WO2011125602A1 - 成形体、その製造方法、電子デバイス用部材及び電子デバイス - Google Patents
成形体、その製造方法、電子デバイス用部材及び電子デバイス Download PDFInfo
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- WO2011125602A1 WO2011125602A1 PCT/JP2011/057610 JP2011057610W WO2011125602A1 WO 2011125602 A1 WO2011125602 A1 WO 2011125602A1 JP 2011057610 W JP2011057610 W JP 2011057610W WO 2011125602 A1 WO2011125602 A1 WO 2011125602A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/16—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers in which all the silicon atoms are connected by linkages other than oxygen atoms
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- 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
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- 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
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- 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
- C08J7/12—Chemical modification
- C08J7/16—Chemical modification with polymerisable compounds
- C08J7/18—Chemical modification with polymerisable compounds using wave energy or particle radiation
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- 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
- C08K3/34—Silicon-containing compounds
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- 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
- C08K3/34—Silicon-containing compounds
- C08K3/346—Clay
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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
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
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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
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/16—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers in which all the silicon atoms are connected by linkages other than oxygen atoms
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/48—Ion implantation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/60—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which all the silicon atoms are connected by linkages other than oxygen atoms
- C08G77/62—Nitrogen atoms
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- 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
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- 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
- C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2483/16—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers in which all the silicon atoms are connected by linkages other than oxygen atoms
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- 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
- C08K2201/00—Specific properties of additives
- C08K2201/008—Additives improving gas barrier properties
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/133305—Flexible substrates, e.g. plastics, organic film
Definitions
- the present invention relates to a molded body, a manufacturing method thereof, an electronic device member made of the molded body, and an electronic device including the electronic device member.
- a polymer molded body such as a plastic film is inexpensive and excellent in workability, and therefore has been used in various fields with a desired function.
- a gas barrier plastic film that prevents the permeation of water vapor and oxygen is used for food and pharmaceutical packaging films to maintain the taste and freshness by suppressing the oxidation and alteration of proteins and fats and oils.
- a transparent plastic film is used instead of a glass plate as a substrate having electrodes in a display such as a liquid crystal display or an electroluminescence (EL) display in order to realize a reduction in thickness, weight, and flexibility. It is being considered.
- the plastic film has a problem that it easily transmits water vapor, oxygen, and the like as compared with a glass plate, and easily causes deterioration of elements inside the display.
- Patent Document 1 proposes a flexible display substrate in which a transparent gas barrier layer made of a metal oxide is laminated on a transparent plastic film.
- the flexible display substrate described in this document is obtained by laminating a transparent gas barrier layer made of a metal oxide on the surface of a transparent plastic film by vapor deposition, ion plating, sputtering, or the like. When it is bent or bent, there is a problem in that the gas barrier layer is cracked and the gas barrier property is lowered.
- Patent Document 2 discloses a gas barrier laminate obtained by laminating a plastic film and a resin layer containing polyorganosilsesquioxane as a main component on at least one surface of the plastic film.
- gas barrier properties such as oxygen and water vapor
- Patent Document 3 discloses a method for producing a gas barrier film by forming a polysilazane film on at least one surface of a film and subjecting the polysilazane film to plasma treatment.
- this method has a problem in that sufficient gas barrier performance cannot be obtained unless the thickness of the gas barrier layer is in the micron order.
- the present invention has been made in view of the above-described prior art, and is a molded body excellent in gas barrier properties, transparency, and bending resistance, a manufacturing method thereof, an electronic device member comprising the molded body, and the electronic device It aims at providing an electronic device provided with a member.
- the present inventors have implanted ions into the layer containing the polysilazane compound and the clay mineral in the molded product having a layer containing the polysilazane compound and the clay mineral on the surface. As a result, it was found that the desired molded article can be produced easily and efficiently, and the present invention has been completed.
- the following molded articles (1) to (6) are provided.
- a molded article comprising a layer containing a polysilazane compound and a clay mineral, and having a water vapor transmission rate of 6.0 g / m 2 / day or less in an atmosphere of 40 ° C. and a relative humidity of 90%.
- the molded article according to (1) which has a layer obtained by injecting ions into a layer containing a polysilazane compound and a clay mineral.
- the ion is characterized in that at least one gas selected from the group consisting of hydrogen, nitrogen, oxygen, argon, helium, neon, xenon, krypton, silicon compound and hydrocarbon is ionized.
- the molded product according to (2) The molded product according to (2).
- the content of the clay mineral in the layer containing the polysilazane compound and the clay mineral is 0.01% by mass to 10% by mass, where the total amount of the polysilazane compound and the clay mineral is 100% by mass.
- the following method (7) to (10) for producing a molded article comprising a step of injecting ions into the surface portion of the layer containing the polysilazane compound and the clay mineral of the molded product having a layer containing the polysilazane compound and the clay mineral on the surface portion.
- Body manufacturing method comprising a step of injecting ions into the surface portion of the layer containing the polysilazane compound and the clay mineral of the molded product having a layer containing the polysilazane compound and the clay mineral on the surface portion.
- the following electronic device member (11) is provided.
- An electronic device member comprising the molded product according to (1) or (2).
- the molded product of the present invention has excellent gas barrier properties, transparency, and bending resistance.
- the molded article of the present invention can be suitably used as a member for an electronic device such as a flexible display or a solar battery (for example, a solar battery back sheet).
- the molded article of the present invention having excellent gas barrier properties, transparency, and bending resistance can be produced simply and efficiently.
- the area can be easily increased at a lower cost than a molded body in which an inorganic film is formed as a gas barrier film. Since the member for electronic devices of this invention has the outstanding gas barrier property, transparency, and bending resistance, it can be used suitably for electronic devices, such as a display and a solar cell.
- the molded body of the present invention comprises a layer containing a polysilazane compound and a clay mineral (hereinafter sometimes referred to as a “clay mineral-containing layer”), and is subjected to an atmosphere of 40 ° C. and a relative humidity of 90%.
- the water vapor transmission rate is 6.0 g / m 2 / day or less.
- the polysilazane compound used in the present invention is a polymer compound having a repeating unit containing a —Si—N— bond (silazane bond) in the molecule. Specifically, the formula (1)
- the compound which has a repeating unit represented by these is preferable.
- the number average molecular weight of the polysilazane compound to be used is not particularly limited, but is preferably 100 to 50,000.
- n represents an arbitrary natural number.
- Rx, Ry, and Rz each independently represent a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted cycloalkyl group, an unsubstituted or substituted alkenyl group, unsubstituted or substituted Represents a non-hydrolyzable group such as an aryl group having a group or an alkylsilyl group;
- alkyl group of the unsubstituted or substituted alkyl group examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, Examples thereof include alkyl groups having 1 to 10 carbon atoms such as n-pentyl group, isopentyl group, neopentyl group, n-hexyl group, n-heptyl group and n-octyl group.
- Examples of the unsubstituted or substituted cycloalkyl group include cycloalkyl groups having 3 to 10 carbon atoms such as a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group.
- alkenyl group of an unsubstituted or substituted alkenyl group examples include, for example, a vinyl group, 1-propenyl group, 2-propenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group and the like having 2 to 2 carbon atoms. 10 alkenyl groups are mentioned.
- substituents for the alkyl group, cycloalkyl group and alkenyl group include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; hydroxyl group; thiol group; epoxy group; glycidoxy group; (meth) acryloyloxy group
- halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom
- hydroxyl group such as hydroxyl group; thiol group; epoxy group; glycidoxy group; (meth) acryloyloxy group
- An unsubstituted or substituted aryl group such as a phenyl group, a 4-methylphenyl group, and a 4-chlorophenyl group;
- aryl group of an unsubstituted or substituted aryl group examples include aryl groups having 6 to 10 carbon atoms such as a phenyl group, a 1-naphthyl group, and a 2-naphthyl group.
- substituent of the aryl group examples include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; alkyl groups having 1 to 6 carbon atoms such as methyl group and ethyl group; carbon numbers such as methoxy group and ethoxy group 1-6 alkoxy groups; nitro groups; cyano groups; hydroxyl groups; thiol groups; epoxy groups; glycidoxy groups; (meth) acryloyloxy groups; unsubstituted phenyl groups, 4-methylphenyl groups, 4-chlorophenyl groups, etc.
- alkylsilyl group examples include trimethylsilyl group, triethylsilyl group, triisopropylsilyl group, tri-t-butylsilyl group, methyldiethylsilyl group, dimethylsilyl group, diethylsilyl group, methylsilyl group, and ethylsilyl group.
- Rx, Ry, and Rz a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group is preferable, and a hydrogen atom is particularly preferable.
- Examples of the polysilazane compound having a repeating unit represented by the formula (1) include inorganic polysilazanes in which Rx, Ry, and Rz are all hydrogen atoms, and organic polysilazanes in which at least one of Rx, Ry, and Rz is not a hydrogen atom. There may be.
- inorganic polysilazane the following formula
- perhydropolysilazane having a linear structure, a branched structure and a cyclic structure in the molecule.
- the organic polysilazane can be produced by a known method. For example, it can be obtained by reacting ammonia or a primary amine with a reaction product of an unsubstituted or substituted halogenosilane compound represented by the following formula (2) and a secondary amine.
