating liquid (T) may be increased to form the layer (W) on the layer (Y).
• the solvent used in the coating liquid (T) may be appropriately selected according to the type of the organic phosphorus compound (BO), polymer (F) and/or other components, but alcohols such as methanol, ethanol and isopropanol; Water; or a mixed solvent thereof is preferred.
• the solid content concentration in the coating liquid (T) is preferably 0.01 to 60% by mass, more preferably 0.1 to 50% by mass, more preferably 0.2 to 40% by mass, from the viewpoint of storage stability and coatability of the solution. % by mass is more preferred.
• the solid content concentration can be determined by a method similar to the method described for the coating liquid (S).
• the method of applying the coating liquid (T) is not particularly limited, and known methods can be employed.
• the conditions for the solvent removal method (drying treatment) after applying the coating liquid (T) in step (III) can be the same as the drying treatment conditions after applying the coating liquid (S) in step (I). .
• the method for producing a multilayer structure of the present invention may include a step of subjecting the base material (X) to a surface treatment as necessary and providing the adhesive layer (I) before performing the step (I). good. More preferably, the production method comprises applying a coating liquid (R) containing a PVA-based resin, a polyester-based resin and a solvent onto the substrate (X), and then removing the solvent to form the adhesive layer (I). A step (IV) may be included.
• a PVA-based resin, a polyester-based resin and a solvent may be mixed as they are, or a solution or dispersion containing a PVA-based resin and a solution or dispersion containing a polyester-based resin may be mixed. may be mixed with.
• a solution or dispersion containing a PVA-based resin and a solution or dispersion containing a polyester-based resin may be mixed.
• the solvent used for the coating liquid (R) is not particularly limited, but preferably contains water as the main component, and may contain only water. Alcohols such as methanol, ethanol and isopropanol are preferably used as other solvents when water is used as the main component.
• the solid content concentration of the coating liquid (R) is preferably 0.01 to 10% by mass from the viewpoint of storage stability of the coating liquid and coatability on the substrate (X).
• the solid content concentration can be calculated, for example, by dividing the mass of the solid content remaining after the solvent of the coating liquid (R) is distilled off by the mass of the coating liquid (R) subjected to the treatment.
• the application of the coating liquid (R) is not particularly limited, and a known method can be adopted.
• coating methods include casting method, dipping method, roll coating method, gravure coating method, screen printing method, reverse coating method, spray coating method, kiss coating method, die coating method, metering bar coating method, and chamber doctor combined coating. method, curtain coating method, bar coating method, and the like.
• the drying method includes, for example, a hot air drying method, a hot roll contact method, an infrared heating method, a microwave heating method, and the like.
• An electronic device using the multilayer structure of the present invention includes an electronic device body and a protective sheet that protects the surface of the electronic device body.
• the electronic device protective sheet of the present invention includes the multilayer structure of the present invention.
• the protective sheet for the electronic device of the present invention may be composed only of the multilayer structure of the present invention, or may be composed of the multilayer structure of the present invention and other members.
• the protective sheet for electronic devices of the present invention has high barrier properties and sharpness. Therefore, by using the protective sheet of the present invention, it is possible to obtain an electronic device which is less deteriorated even in a harsh environment and which can transmit an image with high definition.
• it when it is used as a substrate film for electronic paper, it can be suitably used as a protective material for the ink of electronic paper, which is susceptible to moisture.
• the electronic device of the present invention may be a photoelectric conversion device, an information display device, or a lighting device.
• photoelectric conversion devices include various solar cells and other photoelectric conversion devices.
• information display devices include liquid crystal displays, organic EL displays, plasma displays, electronic paper, and other information display devices.
• lighting devices include LED lighting, organic EL lighting, and other lighting devices.
• the electronic device of the present invention can be used particularly preferably as a device containing an optical element.
• the optical element is appropriately selected according to the application of the electronic device of the present invention.
• the optical element in the present invention has an optical function, and examples of the optical function include an information display function and a light emitting function.
• the electronic device of the present invention can be used as an information display device, and when an optical element having a light emitting function is used, the electronic device of the present invention can be used. It can be used as a light-emitting device (illumination device).
• the optical element having the information display function for example, a liquid crystal cell used in a liquid crystal display device, an organic EL element used in an organic EL display device, and an electronic paper device used in an electronic paper device (particle movement type, liquid crystal type, electrochemical type, etc.).
• the optical device of the present invention becomes a liquid crystal display device by using a liquid crystal cell as the optical element, an organic EL display device by using an organic EL element, and an electronic paper device by using an element for electronic paper. Become.
