WO2013015417A1 - 積層体、ガスバリアフィルム、積層体の製造方法、及び積層体製造装置 - Google Patents
積層体、ガスバリアフィルム、積層体の製造方法、及び積層体製造装置 Download PDFInfo
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- WO2013015417A1 WO2013015417A1 PCT/JP2012/069191 JP2012069191W WO2013015417A1 WO 2013015417 A1 WO2013015417 A1 WO 2013015417A1 JP 2012069191 W JP2012069191 W JP 2012069191W WO 2013015417 A1 WO2013015417 A1 WO 2013015417A1
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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
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/40—Oxides
- C23C16/403—Oxides of aluminium, magnesium or beryllium
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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
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/458—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for supporting substrates in the reaction chamber
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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
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
- C23C16/45544—Atomic layer deposition [ALD] characterized by the apparatus
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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
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
- C23C16/45555—Atomic layer deposition [ALD] applied in non-semiconductor technology
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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
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/54—Apparatus specially adapted for continuous coating
- C23C16/545—Apparatus specially adapted for continuous coating for coating elongated substrates
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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
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/56—After-treatment
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
- Y10T428/2495—Thickness [relative or absolute]
Definitions
- the present invention relates to a laminate in which an atomic layer deposition film is formed on the outer surface of a substrate, a gas barrier film formed by the laminate, a method for producing a laminate in which an atomic layer deposition film is formed on the outer surface of the substrate, and
- the present invention relates to a laminate manufacturing apparatus for manufacturing this laminate.
- CVD chemical vapor deposition
- PVD Physical Vapor Deposition
- PVD Typical examples of PVD include vacuum deposition and sputtering.
- sputtering is generally used to form high-quality thin films with high film quality and excellent film thickness uniformity, although the equipment cost is generally high. Therefore, it is widely applied to display devices such as liquid crystal displays.
- CVD is a method in which a raw material gas is introduced into a vacuum chamber, and one or two or more gases are decomposed or reacted on the substrate by thermal energy to grow a solid thin film. At this time, in order to promote the reaction at the time of film formation or to lower the reaction temperature, there are also those that use plasma and a catalyst (Catalyst) reaction together, such as PECVD (Plasma Enhanced Enhanced CVD), Cat-CVD, being called.
- PECVD Plasma Enhanced Enhanced CVD
- Cat-CVD Cat-CVD
- Such CVD is characterized by few film formation defects and is mainly applied to semiconductor device manufacturing processes such as gate insulating film formation.
- ALD Atomic Layer Deposition
- This ALD method is a method in which a substance adsorbed on the surface is formed one layer at a time by a chemical reaction on the surface, and is classified into the category of CVD.
- the ALD method is distinguished from general CVD by so-called CVD (general CVD) in which a thin film is grown by reacting on a base slope using a single gas or a plurality of gases simultaneously. is there.
- CVD general CVD
- the ALD method alternately uses a precursor (TMA: Tri-Methyl Aluminum) or an active gas called a precursor and a reactive gas (also called a precursor in the ALD method). It is a special film formation method that grows thin films one by one at the atomic level by adsorption on the substrate surface and subsequent chemical reaction.
- a specific film formation method of the ALD method uses a so-called self-limiting effect in which, when the surface is covered with a certain gas in the surface adsorption on the substrate, no further gas adsorption occurs. When only one layer is adsorbed, the unreacted precursor is exhausted. Subsequently, a reactive gas is introduced, and the precursor is oxidized or reduced to obtain only one thin film having a desired composition, and then the reactive gas is exhausted. Such a process is defined as one cycle, and this cycle is repeated to grow a thin film. Therefore, in the ALD method, the thin film grows two-dimensionally.
- the ALD method is characterized in that it has fewer film-forming defects as compared with the conventional vacuum deposition method, sputtering, and the like, as well as general CVD. Therefore, it is expected to be applied to a wide range of fields such as the packaging field for foods and pharmaceuticals and the electronic parts field.
- the ALD method includes a method of using plasma to activate the reaction in the step of decomposing the second precursor and reacting with the first precursor adsorbed on the substrate.
- This method is called plasma activated ALD (PEALD: Plasma Enhanced ALD) or simply plasma ALD.