- m represents 2 or 3
- X represents a halogen atom
- R 1 represents any of the substituents of Rx, Ry, Rz, Rx ′, Ry ′, and Rz ′ described above. .
- the secondary amine, ammonia, and primary amine to be used may be appropriately selected according to the structure of the target polysilazane compound.
- a modified polysilazane compound can also be used as the polysilazane compound.
- the modified polysilazane include, for example, a polymetallosilazane containing a metal atom (the metal atom may be crosslinked) and repeating units of [(SiH 2 ) g (NH) h )] and [(SiH 2 I O] (wherein g, h, and i are each independently 1, 2 or 3), polysiloxazan (Japanese Patent Laid-Open No. 62-195024), and boron compound in polysilazane Polyborosilazane produced by reacting polysilazane (Japanese Patent Laid-Open No.
- polymetallosilazane produced by reacting polysilazane and metal alkoxide Japanese Patent Laid-Open No. 63-81122, etc.
- inorganic silazane high polymer And modified polysilazanes such as JP-A-1-138108
- copolymerized silazanes obtained by introducing an organic component into polysilazane (such as JP-A-2-175726), Low-temperature ceramicized polysilazane (Japanese Patent Laid-Open No. 5-238827, etc.) obtained by adding or adding a catalytic compound for promoting ceramicization to lysilazane,
- Silicon alkoxide-added polysilazane Japanese Patent Laid-Open No. 5-238827
- glycidol-added polysilazane Japanese Patent Laid-Open No. 6-122852
- acetylacetonato complex-added polysilazane Japanese Patent Laid-Open No. 6-306329
- metal carboxylate-added polysilazane JP-A-6-299118
- a polysilazane composition obtained by adding amines and / or acids to the above polysilazane or a modified product thereof Japanese Patent Laid-Open No. 9-31333
- perhydropolysilazane with alcohol such as methanol or hexamethyldisilazane at the terminal N atom
- modified polysilazanes obtained by addition JP-A-5-345826, JP-A-4-63833
- the polysilazane compound used in the present invention is preferably perhydropolysilazane in which Rx, Ry, and Rz are all hydrogen atoms from the viewpoint of availability and excellent gas barrier properties.
- the polysilazane compound a commercially available product as a glass coating material or the like can be used as it is.
- the clay mineral-containing layer contains at least one kind of clay mineral in addition to the polysilazane compound. By blending the clay mineral, a gas barrier molded article having excellent bending resistance and good transparency can be obtained.
- the clay mineral used in the present invention is a mineral constituting clay, and the main component is a layered silicate mineral.
- Clay minerals consist of lamellar platelets that are separated by a gallery (a space between parallel layers of each platelet that contains various ions that join the platelets together).
- the thickness is usually 3 to 3000 mm, and the length in the plane direction is usually 0.01 to 100 ⁇ m.
- the aspect ratio is usually 10 to 10,000.
- the clay mineral examples include smectite clay minerals such as montmorillonite, saponite, beidellite, nontronite, hectorite, and stevensite; vermiculite; halloysite, and the like.
- smectite clay minerals such as montmorillonite, saponite, beidellite, nontronite, hectorite, and stevensite; vermiculite; halloysite, and the like.
- montmorillonite is more preferable.
- montmorillonite is more preferable.
- a commercially available product can be used as it is as a clay mineral.
- examples of commercially available products include CLOISITE (registered trademark) 10A (Organized Montmorillonite, Southern Clay Products, Inc.) (plate thickness: about 0.001 ⁇ m (10 mm), planar length: about 0.15 to about 0.20 ⁇ m) ), Manufactured by Sanyo Trading Co., Ltd., Delite 67G (thickness of the plate: about 0.001 ⁇ m (10 mm), length in the plane direction: about 1 ⁇ m), and the like.
- the total content of the polysilazane compound and the clay mineral in the clay mineral-containing layer is preferably 50% by mass or more, more preferably 70% by mass or more from the viewpoint of having excellent gas barrier properties. .
- the content of the clay mineral in the clay mineral-containing layer is preferably 0.01% by mass to 10% by mass, with the total amount of the polysilazane compound and the clay mineral being 100% by mass, preferably 0.05% by mass to
- the content is more preferably 5.0% by mass, and particularly preferably 0.1% by mass to 1.0% by mass.
- the layer containing clay mineral or the like may contain other components in addition to the polysilazane compound and the clay mineral as long as the object of the present invention is not impaired.
- Other components include other polymers, curing agents, anti-aging agents, light stabilizers, flame retardants, fillers, pigments, leveling agents, antifoaming agents, antistatic agents, UV absorbers, pH adjusters, dispersions Agents, surface modifiers, plasticizers, drying accelerators, flow inhibitors and the like.
- the method for forming the clay mineral-containing layer is not particularly limited.
- a layer forming solution containing at least one polysilazane compound, at least one clay mineral, other components, and a solvent as appropriate is appropriately used.
- coating on an appropriate base material layer, and drying and forming the obtained coating film moderately is mentioned.
- esters such as xylene, toluene, butyl carbitol acetate, n-butyl acetate, ethyl acetate; cellosolve, cellosolve acetate, etc.
- Glycol ethers ketones such as acetone and methyl ethyl ketone; and the like.
- the amount (ratio) of the solvent used is usually 1 to 99% by mass, preferably 5 to 60% by mass, based on the coating method, the type of polysilazane compound used, and the like.
- the coating apparatus known apparatuses such as a spin coater, a knife coater, and a gravure coater can be used.
- Heating is performed at 80 to 150 ° C. for several tens of seconds to several tens of minutes.
- the polysilazane compound is cured by crosslinking, condensation, and in some cases, oxidation and hydrolysis to form a ceramic phase.
- a dense film in which a ceramic phase mainly composed of Si—N bonds or Si—O bonds and a clay mineral phase are combined at a fine structure level can be obtained.
- the thickness of the clay mineral-containing layer to be formed is not particularly limited, but is usually 20 nm to 100 ⁇ m, preferably 30 to 500 nm, more preferably 40 to 200 nm. In the present invention, a molded article having a sufficient gas barrier performance can be obtained even if the thickness of the clay mineral-containing layer is nano-order.
- the molded article of the present invention preferably has a layer obtained by implanting ions into a layer containing a polysilazane compound and a clay mineral (hereinafter sometimes referred to as “ion implantation layer”).
- ion implantation layer a layer obtained by implanting ions into a layer containing a polysilazane compound and a clay mineral.
- the ion-implanted layer is not particularly limited as long as ions are implanted into the clay mineral-containing layer.
- ions to be implanted include rare gases such as argon, helium, neon, krypton, and xenon, ions such as fluorocarbon, hydrogen, nitrogen, oxygen, carbon dioxide, chlorine, fluorine, sulfur, silicon compounds, and hydrocarbons; gold, silver And ions of conductive metals such as copper, platinum, nickel, palladium, chromium, titanium, molybdenum, niobium, tantalum, tungsten, and aluminum.
- rare gases such as argon, helium, neon, krypton, and xenon
- ions such as fluorocarbon, hydrogen, nitrogen, oxygen, carbon dioxide, chlorine, fluorine, sulfur, silicon compounds, and hydrocarbons
- gold, silver And ions of conductive metals such as copper, platinum, nickel, palladium, chromium, titanium, molybdenum, niobium, tantalum, tungsten, and aluminum.
- at least one ion selected from the group consisting of hydrocarbons is preferred.
- Examples of the silicon compound include silane (SiH 4 ) and organosilicon compounds.
- organosilicon compounds include tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetra n-propoxysilane, tetraisopropoxysilane, tetra n-butoxysilane, and tetra t-butoxysilane;
- An alkylalkoxysilane having an unsubstituted or substituted group such as dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, (3,3,3-trifluoropropyl) trimethoxysilane;
- Arylalkoxysilanes such as diphenyldimethoxysilane and phenyltriethoxysilane; Disiloxanes such as hexamethyldisiloxane (HMDSO); Aminosilanes such as bis (dimethylamino) dimethylsilane, bis (dimethylamino) methylvinylsilane, bis (ethylamino) dimethylsilane, diethylaminotrimethylsilane, dimethylaminodimethylsilane, tetrakisdimethylaminosilane, tris (dimethylamino) silane; Silazanes such as hexamethyldisilazane, hexamethylcyclotrisilazane, heptamethyldisilazane, nonamethyltrisilazane, octamethylcyclotetrasilazane, tetramethyldisilazane; Cyanate silanes such
- Silylalkenes such as 1,4-bistrimethylsilyl-1,3-butadiyne, cyclopentadienyltrimethylsilane; Arylalkylsilanes such as phenyldimethylsilane and phenyltrimethylsilane; Alkynylalkylsilanes such as propargyltrimethylsilane; Alkenylalkylsilanes such as vinyltrimethylsilane; Disilanes such as hexamethyldisilane; Siloxanes such as octamethylcyclotetrasiloxane, tetramethylcyclotetrasiloxane, hexamethylcyclotetrasiloxane; N, O-bis (trimethylsilyl) acetamide; Bis (trimethylsilyl) carbodiimide; Etc.