• the liquid crystal cell, organic EL element, and electronic paper element are not particularly limited, and generally known elements can be used.
• the multilayer structure of the present invention can also be used as a film called a substrate film, such as an LCD substrate film, an organic EL substrate film, an electronic paper substrate film, and the like.
• the multilayer structure may serve as both a substrate and a protective sheet.
• the electronic device to be protected by the protective sheet is not limited to the above examples, and may be, for example, an IC tag, an optical communication device, a fuel cell, or the like.
• the protective sheet of the electronic device of the present invention may include a surface protective layer arranged on one surface of the multilayer structure.
• a surface protective layer a layer made of a resin that is highly transparent and resistant to scratches is preferable.
• the surface protective layer in the protective sheet of a device such as a solar cell that may be used outdoors is made of a resin having high weather resistance (for example, light resistance).
• a surface protective layer having high translucency is preferable.
• Examples of materials for the surface protective layer include acrylic resin, polycarbonate, polyethylene terephthalate, polyethylene naphthalate, triacetyl cellulose, cycloolefin polymer, ethylene-tetrafluoroethylene copolymer (ETFE), and polytetrafluoro.
• UV absorbers In order to increase the durability of the surface protective layer, various additives (for example, ultraviolet absorbers) may be added to the surface protective layer.
• a preferred example of a surface protective layer with high weather resistance is an acrylic resin layer to which an ultraviolet absorber is added.
• UV absorbers include, but are not limited to, benzotriazole, benzophenone, salicylate, cyanoacrylate, nickel, and triazine UV absorbers. Further, other stabilizers, light stabilizers, antioxidants, etc. may be used in combination.
• the surface may be coated with a weather resistant coating such as a hard coat.
• a weather resistant coating such as a hard coat.
• the type of coating is not particularly limited, and known materials can be used.
• the configuration of the protective sheet is not particularly limited, for example, the following configuration may be preferably used.
• Multilayer structure (2) Multilayer structure/adhesive layer/polyethylene terephthalate (3) Multilayer structure/adhesive layer/triacetylcellulose (4) Multilayer structure/adhesive layer/acrylic resin (5) Multilayer structure/ Adhesive layer/polycarbonate (6) Multilayer structure/adhesive layer/cycloolefin polymer (7) Multilayer structure/adhesive layer/ETFE
• the multilayer structure of the present invention is laminated with another material, it may be preferable to place the other material on the outside in order to protect the multilayer structure.
• ⁇ PET23-A Biaxially stretched polyethylene terephthalate film; manufactured by Toray Industries, Inc., “Lumirror (trademark) U403” (trade name), surface layer provided on both sides, thickness 23 ⁇ m, image clarity 94%, heat shrinkage in MD direction 2.16%
• ⁇ PET23-B Biaxially stretched polyethylene terephthalate film; manufactured by Toray Industries, Inc., “Lumirror (trademark) XW731C” (trade name), provided with a surface layer on one side, thickness 23 ⁇ m, image clarity 93%, heat shrinkage in the MD direction 2.79%
• ⁇ PET23-C Biaxially stretched polyethylene retefphthalate film; manufactured by HYOSUNG, "RH210" (trade name), surface layer provided on both sides, thickness 23 ⁇ m, image clarity 94%, heat shrinkage in MD direction 2.70%
• ⁇ PET23-D Biaxially stretched polyethylene terephthalate film
• PET50 Biaxially stretched polyethylene terephthalate film; manufactured by Toray Industries, Inc., "Lumirror (trademark) U403” (trade name), provided with surface layers on both sides, thickness 50 ⁇ m, image clarity 94%, heat shrinkage in MD direction 2.
• 04% ⁇ PET75 Biaxially stretched polyethylene terephthalate film; manufactured by Toray Industries, Inc., “Lumirror (trademark) U483” (trade name), provided with surface layers on both sides, thickness 75 ⁇ m, image clarity 93%, heat shrinkage in MD direction 2.
• ⁇ Evaluation method> Measurement of maximum absorption wave number (Imax) of infrared absorption spectrum For the layer (Y) of the multilayer structure obtained in Examples and Comparative Examples, using a Fourier transform infrared spectrophotometer, the attenuated total reflection method The maximum absorption wave number (Imax) in the region of 800 to 1400 cm -1 was calculated.