- the ALD method is capable of obtaining high-quality and high-density film formation, and is therefore being applied in the field of semiconductors such as gate insulating films. ITRS (International Technology Roadmap for Semiconductors) also describes them. .
- the ALD method has a characteristic that there is no oblique effect (a phenomenon in which sputtering particles are incident on the substrate surface obliquely to cause film formation variation) compared to other film formation methods, so that there is no gap for gas to enter. If so, film formation is possible. Therefore, the ALD method can be applied to MEMS (Micro Electro Mechanical Systems) related to coating of 3D structures as well as coatings of lines and holes on a substrate having a high aspect ratio with a large depth to width ratio. Expected.
- MEMS Micro Electro Mechanical Systems
- the ALD method also has drawbacks. That is, in order to execute the ALD method, a special material is used and the cost is increased due to this, but the biggest drawback is that the film forming speed is low. For example, the film formation rate is about 5 to 10 times slower than a film formation method such as normal vacuum deposition or sputtering.
- the target for forming a thin film by the ALD method using the film forming method as described above is a small plate-like substrate such as a wafer or a photomask, or a substrate having a large area and no flexibility such as a glass plate. Or a substrate having a large area and flexibility such as a film.
- mass production facilities for forming thin films on these substrates have been proposed and put to practical use by various substrate handling methods depending on cost, ease of handling, film formation quality, etc. ing.
- a single substrate is supplied to a film forming apparatus to form a film, and then the wafer is replaced with the next substrate to form a film again, or a plurality of substrates are set together and all wafers are set.
- a batch type film forming apparatus for performing the same film forming.
- an in-line type film forming apparatus that performs film formation at the same time while sequentially transporting the substrate to a part serving as a film formation source.
- a so-called roll-to-roll coating film forming apparatus in which a flexible substrate is mainly unwound from a roll and film is formed while being conveyed, and the substrate is wound on another roll.
- the latter includes not only a flexible substrate but also a flexible coating sheet that can continuously convey a substrate to be deposited, or a web coating deposition apparatus that continuously deposits on a tray that is partially flexible.
- the film forming method and the substrate handling method using any of the film forming apparatuses a combination of film forming apparatuses having the fastest film forming speed is adopted in view of cost, quality, and ease of handling.
- a technique for forming a gas permeable barrier layer on a plastic substrate or a glass substrate by performing atomic layer deposition by the ALD method is disclosed (for example, see Patent Document 1).
- a light-emitting polymer is mounted on a flexible and light-transmitting plastic substrate, and atomic layer deposition is performed on the surface and side surfaces of the light-emitting polymer by ALD (top coating is applied). ).
- top coating is applied.
- a technique related to a barrier layer processing apparatus for forming a barrier layer on a substrate using an ALD method is disclosed (for example, see Patent Document 2).
- an atomic layer deposition film is formed on the surface of a substrate mounted on the conveyor in a flow in which a film-like substrate is mounted on the conveyor and moved through the vacuum chamber.
- a film having a high gas barrier property is produced at high speed by winding a film-like substrate on which an atomic layer deposition film is formed on a winding drum.
- laminates in which an atomic layer deposition film is provided on the outer surface of a substrate (substrate) by the ALD method are widely known, and these laminates are preferable for gas barrier films having gas barrier properties. It is used in.
- the atomic layer deposited film may be easily damaged by an external force or the like.
- a through hole extending in the film thickness direction of the atomic layer deposition film may be generated depending on the size of the scratch.
- gas enters and exits through the through-hole, so that the gas barrier property is deteriorated.
- the gas barrier in the case of manufacturing a laminate having an atomic layer deposition film that is easily damaged in this way, after the atomic layer deposition film is formed, the gas barrier must be used unless the production line is such that the rigid body does not contact the atomic layer deposition film. It will be a factor that decreases the performance. For this reason, for example, in the case of producing a film-like laminate (that is, a gas barrier film), when the gas barrier film is wound into a roll with a take-up roller, the atomic layer deposition film on the surface of the substrate is damaged, and the gas barrier property There is a risk of lowering. That is, in the manufacturing process of a laminated body, winding and transporting and storing a gas barrier film in a roll form has a problem from the viewpoint of maintaining high gas barrier properties.
- a film-like laminate that is, a gas barrier film
- the present invention has been made in view of such circumstances, and a laminated body in which an atomic layer deposition film formed on the outer surface of a base material is not easily damaged by an external force and has an improved gas barrier property, and the laminated body.