- Arylalkylsilanes such as phenyldimethylsilane and phenyltrimethyls
- hydrocarbons examples include alkanes such as methane, ethane, propane, butane, pentane, and hexane; alkenes such as ethylene, propylene, butene, and pentene; alkadienes such as pentadiene and butadiene; alkynes such as acetylene and methylacetylene; benzene, toluene, Aromatic hydrocarbons such as xylene, indene, naphthalene and phenanthrene; cycloalkanes such as cyclopropane and cyclohexane; cycloalkenes such as cyclopentene and cyclohexene; and the like. These ions can be used alone or in combination of two or more.
- the ion implantation amount may be appropriately determined according to the intended use (necessary gas barrier property, transparency, etc.) of the formed article to be formed.
- the method for injecting ions is not particularly limited, and examples thereof include a method in which a layer containing clay mineral or the like (hereinafter, also referred to as “a layer for injecting ions”) is formed and then ions are injected into this layer. .
- Examples of the method of implanting ions include a method of irradiating ions accelerated by an electric field (ion beam), a method of implanting ions in plasma (plasma ion implantation method), and the like.
- ion beam an electric field
- plasma ion implantation method a method of implanting ions in plasma
- the latter plasma ion implantation method is preferable because a molded article having excellent gas barrier properties and the like can be obtained easily.
- plasma is generated in an atmosphere containing a plasma generation gas, and a negative high voltage pulse is applied to a layer into which ions are implanted, whereby ions (positive ions) in the plasma are ionized. Can be performed by injecting into the surface portion of the layer to be injected.
- the thickness of the portion where the ion-implanted layer is formed can be controlled by the implantation conditions such as ion type, applied voltage, treatment time, etc. Usually, it is 10 to 1000 nm.
- the ion implantation can be confirmed by performing an elemental analysis measurement at around 10 nm from the surface using X-ray photoelectron spectroscopy (XPS).
- XPS X-ray photoelectron spectroscopy
- the shape of the molded product of the present invention is not particularly limited, and examples thereof include a film shape, a sheet shape, a rectangular parallelepiped shape, a polygonal column shape, and a cylindrical shape.
- a film shape When used as an electronic device member as described later, it is preferably a film or sheet.
- the thickness of the film can be appropriately determined depending on the intended use of the electronic device.
- the molded body of the present invention may be composed of only a layer containing a polysilazane compound and a clay mineral or an ion-implanted layer, or may further contain another layer. Further, the other layer may be a single layer or two or more layers of the same type or different types. Examples of other layers include a base material layer, an inorganic compound layer, a shock absorbing layer, a conductor layer, and a primer layer.
- the order of lamination of each layer may be any.
- the arrangement position of the layer containing the polysilazane compound and the clay mineral or the ion-implanted layer is not particularly limited, but it has a layer containing the polysilazane compound and the clay mineral or the ion-implanted layer on the surface for the reason that it can be produced efficiently. Is preferred.
- the layer containing the polysilazane compound and the clay mineral or the ion-implanted layer may be formed only on one side of the other layer or on both sides of the other layer.
- the thickness of the laminate is not particularly limited and can be appropriately determined depending on the intended use of the electronic device.
- the material of the base material layer is not particularly limited as long as it matches the purpose of the molded body, for example, Polyimide, polyamide, polyamideimide, polyphenylene ether, polyether ketone, polyether ether ketone, polyolefin, polyester, polycarbonate, polysulfone, polyethersulfone, polyphenylene sulfide, polyarylate, clay mineral, cycloolefin polymer, aromatic heavy Examples include coalescence.
- polyester, polyamide or cycloolefin polymer is preferable, and polyester or cycloolefin polymer is more preferable because of excellent transparency and versatility.
- polyester examples include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and polyarylate.
- polyamide examples include wholly aromatic polyamide, nylon 6, nylon 66, nylon copolymer, and the like.
- cycloolefin polymers include norbornene polymers, monocyclic olefin polymers, cyclic conjugated diene polymers, vinyl alicyclic hydrocarbon polymers, and hydrides thereof. Specific examples thereof include Apel (an ethylene-cycloolefin copolymer manufactured by Mitsui Chemicals), Arton (a norbornene polymer manufactured by JSR), Zeonoa (a norbornene polymer manufactured by Nippon Zeon), and the like. .
- Apel an ethylene-cycloolefin copolymer manufactured by Mitsui Chemicals
- Arton a norbornene polymer manufactured by JSR
- Zeonoa a norbornene polymer manufactured by Nippon Zeon
- the inorganic compound layer is a layer made of one or more inorganic compounds.
- the inorganic compound that constitutes the inorganic compound layer is generally capable of vacuum film formation and has a gas barrier property, such as an inorganic oxide, an inorganic nitride, an inorganic carbide, an inorganic sulfide, or a composite of these. Examples thereof include nitrides, inorganic oxide carbides, inorganic nitride carbides, and inorganic oxynitride carbides. In the present invention, among these, inorganic oxides, inorganic nitrides, and inorganic oxynitrides are preferable.
- Examples of the inorganic oxide include metal oxides represented by the general formula MOx.
- M represents a metal element.
- x has a different range depending on M. For example, if M is silicon (Si), 0.1 to 2.0, if aluminum (Al), 0.1 to 1.5, and if magnesium (Mg), 0.1 to 1.0, 0.1 to 1.0 for calcium (Ca), 0.1 to 0.5 for potassium (K), 0.1 to 2 for tin (Sn) 0.0, 0.1 to 0.5 for sodium (Na), 0.1 to 1.5 for boron (B), 0.1 to 2.0 for titanium (Ti), lead ( The value is in the range of 0.1 to 1.0 for Pb), 0.1 to 2.0 for zirconium (Zr), and 0.1 to 1.5 for yttrium (Y).
- a silicon oxide in which M is silicon, an aluminum oxide that is aluminum, and a titanium oxide that is titanium are preferable, and a silicon oxide is more preferable.
- the value of x ranges from 1.0 to 2.0 if M is silicon, 0.5 to 1.5 if aluminum, and 1.3 to 2.0 if titanium. Those are preferred.
- Examples of the inorganic nitride include metal nitrides represented by the general formula MNy.
- M represents a metal element.
- silicon nitride in which M is silicon, aluminum nitride as aluminum, titanium nitride as titanium, and tin nitride as tin are preferable, and silicon nitride (SiN) Is more preferable.
- Examples of inorganic oxynitrides include metal oxynitrides represented by the general formula MOxNy.
- M represents a metal element.
- silicon oxynitride where M is silicon, aluminum oxynitride which is aluminum, and titanium oxynitride which is titanium are preferable, and silicon oxynitride is more preferable.
- the metal oxide, the metal nitride, and the metal oxynitride may contain two or more kinds of metals.
- the method for forming the inorganic compound layer is not particularly limited, and examples thereof include a vapor deposition method, a sputtering method, an ion plating method, a thermal CVD method, a plasma CVD method, and a dynamic ion mixing method.
- a magnetron sputtering method is preferable because a laminate having an excellent gas barrier property can be easily obtained.
- the thickness of the inorganic compound layer is not particularly limited, but is preferably 10 to 1000 nm, more preferably 20 to 500 nm, and particularly preferably 50 to 200 nm from the viewpoint of obtaining gas barrier properties.
- the shock absorbing layer is for preventing cracking when an impact is applied to the inorganic compound layer, and the material for forming the shock absorbing layer is not particularly limited.
- acrylic resin, urethane type Resins, silicone resins, olefin resins, rubber materials, and the like can be used. Among these, acrylic resins, silicone resins, and rubber materials are preferable.
- (meth) acrylic acid ester homopolymers, copolymers containing two or more (meth) acrylic acid ester units, and (meth) acrylic acid esters and other functional monomers are used as main components. What contains at least 1 sort (s) chosen from the copolymer with a monomer is mentioned.
- “(Meth) acrylic acid” means acrylic acid or methacrylic acid (the same shall apply hereinafter).
- (meth) acrylic acid ester (meth) acrylic acid having 1 to 20 carbon atoms in the ester portion is preferable, and (meth) acrylic acid ester having 4 to 10 carbon atoms in the ester portion is more preferable.
- Such (meth) acrylic acid esters include butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, (meth) Examples include 2-ethylhexyl acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, and the like.
- Functional monomers include hydroxyl group-containing monomers such as hydroxyethyl (meth) acrylate, amide group-containing monomers such as (meth) acrylamide, and carboxylic acid group-containing single monomers such as (meth) acrylic acid Examples include the body.
- the (meth) acrylic acid ester (co) polymer can be obtained by a known polymerization method such as a solution polymerization method, an emulsion polymerization method, or a suspension polymerization method.
- the (co) polymer means a homopolymer or a copolymer (hereinafter the same).
- the (meth) acrylic acid ester (co) polymer may be mixed with a crosslinking agent to form a crosslinked body at least partially.
- Crosslinking agents include tolylene diisocyanate, hexamethylene diisocyanate, etc., or adducts thereof, such as isocyanate crosslinking agents; ethylene glycol glycidyl ether and other epoxy crosslinking agents; hexa [1- (2-methyl) -aziridinyl ] Aziridine type crosslinking agents such as triphosphatriazine; Chelate type crosslinking agents such as aluminum chelate;
- the amount of the crosslinking agent used is usually 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the solid content of the (meth) acrylic acid ester (co) polymer.