• the measurement conditions were as follows. Apparatus: Spectrum One manufactured by PerkinElmer Co., Ltd. Measurement mode: Attenuated total reflection method Measurement area: 800 to 1400 cm -1
• Oxygen Permeability A piece of 10 mm ⁇ 10 mm was cut out from each of the multilayer structures obtained in Examples and Comparative Examples. The multilayer structure cut out was attached to an oxygen permeation measuring device, and the oxygen permeation rate was measured by the isobaric method. The measurement conditions were as follows. Device: OX-TRAN2/21 manufactured by MOCON Temperature: 20°C Humidity on the oxygen supply side: 85% RH Carrier gas side humidity: 85% RH Carrier gas flow rate: 10 mL/min Oxygen pressure: 1.0 atm Carrier gas pressure: 1.0 atm
• PET23-A (width 21 cm) was used as the substrate (X-1).
• One surface of the substrate was surface-treated at an intensity of 130 W ⁇ min/m 2 using a corona treatment apparatus TEC-4AC manufactured by Kasuga Denki Co., Ltd.
• Coating liquid (R-1) was applied to one side of the substrate after the surface treatment using a bar coater so that the thickness after drying was 10 nm.
• the coated substrate was dried at 140° C. for 1 minute to form an adhesive layer (I-1) on one side of the substrate.
• the coating speed is 12.6 cm / s (coating width).
• the coating liquid (S-1) was applied under the condition that the coating speed per 1 cm was 0.6 cm/s.
• the coated substrate was dried at 120° C. for 3 minutes and then heat-treated at 180° C. for 1 minute to form a precursor layer of layer (Y-1) on the substrate.
• the other surface was subjected to surface treatment in the same manner, and then an adhesive layer (I-1) and a precursor layer of the layer (Y-1) were formed.
• the film on which the precursor layer of the obtained layer (Y-1) was formed was heat-treated at 210° C.
• a multilayer structure of /base material (X-1) (23 ⁇ m)/adhesive layer (I-1) (10 nm)/layer (Y-1) (0.4 ⁇ m) was obtained.
• the layer (Y-1) of the obtained multilayer structure and the multilayer structure according to the methods described in the evaluation methods (1), (3), (4), (5), (6) and (8) evaluated. Table 1 shows the results.
• Lumirror (trademark) U403 manufactured by Toray Industries, Inc., thickness 50 ⁇ m) 2.
• Cosmoshine SRF (trademark) (manufactured by Toyobo Co., Ltd., thickness 80 ⁇ m) 3.
• Triacetyl cellulose (TAC) film manufactured by Konica Minolta, thickness 80 ⁇ m) 4.
• OXIS (trademark) PMMA (manufactured by Okura Kogyo Co., Ltd., thickness 40 ⁇ m) 5.
• Polycarbonate film Pure Ace (trademark) (manufactured by Teijin Limited, thickness 70 ⁇ m) 6.
• Zeonor film (trademark) manufactured by Nippon Zeon Co., Ltd., thickness 70 ⁇ m)
• Example 2 In the same manner as in Example 1, except that PET23-B was used instead of PET23-A used in Example 1 and the adhesive layer (I-1) was not provided on the side not provided with the surface layer. A multilayer structure and a protective sheet for an electronic device were produced and evaluated. Table 1 shows the results.
• Example 1 A multilayer structure and a protective sheet for an electronic device were prepared and evaluated in the same manner as in Example 1 except that the substrate (X) shown in Table 1 was used instead of PET23-A used in Example 1. . Table 1 shows the results.
• Example 7 The layer (Y-1) (0.4 ⁇ m )/adhesive layer (I-1) (10 nm)/(surface-treated surface) substrate (X-1) (23 ⁇ m) (non-surface-treated surface). A multilayer structure and a protective sheet for an electronic device were produced and evaluated. Table 1 shows the results.
• Examples 8 to 10, Comparative Example 2, Comparative Example 3> A multilayer structure and a protective sheet for an electronic device were prepared and evaluated in the same manner as in Example 1, except that the coating speed of the coating liquid (S) of Example 1 was changed as shown in Table 1. Table 1 shows the results. In addition, in the multilayer structure of Comparative Example 3, the coating liquid (S) applied to the base material was repelled from the base material, and the layer (Y) could not be uniformly constructed. 4), (5), (6) and (8) were not evaluated.
• the multilayer structures of Examples 1-10 have high barrier properties and visibility. Further, from the comparison of Examples 1, 8 to 10 and Comparative Examples 2 and 3, etc., the coating speed of the coating liquid (S) for forming the layer (Y) greatly affects the image clarity of the resulting multilayer structure. know that it affects.

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