- An object of the present invention is to provide a gas barrier film formed by the method, a method for producing the laminate, and a laminate production apparatus for producing the laminate.
- a base material an atomic layer deposition film formed along an outer surface of the base material, and a film having a mechanical strength higher than that of the atomic layer deposition film.
- An overcoat layer covering the laminate.
- a base material an atomic layer deposition film formed along an outer surface of the base material, a mechanical strength equivalent to that of the atomic layer deposition film, and the atomic layer deposition film.
- an overcoat layer that covers the atomic layer deposition film with a thicker film.
- the overcoat layer may be formed of an aqueous barrier coat.
- the aqueous barrier coat may have at least one of an OH group and a COOH group.
- the overcoat layer may contain an inorganic substance.
- the laminates of the first and second aspects further include an undercoat layer in which an inorganic substance that binds to the atomic layer deposition film is dispersed between the base material and the atomic layer deposition film. May be.
- the laminates of the first and second aspects further include an undercoat layer containing an organic polymer that binds to the atomic layer deposition film between the base material and the atomic layer deposition film.
- An undercoat layer containing an organic polymer that binds to the atomic layer deposition film between the base material and the atomic layer deposition film is characterized by the above.
- a third aspect of the present invention is a gas barrier film having the laminate according to the first aspect or the second aspect, wherein the laminate is formed in a film shape.
- the atomic layer in the first step of forming a thin-film atomic layer deposition film along the outer surface of the substrate, and in-line in a step in series with the first step, the atomic layer A second step of forming an overcoat layer having a mechanical strength higher than that of the atomic layer deposition film along the outer surface of the deposition film to generate a laminate, and the overcoat layer formed in the second step And a third step of storing the laminate so that the laminate contacts the rigid body.
- the atomic layer A second layer is formed by forming an overcoat layer with a film having a mechanical strength equivalent to that of the atomic layer deposition film and having a thickness larger than that of the atomic layer deposition film along the outer surface of the deposition film.
- a third step of storing the laminate so that the overcoat layer formed in the second step is in contact with the rigid body.
- the sixth aspect of the present invention is formed by the first step of forming an undercoat layer containing at least one of an inorganic substance and an organic polymer along the outer surface of the substrate, and the first step.
- the seventh aspect of the present invention is formed by the first step of forming an undercoat layer containing at least one of an inorganic substance and an organic polymer along the outer surface of the substrate, and the first step.
- the rigid body is a winding roller, and after the third step or the third step, the laminated body may be wound and stored in contact with the winding roller in a roll shape. Good.
- the overcoat layer may be formed by forming an acrylic film on the outer surface of the atomic layer deposition film by a flash vapor deposition method.
- the overcoat layer may be formed by a chemical vapor deposition method.
- a laminate in which an atomic layer deposition film is formed on a thin plate, a film, or a belt-like substrate formed in a film shape is conveyed by a roll-to-roll method in an in-line process.
- An apparatus for manufacturing a laminated body comprising: a support that supports one surface in the thickness direction of the substrate; a transport mechanism that transports the substrate in one direction along an outer surface of the support; and the support Between the outer surface of the substrate and the ALD film forming portion for forming the atomic layer deposition film on the other surface in the thickness direction of the substrate, and the transport direction of the substrate In FIG.
- an overcoat layer having a mechanical strength stronger than the atomic layer deposition film or thicker than the atomic layer deposition film is formed on the surface of the atomic layer deposition film.
- a laminate manufacturing apparatus characterized by comprising a winding mechanism for winding into a roll of the laminate as the contact surface of the overcoat layer.
- the overcoat forming part may form the overcoat layer by flash vapor deposition or chemical vapor deposition.
- the laminate manufacturing apparatus further includes an undercoat forming unit disposed upstream of the ALD film forming unit in the transport direction of the base material, and the undercoat forming unit includes the atoms.
- An undercoat layer having a binding site that binds to the layer deposition film may be formed on the outer surface of the substrate.
- the laminate and gas barrier film of the present invention have high gas barrier properties. Moreover, the manufacturing method of a laminated body and the laminated body manufacturing apparatus of this invention can manufacture a laminated body with high gas barrier property easily.