- a crosslinking agent can be used individually by 1 type or in combination of 2 or more types.
- silicone resin examples include those containing dimethylsiloxane as a main component.
- rubber-based material examples include those mainly composed of isoprene rubber, styrene-butadiene rubber, polyisobutylene rubber, styrene-butadiene-styrene rubber and the like.
- the impact absorbing layer may contain other additives such as antioxidants, tackifiers, plasticizers, ultraviolet absorbers, colorants, antistatic agents and the like.
- the material for forming the shock absorbing layer may be a commercially available material such as an adhesive, a coating agent, and a sealant, and in particular, an acrylic adhesive, a silicone adhesive, a rubber adhesive, etc. An adhesive is preferred.
- the method for forming the shock absorbing layer is not particularly limited.
- the material for forming the shock absorbing layer such as an adhesive
- Examples include a method in which an impact absorbing layer forming solution containing other components such as a solvent is applied onto a layer to be laminated, and the resulting coating film is dried and heated as necessary.
- a shock absorbing layer may be separately formed on the release substrate, and the obtained film may be transferred and stacked on the layer to be stacked.
- the thickness of the shock absorbing layer is usually 1 to 100 ⁇ m, preferably 5 to 50 ⁇ m.
- Conductor layer examples of the material constituting the conductor layer include metals, alloys, metal oxides, electrically conductive compounds, and mixtures thereof. Specifically, tin oxide (ATO) doped with antimony; tin oxide (FTO) doped with fluorine; conductive such as tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO) Metal such as gold, silver, chromium and nickel; mixtures of these metals and conductive metal oxides; inorganic conductive materials such as copper iodide and copper sulfide; organic conductive materials such as polyaniline, polythiophene and polypyrrole Material, etc.
- the conductor layer may be a laminate in which a plurality of layers made of these materials are laminated. Among these, a conductive metal oxide is preferable from the viewpoint of transparency, and ITO is particularly preferable.
- Examples of the method for forming the conductor layer include a vapor deposition method, a sputtering method, an ion plating method, a thermal CVD method, a plasma CVD method, and the like.
- the sputtering method is preferable because the conductor layer can be easily formed.
- the sputtering method introduces a discharge gas (such as argon) into a vacuum chamber, applies a high-frequency voltage or a direct current voltage between the target and the substrate to turn the discharge gas into plasma, and collides the plasma with the target material.
- a discharge gas such as argon
- This is a method of obtaining a thin film by skipping and attaching to a substrate.
- a target made of a material for forming the conductor layer is used as the target.
- the thickness of a conductor layer suitably according to the use. Usually, it is 10 nm to 50 ⁇ m, preferably 20 nm to 20 ⁇ m.
- the surface resistivity of the obtained conductor layer is usually 1000 ⁇ / ⁇ or less.
- the formed conductor layer may be patterned as necessary.
- the patterning method include chemical etching by photolithography and the like, physical etching using a laser and the like, vacuum deposition method using a mask, sputtering method, lift-off method, printing method, and the like.
- the primer layer plays a role of enhancing interlayer adhesion between the base material layer, the layer containing the polysilazane compound and the clay mineral, or the ion implantation layer. By providing the primer layer, it is possible to obtain a gas barrier film that is extremely excellent in interlayer adhesion and surface smoothness.
- the material constituting the primer layer is not particularly limited, and known materials can be used.
- a photopolymerizable composition comprising a silicon-containing compound; a photopolymerizable compound comprising a photopolymerizable monomer and / or a photopolymerizable prepolymer, and a polymerization initiator that generates radicals at least in the visible light region; Resin, polyurethane resin (especially two-part curable resin of polyacryl polyol, polyester polyol, polyether polyol, etc.
- acrylic resin polycarbonate resin
- vinyl chloride / vinyl acetate copolymer vinyl chloride / vinyl acetate copolymer
- polyvinyl butyral Resins such as resins and nitrocellulose resins
- alkyl titanates alkyl titanates
- ethyleneimines ethyleneimines
- a primer layer forming solution obtained by dissolving or dispersing the material constituting the primer layer in an appropriate solvent is applied to one or both sides of the base material layer, and the obtained coating film is dried to obtain a desired layer. It can form by heating by.
- a normal wet coating method can be used as a method for applying the primer layer forming solution to the base material layer. Examples include dipping method, roll coating, gravure coating, knife coating, air knife coating, roll knife coating, die coating, screen printing method, spray coating, gravure offset method and the like.
- a conventionally known drying method such as hot air drying, hot roll drying, infrared irradiation or the like can be employed.
- the thickness of the primer layer is usually 10 to 1000 nm.
- ion implantation may be performed on the obtained primer layer by a method similar to the method of ion implantation into the ion implantation layer described later. By performing ion implantation also on the primer layer, a more excellent gas barrier film can be obtained.
- the molded article of the present invention is characterized in that the water vapor permeability in an atmosphere of 40 ° C. and 90% relative humidity is 6.0 g / m 2 / day or less.
- the water vapor transmission rate is preferably 1.0 g / m 2 / day or less, more preferably 0.7 g / m 2 / day or less, and 0.4 g / m 2 / day or less. Particularly preferred.
- the water vapor transmission rate can be measured using a known gas transmission rate measuring device.
- the molded body of the present invention further has excellent transparency, and when the shape thereof is a film or sheet (hereinafter referred to as “film”), it has excellent bending resistance and can be bent. Those that maintain the gas barrier properties even when they are used are preferable.
- the total light transmittance is a transmittance at a wavelength of 550 nm, and preferably 86% or more.
- the total light transmittance of the molded product can be measured using a known total light transmittance measuring device.
- the molded product of the present invention has excellent folding resistance and can maintain gas barrier properties even when folded, etc.
- the molded product of the present invention has the following formula:
- the film-shaped molded article of the present invention is excellent in maintaining gas barrier properties even after folding, as compared with an inorganic film having the same thickness.
- the manufacturing method of the molded object of this invention has the process of inject
- a molded body is produced by injecting ions into a clay mineral etc. containing layer while conveying a long shaped molding having a clay mineral etc. containing layer on the surface portion in a certain direction. It is preferable to do this.
- a long shaped product can be unwound from an unwinding roll, and ions can be injected while being conveyed in a certain direction, and can be taken up by a winding roll.
- the formed molded body can be continuously produced.
- the shape of the elongated molded product is a film, and may be composed only of a clay mineral-containing layer, or may be a laminate including other layers having a clay mineral-containing layer on the surface portion. .
- the thickness of the molded product is preferably 1 ⁇ m to 500 ⁇ m, more preferably 5 ⁇ m to 300 ⁇ m, from the viewpoint of unwinding, winding and conveying operability.
- the method for injecting ions into the clay mineral-containing layer is not particularly limited.
- a method of forming an ion implantation layer on the surface portion of the layer by plasma ion implantation is particularly preferable.
- a negative high-voltage pulse is applied to a molded article that is exposed to plasma and has a clay mineral-containing layer on its surface to inject ions in the plasma into the surface of the layer. This is a method of forming an ion implantation layer.
- (A) a method in which ions existing in plasma generated using an external electric field are implanted into the surface portion of the layer, or (B) the layer is formed without using an external electric field.
- a method of injecting ions present in the plasma generated only by the electric field by the negative high voltage pulse to be applied to the surface portion of the layer is preferable.
- the pressure during ion implantation is preferably 0.01 to 1 Pa.
- the pressure at the time of plasma ion implantation is in such a range, a uniform ion implantation layer excellent in gas barrier properties and the like can be formed easily and efficiently.
- the processing operation is simple, and the processing time can be greatly shortened. Further, the entire layer can be processed uniformly, and ions in the plasma can be continuously injected into the surface portion of the layer with high energy when a negative high voltage pulse is applied. Furthermore, without applying special other means such as radio frequency (hereinafter abbreviated as “RF”) or a high frequency power source such as a microwave, just applying a negative high voltage pulse to the layer, A high-quality ion-implanted layer can be uniformly formed on the surface of the layer.
- RF radio frequency
- a high frequency power source such as a microwave
- the pulse width when applying a negative high voltage pulse is preferably 1 to 15 ⁇ sec.
- the pulse width is in such a range, a transparent and uniform ion implantation layer can be formed more easily and efficiently.
- the applied voltage when generating plasma is preferably -1 kV to -50 kV, more preferably -1 kV to -30 kV, and particularly preferably -5 kV to -20 kV. If ion implantation is performed at an applied voltage greater than ⁇ 1 kV, the ion implantation amount (dose amount) becomes insufficient, and desired performance cannot be obtained. On the other hand, if ion implantation is performed at a value smaller than ⁇ 50 kV, the molded body is charged at the time of ion implantation, and defects such as coloring of the molded body occur.
- Examples of the source gas for generating plasma ions include the same materials as those exemplified in the section 1) Molded body.
- a plasma ion implantation apparatus When ions in plasma are implanted into the surface portion of the layer, a plasma ion implantation apparatus is used. Specifically, the plasma ion implantation apparatus ( ⁇ ) uniformly surrounds the periphery of the layer to be ion-implanted by superimposing high-frequency power on a feedthrough that applies a negative high voltage pulse to the layer to be ion-implanted, A device for attracting, implanting, colliding and depositing ions in plasma (Japanese Patent Laid-Open No. 2001-26887), ( ⁇ ) An antenna is provided in the chamber, and a plasma is generated by applying high-frequency power around the layer where ions are implanted.
- the positive ion pulse By applying positive and negative pulses alternately to the ion-implanted layer after the plasma arrives, the positive ion pulse attracts and collides electrons in the plasma to heat the ion-implanted layer and controls the pulse constant.
- An apparatus for attracting and injecting ions in plasma by applying a negative pulse while performing temperature control Japanese Patent Laid-Open No. 2001-156013
- ⁇ high-frequency electric power
- microwave Plasma ion implantation device that generates plasma using an external electric field such as a force source and attracts and injects ions in the plasma by applying a high voltage pulse
- ⁇ By applying a high voltage pulse without using an external electric field
- Examples include a plasma ion implantation apparatus that implants ions in plasma generated only by an electric field generated.
- the plasma ion implantation apparatus ( ⁇ ) or ( ⁇ ) because the processing operation is simple, the processing time can be greatly shortened, and it is suitable for continuous use.
- a method using the plasma ion implantation apparatuses ( ⁇ ) and ( ⁇ ) will be described in detail with reference to the drawings.
- FIG. 1 is a diagram showing an outline of a continuous plasma ion implantation apparatus including the plasma ion implantation apparatus ( ⁇ ).
- 1a is a long film-like molded product (hereinafter referred to as “film”) having a clay mineral-containing layer on the surface
- 11a is a chamber
- 20a is a turbo molecular pump
- 3a is ion implantation.
- Unwinding roll for feeding out the film 1a before being wound 5a is a winding roll for winding the ion-implanted film (molded body) 1a into a roll
- 2a is a high-voltage applied rotation can
- 6a is a film feeding roll
- 10a Is a gas inlet
- 7a is a high voltage pulse power supply
- 4 is a plasma discharge electrode (external electric field).
- FIG. 1B is a perspective view of the high-voltage applying rotation can 2a
- 15 is a high-voltage introduction terminal (feedthrough).
- the long film 1a having a layer for ion implantation to be used on the surface is a film in which a layer containing clay mineral or the like is formed on a base material layer.
- the film 1a is transported in the chamber 11a from the unwinding roll 3a in the direction of the arrow X in FIG. It is wound up on a roll 5a.
- the film 1a is transported by rotating the high voltage application rotating can 2a at a constant speed. ing.
- the rotation of the high voltage application rotation can 2a is performed by rotating the central shaft 13 of the high voltage introduction terminal 15 by a motor.
- the high voltage introduction terminal 15 and the plurality of delivery rolls 6a with which the film 1a comes into contact are made of an insulator, for example, formed by coating the surface of alumina with a resin such as polytetrafluoroethylene.
- the high voltage application rotation can 2a is made of a conductor, and can be formed of stainless steel, for example.
- the conveyance speed of the film 1a can be set as appropriate.
- the film 1a is transported from the unwinding roll 3a and is ion-implanted into the surface portion (clay mineral-containing layer) of the film 1a until the film 1a is wound on the winding roll 5a, thereby forming a desired ion-implanted layer.
- the film winding speed (conveyance speed) is usually 0.1 to 3 m / min, preferably 0.2 to 2.5 m / min, although it depends on the applied voltage and the scale of the apparatus.
- the chamber 11a is evacuated by a turbo molecular pump 20a connected to a rotary pump to reduce the pressure.
- the degree of reduced pressure is usually 1 ⁇ 10 ⁇ 4 Pa to 1 ⁇ 10 0 Pa, preferably 1 ⁇ 10 ⁇ 3 Pa to 1 ⁇ 10 ⁇ 2 Pa.
- a gas for ion implantation (hereinafter sometimes referred to as “ion implantation gas”) is introduced into the chamber 11a from the gas inlet 10a, and the inside of the chamber 11a is set to a reduced pressure ion implantation gas atmosphere.
- the ion implantation gas is also a plasma generation gas.
- plasma is generated by the plasma discharge electrode 4 (external electric field).
- a method for generating plasma a known method using a high-frequency power source such as a microwave or RF may be used.
- the negative high voltage pulse 9a is applied by the high voltage pulse power source 7a connected to the high voltage application rotation can 2a via the high voltage introduction terminal 15.
- a negative high-voltage pulse is applied to the high-voltage application rotation can 2a, ions in the plasma are induced and injected into the surface of the film around the high-voltage application rotation can 2a (in FIG. 1A, the arrow Y) A film-like molded body 1b is obtained.
- the pressure during ion implantation (the pressure of the plasma gas in the chamber 11a) is preferably 0.01 to 1 Pa, and the pulse width during ion implantation is 1 to 15 ⁇ sec.
- the applied voltage when applying a negative high voltage to the high-voltage applying rotation can 2a is preferably ⁇ 1 kV to ⁇ 50 kV.
- the apparatus shown in FIG. 2 includes the plasma ion implantation apparatus ( ⁇ ).
- This plasma ion implantation apparatus generates plasma only by an electric field by a high voltage pulse applied without using an external electric field (that is, plasma discharge electrode 4 in FIG. 1).
- the film (film-like molded product) 1c is removed from the unwinding roll 3b by rotating the high-voltage applied rotation can 2b, as in the apparatus of FIG. In FIG. 2, it is conveyed in the direction of the arrow X and is taken up by the take-up roll 5b.
- ion implantation into the surface portion of the clay mineral-containing layer of the film is performed as follows.
- the film 1c is placed in the chamber 11b, and the inside of the chamber 11b is evacuated by the turbo molecular pump 20b connected to the rotary pump to reduce the pressure.
- an ion implantation gas is introduced into the chamber 11b from the gas introduction port 10b, and the inside of the chamber 11b is made a reduced pressure ion implantation gas atmosphere.
- the pressure at the time of ion implantation (the pressure of the plasma gas in the chamber 11b) is 10 Pa or less, preferably 0.01 to 5 Pa, more preferably 0.01 to 1 Pa.
- the high voltage pulse power supply 7b connected to the high voltage application rotation can 2b through the high voltage introduction terminal (not shown) is conveyed while the film 1c is conveyed in the direction of X in FIG. Apply 9b.
- the applied voltage when applying a negative high voltage to the high-voltage applying rotation can 2b, the pulse width, and the pressure during ion implantation are the same as those in the continuous plasma ion implantation apparatus shown in FIG.
- the plasma generating means for generating plasma is also used by the high voltage pulse power source, no special other means such as a high frequency power source such as RF or microwave is required.
- a high frequency power source such as RF or microwave
- plasma is generated, ions in the plasma are injected into the surface of the clay mineral containing layer of the film, and an ion-implanted layer is continuously formed on the surface of the film. It is possible to mass-produce molded bodies on which ion-implanted layers are formed.
- the electronic device member of the present invention is characterized by comprising the molded article of the present invention. Therefore, since the electronic device member of the present invention has excellent gas barrier properties, it is possible to prevent deterioration of the element due to gas such as water vapor. Moreover, since the light transmittance is high, it is suitable as a display member such as a liquid crystal display or an EL display; a back sheet for a solar cell;
- the electronic device of the present invention includes the electronic device member of the present invention.
- Specific examples include a liquid crystal display, an organic EL display, an inorganic EL display, electronic paper, and a solar battery. Since the electronic device of the present invention includes the electronic device member comprising the molded article of the present invention, it has excellent gas barrier properties, transparency, and bending resistance.
- the plasma ion implantation apparatus, water vapor transmission rate measurement apparatus and measurement conditions, total light transmittance measurement apparatus, and bending test method used are as follows.
- the plasma ion implantation apparatus used is an apparatus for ion implantation using an external electric field.
- RF power source JEOL Ltd., model number “RF” 56000
- High voltage pulse power supply “PV-3-HSHV-0835” manufactured by Kurita Manufacturing Co., Ltd.
- Total light transmittance measuring device “UV-3101PC” manufactured by Shimadzu Corporation was used to measure the total light transmittance at a wavelength of 550 nm.
- Example 1 A coating agent mainly composed of perhydropolysilazane as a polysilazane compound on a polyethylene terephthalate film (“PET38 T-100”, thickness 38 ⁇ m, hereinafter referred to as “PET film”, manufactured by Mitsubishi Plastics) as a base material layer (Clariant Japan, “Aquamica NL110-20”) and a 0.2% by mass xylene solution in which clay mineral (Sanyo Trading Co., Ltd., Dellite 67G) is dispersed, An amount of 150 nm was applied and heated at 120 ° C. for 2 minutes to form a layer containing perhydropolysilazane and clay mineral on the PET film.
- PET38 T-100 polyethylene terephthalate film
- PET film manufactured by Mitsubishi Plastics
- clay mineral Sanyo Trading Co., Ltd., Dellite 67G
- argon (Ar) is ion-implanted on the surface of the layer containing the perhydropolysilazane and clay mineral under the conditions shown below to produce a compact 1. did.
- the molded body 2 was produced in the same manner as described above.
- the molded body 3 was produced in the same manner as described above.
- Example 1 A molded body was produced in the same manner as in Example 1 except that ion implantation was not performed. That is, a layer containing perhydropolysilazane and clay mineral was formed on a PET film, and this was used as a molded body 4.
- a molded body 5 was produced by forming a silicon nitride (SiN) film having a thickness of 60 nm on a PET film by a sputtering method.
- SiN silicon nitride
- Example 3 A molded body was produced in the same manner as in Example 1 except that a layer containing perhydropolysilazane and clay mineral was not formed on the PET film. That is, argon (Ar) was ion-implanted into the surface of the PET film under the same conditions as in Example 1 to produce a molded body 6.
- Example 4 A molded body 7 was produced in the same manner as in Example 1 except that no clay mineral was used in Example 1.
- the molded products 1 to 7 were subjected to a bending test to confirm the presence or absence of cracks. The results are shown in Table 1. Furthermore, the water vapor transmission rate after the bending test was measured, and the water vapor transmission increase rate was calculated. The results are shown in Table 1.
- the molded bodies 4 and 6 of Comparative Examples 1 and 3 had high water vapor permeability and poor gas barrier properties.
- the molded bodies 5 and 7 of Comparative Examples 2 and 4 had a large increase in water vapor transmission rate after the bending test, and the molded body 5 of Comparative Example 2 also had cracks and was inferior in bending resistance.
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Abstract
Description
例えば、食品や医薬品の包装用フィルムには、蛋白質や油脂等の酸化や変質を抑制して味や鮮度を保持するため、水蒸気や酸素の透過を防ぐガスバリア性のプラスチックフィルムが用いられている。
しかしながら、この文献記載のフレキシブルディスプレイ基板は、透明プラスチックフィルム表面に、蒸着法、イオンプレーティング法、スパッター法等により、金属酸化物からなる透明ガスバリア層を積層したものであるため、該基板を丸めたり折り曲げたりすると、ガスバリア層にクラックが発生してガスバリア性が低下するという問題があった。
しかしながら、酸素、水蒸気等のガスバリア性を得るためには、さらに無機化合物層を積層する必要があるため、工程が煩雑であったりコストがかかったり、毒性を有するガスを使用する危険性がある等の問題があった。
しかしながら、この方法では、ガスバリア層の厚みをミクロンオーダーにしなければ充分なガスバリア性能を出せないという問題があった。
(1)ポリシラザン化合物と粘土鉱物とを含む層からなり、40℃、相対湿度90%雰囲気下での水蒸気透過率が、6.0g/m2/day以下であることを特徴とする成形体。
(2)ポリシラザン化合物と粘土鉱物とを含む層にイオンが注入されて得られる層を有することを特徴とする(1)に記載の成形体。
(3)前記イオンが、水素、窒素、酸素、アルゴン、ヘリウム、ネオン、キセノン、クリプトン、ケイ素化合物及び炭化水素からなる群から選ばれる少なくとも一種のガスがイオン化されたものであることを特徴とする(2)に記載の成形体。
(4)前記ポリシラザン化合物と粘土鉱物を含む層に、プラズマイオン注入によりイオンが注入されて得られる層を有することを特徴とする(2)又は(3)に記載の成形体。
(5)前記ポリシラザン化合物が、ペルヒドロポリシラザンであることを特徴とする(1)又は(2)に記載の成形体。
(6)前記ポリシラザン化合物と粘土鉱物とを含む層中の粘土鉱物の含有量が、ポリシラザン化合物と粘土鉱物の合計量を100質量%として、0.01質量%~10質量%であることを特徴とする(1)又は(2)に記載の成形体。
(7)ポリシラザン化合物と粘土鉱物とを含む層を表面部に有する成形物の、前記ポリシラザン化合物と粘土鉱物とを含む層の表面部に、イオンを注入する工程を有する(2)に記載の成形体の製造方法。
(8)ポリシラザン化合物と粘土鉱物とを含む表面部を有する成形物の、前記ポリシラザン化合物と粘土鉱物とを含む層の表面部に、水素、窒素、酸素、アルゴン、ヘリウム、キセノン、ネオン、クリプトン、ケイ素化合物及び炭化水素からなる群から選ばれる少なくとも一種のガスをイオン注入する工程を有する(7)に記載の成形体の製造方法。
(9)前記イオン注入する工程が、プラズマイオン注入する工程であることを特徴とする(7)又は(8)に記載の成形体の製造方法。
(10)ポリシラザン化合物と粘土鉱物とを含む層を表面部に有する長尺状の成形物を一定方向に搬送しながら、前記ポリシラザン化合物と粘土鉱物とを含む層に、イオンを注入することを特徴とする(2)に記載の成形体の製造方法。
(11)(1)又は(2)に記載の成形体からなる電子デバイス用部材。
本発明の第4によれば、下記(12)の電子デバイスが提供される。
(12)(11)に記載の電子デバイス用部材を備える電子デバイス。
本発明の製造方法によれば、優れたガスバリア性、透明性、耐折り曲げ性を有する本発明の成形体を簡便かつ効率よく製造することができる。また、ガスバリア膜として無機膜が成膜された成形体に比して、低コストにて容易に大面積化を図ることができる。
本発明の電子デバイス用部材は、優れたガスバリア性、透明性及び耐折り曲げ性を有するため、ディスプレイ、太陽電池等の電子デバイスに好適に用いることができる。
本発明の成形体は、ポリシラザン化合物と粘土鉱物とを含む層(以下、「粘土鉱物等含有層」ということがある。)からなり、40℃、相対湿度90%雰囲気下での水蒸気透過率が、6.0g/m2/day以下であることを特徴とする。
Rx、Ry、Rzは、それぞれ独立して、水素原子、無置換若しくは置換基を有するアルキル基、無置換若しくは置換基を有するシクロアルキル基、無置換若しくは置換基を有するアルケニル基、無置換若しくは置換基を有するアリール基又はアルキルシリル基等の非加水分解性基を表す。
無機ポリシラザンとしては、下記式
(i)-(Rx’SiHNH)-(Rx’は、無置換若しくは置換基を有するアルキル基、無置換若しくは置換基を有するシクロアルキル基、無置換若しくは置換基を有するアルケニル基、無置換若しくは置換基を有するアリール基、又はアルキルシリル基を表す。以下のRx’も同様である。)を繰り返し単位として、主として重合度が3~5の環状構造を有するもの、
(ii)-(Rx’SiHNRz’)-(Rz’は、無置換若しくは置換基を有するアルキル基、無置換若しくは置換基を有するシクロアルキル基、無置換若しくは置換基を有するアルケニル基、無置換若しくは置換基を有するアリール基、又はアルキルシリル基を表す。)を繰り返し単位として、主として重合度が3~5の環状構造を有するもの、
(iii)-(Rx’Ry’SiNH)-(Ry’は、無置換若しくは置換基を有するアルキル基、無置換若しくは置換基を有するシクロアルキル基、無置換若しくは置換基を有するアルケニル基、無置換若しくは置換基を有するアリール基、又はアルキルシリル基を表す。)を繰り返し単位として、主として重合度が3~5の環状構造を有するもの、
(iv)下記式で表される構造を分子内に有するポリオルガノ(ヒドロ)シラザン、
で表される繰り返し構造を有するポリシラザン等が挙げられる。
用いる2級アミン、アンモニア及び1級アミンは、目的とするポリシラザン化合物の構造に応じて、適宜選択すればよい。
各小板の大きさは、厚さが、通常3~3000Åであり、平面方向の長さが通常0.01~100μmである。また、アスペクト比は、通常10~10000である。
これらは、一種単独で、或いは二種以上を組み合わせて用いることができる。
市販品としては、例えば、有機化モンモリロナイトSouthern Clay Products社製、CLOISITE(登録商標)10A(小板の厚み:約0.001μm(10Å)、平面方向長さ:約0.15~約0.20μm)、三洋貿易株式会社製、Dellite67G(小板の厚み:約0.001μm(10Å)、平面方向長さ:約1μm)等が挙げられる。
本発明においては、粘土鉱物等含有層の厚さがナノオーダーであっても、充分なガスバリア性能を有する成形体を得ることができる。
有機ケイ素化合物としては、テトラメトキシシラン、テトラエトキシシラン、テトラn-プロポキシシラン、テトライソプロポキシシラン、テトラn-ブトキシシラン、テトラt-ブトキシシラン等のテトラアルコキシシラン;
ジメチルジメトキシシラン、ジメチルジエトキシシラン、ジエチルジメトキシシラン、メチルトリエトキシシラン、エチルトリメトキシシラン、(3,3,3-トリフルオロプロピル)トリメトキシシラン等の無置換若しくは置換基を有するアルキルアルコキシシラン;
ヘキサメチルジシロキサン(HMDSO)等のジシロキサン;
ビス(ジメチルアミノ)ジメチルシラン、ビス(ジメチルアミノ)メチルビニルシラン、ビス(エチルアミノ)ジメチルシラン、ジエチルアミノトリメチルシラン、ジメチルアミノジメチルシラン、テトラキスジメチルアミノシラン、トリス(ジメチルアミノ)シラン等のアミノシラン;
ヘキサメチルジシラザン、ヘキサメチルシクロトリシラザン、ヘプタメチルジシラザン、ノナメチルトリシラザン、オクタメチルシクロテトラシラザン、テトラメチルジシラザン等のシラザン;
テトライソシアナートシラン等のシアナートシラン;
トリエトキシフルオロシラン等のハロゲノシラン;
ジアリルジメチルシラン、アリルトリメチルシラン等のアルケニルシラン;
ジ-t-ブチルシラン、1,3-ジシラブタン、ビス(トリメチルシリル)メタン、トリメチルシラン、テトラメチルシラン、トリス(トリメチルシリル)メタン、トリス(トリメチルシリル)シラン、ベンジルトリメチルシラン等の無置換若しくは置換基を有するアルキルシラン;
ビス(トリメチルシリル)アセチレン、トリメチルシリルアセチレン、1-(トリメチルシリル)-1-プロピン等のシリルアルキン;
フェニルジメチルシラン、フェニルトリメチルシラン等のアリールアルキルシラン;
プロパルギルトリメチルシラン等のアルキニルアルキルシラン;
ビニルトリメチルシラン等のアルケニルアルキルシラン;
ヘキサメチルジシラン等のジシラン;
オクタメチルシクロテトラシロキサン、テトラメチルシクロテトラシロキサン、ヘキサメチルシクロテトラシロキサン等のシロキサン;
N,O-ビス(トリメチルシリル)アセトアミド;
ビス(トリメチルシリル)カルボジイミド;
等が挙げられる。
これらのイオンは、一種単独で、或いは二種以上を組み合わせて用いることができる。
他の層としては、基材層、無機化合物層、衝撃吸収層、導電体層、プライマー層等が挙げられる。
基材層の素材は、成形体の目的に合致するものであれば特に制限されず、例えば、
ポリイミド、ポリアミド、ポリアミドイミド、ポリフェニレンエーテル、ポリエーテルケトン、ポリエーテルエーテルケトン、ポリオレフィン、ポリエステル、ポリカーボネート、ポリスルフォン、ポリエーテルスルフォン、ポリフェニレンスルフィド、ポリアリレート、粘土鉱物、シクロオレフィン系ポリマー、芳香族系重合体等が挙げられる。
ポリアミドとしては、全芳香族ポリアミド、ナイロン6、ナイロン66、ナイロン共重合体等が挙げられる。
無機化合物層は、無機化合物の一種又は二種以上からなる層である。無機化合物層を構成する無機化合物としては、一般的に真空成膜可能で、ガスバリア性を有するもの、例えば無機酸化物、無機窒化物、無機炭化物、無機硫化物、これらの複合体である無機酸化窒化物、無機酸化炭化物、無機窒化炭化物、無機酸化窒化炭化物等が挙げられる。本発明においては、これらの中でも、無機酸化物、無機窒化物、無機酸化窒化物が好ましい。
式中、Mは金属元素を表す。xはMによってそれぞれ範囲が異なり、例えば、Mがケイ素(Si)であれば0.1~2.0、アルミニウム(Al)であれば0.1~1.5、マグネシウム(Mg)であれば0.1~1.0、カルシウム(Ca)であれば0.1~1.0、カリウム(K)であれば0.1~0.5、スズ(Sn)であれば0.1~2.0、ナトリウム(Na)であれば0.1~0.5、ホウ素(B)であれば0.1~1.5、チタン(Ti)であれば0.1~2.0、鉛(Pb)であれば0.1~1.0、ジルコニウム(Zr)であれば0.1~2.0、イットリウム(Y)であれば、0.1~1.5の範囲の値である。
式中、Mは金属元素を表す。yはMによってそれぞれ範囲が異なり、Mがケイ素(Si)であればy=0.1~1.3、アルミニウム(Al)であればy=0.1~1.1、チタン(Ti)であればy=0.1~1.3、すず(Sn)であればy=0.1~1.3の範囲の値である。
式中、Mは金属元素を表す。x及びyの値は、Mによってそれぞれ範囲が異なる。すなわち、x、yは、例えば、Mがケイ素(Si)であればx=1.0~2.0、y=0.1~1.3、アルミニウム(Al)であればx=0.5~1.0、y=0.1~1.0、マグネシウム(Mg)であればx=0.1~1.0、y=0.1~0.6、カルシウム(Ca)であればx=0.1~1.0、y=0.1~0.5、カリウム(K)であればx=0.1~0.5、y=0.1~0.2、スズ(Sn)であればx=0.1~2.0、y=0.1~1.3、ナトリウム(Na)であればx=0.1~0.5、y=0.1~0.2、ホウ素(B)であればx=0.1~1.0、y=0.1~0.5、チタン(Ti)であればx=0.1~2.0、y=0.1~1.3、鉛(Pb)であればx=0.1~1.0、y=0.1~0.5、ジルコニウム(Zr)であればx=0.1~2.0、y=0.1~1.0、イットリウム(Y)であればx=0.1~1.5、y=0.1~1.0の範囲の値である。
なお、金属酸化物、金属窒化物及び金属酸化窒化物には、2種類以上の金属が含まれていても良い。
衝撃吸収層は、前記無機化合物層に衝撃が加わった際に、割れを防止するためのものであり、衝撃吸収層を形成する素材としては、特に限定されないが、例えば、アクリル系樹脂、ウレタン系樹脂、シリコーン系樹脂、オレフィン系樹脂、ゴム系材料等を用いることができる。これらの中でも、アクリル系樹脂、シリコーン系樹脂、ゴム系材料が好ましい。
このような(メタ)アクリル酸エステルとしては、(メタ)アクリル酸ブチル、(メタ)アクリル酸ペンチル、(メタ)アクリル酸ヘキシル、(メタ)アクリル酸ヘプチル、(メタ)アクリル酸オクチル、(メタ)アクリル酸2-エチルヘキシル、(メタ)アクリル酸ノニル、(メタ)アクリル酸デシル等が挙げられる。
架橋剤としては、トリレンジイソシアネート、ヘキサメチレンジイソシアナート等、或いはそれらのアダクト体等のイソシアネート系架橋剤;エチレングリコールグリシジルエーテル等のエポキシ系架橋剤;ヘキサ〔1-(2-メチル)-アジリジニル〕トリフオスファトリアジン等のアジリジン系架橋剤;アルミニウムキレート等のキレート系架橋剤;等が挙げられる。
ゴム系材料としては、イソプレンゴム、スチレン-ブタジエンゴム、ポリイソブチレンゴム、スチレン-ブタジエン-スチレンゴム等を主成分とするものが挙げられる。
また、別途、剥離基材上に衝撃吸収層を成膜し、得られた膜を、積層すべき層上に転写して積層してもよい。
衝撃吸収層の厚みは、通常1~100μm、好ましくは5~50μmである。
導電体層を構成する材料としては、金属、合金、金属酸化物、電気伝導性化合物、これらの混合物等が挙げられる。具体的には、アンチモンをドープした酸化スズ(ATO);フッ素をドープした酸化スズ(FTO);酸化スズ、酸化亜鉛、酸化インジウム、酸化インジウムスズ(ITO)、酸化亜鉛インジウム(IZO)等の導電性金属酸化物;金、銀、クロム、ニッケル等の金属;これら金属と導電性金属酸化物との混合物;ヨウ化銅、硫化銅等の無機導電性物質;ポリアニリン、ポリチオフェン、ポリピロール等の有機導電性材料;等が挙げられる。導電体層は、これらの材料からなる層が複数積層されてなる積層体であってもよい。
これらの中でも、透明性の点から、導電性金属酸化物が好ましく、ITOが特に好ましい。
得られる導電体層の表面抵抗率は、通常1000Ω/□以下である。
プライマー層は、基材層とポリシラザン化合物と粘土鉱物とを含む層あるいはイオン注入層との層間密着性を高める役割を果たす。プライマー層を設けることにより、層間密着性及び表面平滑性に極めて優れるガスバリア性フィルムを得ることができる。
本発明の成形体の製造方法は、粘土鉱物等含有層を表面部に有する成形物の、前記粘土鉱物等含有層に、イオンを注入する工程を有することを特徴とする。
この製造方法によれば、例えば、長尺状の成形物を巻き出しロールから巻き出し、それを一定方向に搬送しながらイオンを注入し、巻き取りロールで巻き取ることができるので、イオンが注入された成形体を連続的に製造することができる。
プラズマイオン注入装置としては、具体的には、(α)イオン注入する層に負の高電圧パルスを印加するフィードスルーに高周波電力を重畳してイオン注入する層の周囲を均等にプラズマで囲み、プラズマ中のイオンを誘引、注入、衝突、堆積させる装置(特開2001-26887号公報)、(β)チャンバー内にアンテナを設け、高周波電力を与えてプラズマを発生させてイオン注入する層周囲にプラズマが到達後、イオン注入する層に正と負のパルスを交互に印加することで、正のパルスでプラズマ中の電子を誘引衝突させてイオン注入する層を加熱し、パルス定数を制御して温度制御を行いつつ、負のパルスを印加してプラズマ中のイオンを誘引、注入させる装置(特開2001-156013号公報)、(γ)マイクロ波等の高周波電力源等の外部電界を用いてプラズマを発生させ、高電圧パルスを印加してプラズマ中のイオンを誘引、注入させるプラズマイオン注入装置、(δ)外部電界を用いることなく高電圧パルスの印加により発生する電界のみで発生するプラズマ中のイオンを注入するプラズマイオン注入装置等が挙げられる。
以下、前記(γ)及び(δ)のプラズマイオン注入装置を用いる方法について、図面を参照しながら詳細に説明する。
図1(a)において、1aは粘土鉱物等含有層を表面部に有する長尺フィルム状の成形物(以下、「フィルム」という。)、11aはチャンバー、20aはターボ分子ポンプ、3aはイオン注入される前のフィルム1aを送り出す巻き出しロール、5aはイオン注入されたフィルム(成形体)1aをロール状に巻き取る巻取りロール、2aは高電圧印加回転キャン、6aはフィルムの送り出しロール、10aはガス導入口、7aは高電圧パルス電源、4はプラズマ放電用電極(外部電界)である。図1(b)は、前記高電圧印加回転キャン2aの斜視図であり、15は高電圧導入端子(フィードスルー)である。
本発明の電子デバイス用部材は、本発明の成形体からなることを特徴とする。従って、本発明の電子デバイス用部材は、優れたガスバリア性を有しているので、水蒸気等のガスによる素子の劣化を防ぐことができる。また、光の透過性が高いので、液晶ディスプレイ、ELディスプレイ等のディスプレイ部材;太陽電池用バックシート;等として好適である。
本発明の電子デバイスは、本発明の成形体からなる電子デバイス用部材を備えているので、優れたガスバリア性、透明性及び耐折り曲げ性を有する。
RF電源:日本電子社製、型番号「RF」56000
高電圧パルス電源:栗田製作所社製、「PV-3-HSHV-0835」
ガス透過率測定装置:水蒸気透過率が0.01g/m2/day以上のとき、LYSSY社製、「L89-500」を用い、水蒸気透過率が0.01g/m2/day未満のとき、TECHNOLOX社製、「deltaperm」を用いた。
測定は相対湿度90%、40℃の条件下で行った。
全光線透過率測定装置:島津製作所社製、「UV-3101PC」を使用して、波長550nmの全光線透過率を測定した
得られた成形体のイオン注入面(比較例1はペルヒドロポリシラザン等を含む層側、比較例2は窒化ケイ素膜側)を外側にし、中央部分で半分に折り曲げてラミネーター(フジプラ社製、「LAMIPACKER LPC1502」)の2本のロール間を、ラミネート速度5m/min、温度23℃の条件で通した後、折り曲げた部分を顕微鏡で観察(100倍)してクラック発生の有無を観察した。クラックの発生が認められなかった場合を「なし」、クラックの発生が認められた場合を「あり」と評価した。さらに、水蒸気透過率(折り曲げ後の水蒸気透過率)を測定し、下記式により水蒸気透過上昇率を計算した。
基材層としてのポリエチレンテレフタレートフィルム(三菱樹脂社製、「PET38 T-100」、厚さ38μm、以下、「PETフィルム」という。)に、ポリシラザン化合物としてのペルヒドロポリシラザンを主成分とするコーティング剤(クラリアントジャパン社製、「アクアミカNL110-20」)と、粘土鉱物(三洋貿易株式会社製、Dellite67G)が分散した0.2質量%キシレン溶液との混合液を、乾燥後の塗膜の厚みが150nmとなる量塗布し、120℃で2分間加熱して、PETフィルム上に、ペルヒドロポリシラザンと粘土鉱物とを含む層を形成した。粘土鉱物の添加量は全固形分(ポリシラザン化合物と粘土鉱物の合計量)を100質量%として、0.1質量%〔粘土鉱物:ペルヒドロポリシラザン=0.1:99.9(質量比)〕とした。
次に、前記ペルヒドロポリシラザンと粘土鉱物を含む層の表面に、図1に示すプラズマイオン注入装置を用いて、アルゴン(Ar)を以下に示す条件にてプラズマイオン注入して成形体1を作製した。
・プラズマ生成ガス:アルゴン
・ガス流量:100sccm
・Duty比:0.5%
・繰り返し周波数:1000Hz
・印加電圧:-5kV
・RF電源:周波数 13.56MHz、印加電力 1000W
・チャンバー内圧:0.2Pa
・パルス幅:5μsec
・処理時間(イオン注入時間):5分間
・搬送速度:0.2m/min
実施例1において、粘土鉱物の添加量を、全固形分の0.1質量%ではなく1質量%〔粘土鉱物:ペルヒドロポリシラザン=1:99(質量比)〕とした以外は、実施例1と同様にして成形体2を作製した。
実施例1において、粘土鉱物の添加量を、全固形分の0.1質量%ではなく10質量%〔粘土鉱物:ペルヒドロポリシラザン=10:90(質量比)〕とした以外は、実施例1と同様にして成形体3を作製した。
イオン注入を行わない以外は、実施例1と同様にして成形体を作製した。すなわち、PETフィルム上にペルヒドロポリシラザンと粘土鉱物を含む層を形成し、このものを成形体4とした。
PETフィルムに、スパッタリング法により、厚さ60nmの窒化ケイ素(SiN)の膜を形成して、成形体5を作製した。
PETフィルム上にペルヒドロポリシラザンと粘土鉱物とを含む層を形成しない以外は、実施例1と同様にして成形体を作製した。すなわち、PETフィルムの表面にアルゴン(Ar)を実施例1と同様の条件にてプラズマイオン注入して成形体6を作製した。
実施例1において、粘土鉱物を使用しない以外は、実施例1と同様にして成形体7を作製した。
さらに、折り曲げ試験後の水蒸気透過率を測定し、水蒸気透過上昇率を算出した。結果を第1表に示す。
また、折り曲げ試験後においてクラックの発生がみられず、水蒸気透過上昇率も600%以下であり、耐折り曲げ性に優れていることがわかった。
1b、1d・・・フィルム状の成形体
2a、2b・・・回転キャン
3a、3b・・・巻き出しロール
4・・・プラズマ放電用電極
5a、5b・・・巻き取りロール
6a、6b・・・送り出し用ロール
7a、7b・・・パルス電源
9a、9b・・・高電圧パルス
10a、10b・・・ガス導入口
11a、11b・・・チャンバー
13・・・中心軸
15・・・高電圧導入端子
20a、20b・・・ターボ分子ポンプ
Claims (12)
- ポリシラザン化合物と粘土鉱物とを含む層からなり、40℃、相対湿度90%雰囲気下での水蒸気透過率が、6.0g/m2/day以下であることを特徴とする成形体。
- ポリシラザン化合物と粘土鉱物とを含む層にイオンが注入されて得られる層を有することを特徴とする請求項1に記載の成形体。
- 前記イオンが、水素、窒素、酸素、アルゴン、ヘリウム、ネオン、キセノン、クリプトン、ケイ素化合物及び炭化水素からなる群から選ばれる少なくとも一種のガスがイオン化されたものであることを特徴とする請求項2に記載の成形体。
- 前記ポリシラザン化合物と粘土鉱物とを含む層に、プラズマイオン注入法によりイオンが注入されて得られる層を有することを特徴とする請求項2又は3に記載の成形体。
- 前記ポリシラザン化合物が、ペルヒドロポリシラザンであることを特徴とする請求項1又は2に記載の成形体。
- 前記ポリシラザン化合物と粘土鉱物とを含む層中の粘土鉱物の含有量が、ポリシラザン化合物と粘土鉱物の合計量を100質量%として、0.01質量%~10質量%であることを特徴とする請求項1又は2に記載の成形体。
- ポリシラザン化合物と粘土鉱物とを含む層を表面部に有する成形物の、前記ポリシラザン系化合物と粘土鉱物とを含む層の表面部に、イオンを注入する工程を有する請求項2に記載の成形体の製造方法。
- ポリシラザン化合物と粘土鉱物とを含む層を表面部に有する成形物の、前記ポリシラザン系化合物と粘土鉱物とを含む層の表面部に、水素、窒素、酸素、アルゴン、ヘリウム、キセノン、ネオン、クリプトン、ケイ素化合物及び炭化水素からなる群から選ばれる少なくとも一種のガスをイオン注入する工程を有する請求項7に記載の成形体の製造方法。
- 前記イオン注入する工程が、プラズマイオン注入する工程であることを特徴とする請求項7又は8に記載の成形体の製造方法。
- ポリシラザン化合物と粘土鉱物とを含む層を表面部に有する長尺状の成形物を、一定方向に搬送しながら、前記ポリシラザン化合物と粘土鉱物とを含む層に、イオンを注入することを特徴とする請求項2に記載の成形体の製造方法。
- 請求項1又は2に記載の成形体からなる電子デバイス用部材。
- 請求項11に記載の電子デバイス用部材を備える電子デバイス。
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EP2554602B1 (en) | 2015-01-14 |
JP2011213907A (ja) | 2011-10-27 |
CN102834466B (zh) | 2014-10-22 |
KR101476020B1 (ko) | 2014-12-23 |
EP2554602A4 (en) | 2013-10-02 |
JP5697230B2 (ja) | 2015-04-08 |
EP2554602A1 (en) | 2013-02-06 |
CN102834466A (zh) | 2012-12-19 |
TWI478966B (zh) | 2015-04-01 |
US20130068136A1 (en) | 2013-03-21 |
US9540519B2 (en) | 2017-01-10 |
KR20130027471A (ko) | 2013-03-15 |
TW201204772A (en) | 2012-02-01 |
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