- the laminate according to the embodiment of the present invention basically has a configuration in which an atomic layer deposition film is formed on the surface of a base material, and an overcoat layer is formed so as to cover the surface of the atomic layer deposition film. It has become.
- This overcoat layer may be a layer having any characteristics as long as it does not impair the characteristics of the substrate and the ALD film.
- the magnitude of the external force required to generate a through hole extending in the film thickness direction in the overcoat layer is greater than the magnitude of the external force required to generate a through hole extending in the film thickness direction in the atomic layer deposition film. is required.
- the overcoat layer needs to be a film having higher mechanical strength than the atomic layer deposition film.
- the overcoat layer needs to be a layer formed with a thickness larger than that of the atomic layer deposition film.
- the laminated body which concerns on embodiment of this invention may be provided with the undercoat layer between the base material and the atomic layer deposition film. That is, an undercoat layer is formed on the surface of the substrate, an atomic layer deposition film is formed on the surface of the undercoat layer, and an overcoat layer is formed so as to cover the surface of the atomic layer deposition film. May be.
- FIG. 1 is a cross-sectional view showing the configuration of the laminate according to the first embodiment of the present invention.
- a laminate 1a according to the first embodiment includes a base material 2 formed of a polymer material, and an atomic layer deposition film (hereinafter referred to as an ALD film) formed in a film shape on the surface of the base material 2. 4) and an overcoat layer (hereinafter referred to as OC layer) 5 that covers the ALD film 4 with a film having higher mechanical strength than the ALD film 4.
- the OC layer 5 has the same mechanical strength as the ALD film 4 and may cover the ALD film 4 with a film thicker than the ALD film 4.
- the OC layer 5 having a mechanical strength higher than that of the ALD film 4 is formed on the surface of the ALD film 4, an external force acting to the extent that the ALD film 4 is damaged and a through hole is formed in the film thickness direction is applied.
- the OC layer 5 is not likely to have a through hole in the film thickness direction with such an external force. Therefore, by forming the OC layer 5 on the surface of the ALD film 4, the gas barrier property of the stacked body 1a can be enhanced.
- the OC layer 5 having the same mechanical strength as that of the ALD film 4 is formed, if the OC layer 5 is formed with a film thicker than the ALD film 4, the ALD film 4 is damaged. Even if a through-hole is generated in the film thickness direction, the OC layer 5 is not likely to have a through-hole in the film thickness direction with such an external force. Therefore, the gas barrier property of the laminated body 1a can be improved.
- the OC layer 5 is formed of an aqueous barrier coat, and the aqueous barrier coat has a functional group having an OH group or a COOH group.
- the OC layer 5 may contain an inorganic substance.
- Water-based barrier coats are water-based organic polymers, hydrolyzed polymers composed of organometallic compounds such as metal alkoxides and silane coupling agents, and coat films having a barrier property composed of composites thereof. Examples of the polymer include polyvinyl alcohol, polyacrylic acid, and polyethyleneimine.
- R1 metal alkoxide
- Rl and R2 are organic groups having 1 to 8 carbon atoms, and M is a metal atom.
- the metal atom M is Si, Ti, Al, Zr, or the like.
- Examples of the metal atom M represented by Rl (Si-OR2) in Si include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraptoxysilane, methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, Examples include dimethyldiethoxysilane.
- Examples of the metal atom M in which Zr is represented by R1 include tetramethoxyzirconium, tetraethoxyzirconium, tetraisopropoxyzirconium, and tetraptoxyzirconium.
- Examples of the metal atom M that is Ti and represented by R1 include tetramethoxytitanium, tetraethoxytitanium, tetraisopropoxytitanium, and tetrapoxytitanium.
- Examples of the metal atom M that is Al and represented by R1 include tetramethoxyaluminum, tetraethoxyaluminum, tetraisopropoxyaluminum, and tetraptoxyaluminum.
- a material candidate in the case of using an inorganic substance as an inorganic particle has a particle size larger than that of a extender candidate, for example, kaolinite, which is a kind of viscosity mineral, halloysite, calcium carbonate, anhydrous silica. Examples include acid, hydrous silicic acid, and alumina.
- artificial clay When the inorganic substance is a layered compound, artificial clay, fluorine phlogopite, fluorine tetrasilicon mica, teniolite, fluorine vermiculite, fluorine hectorite, hectorite, sapolite, stevensite, montmorillonite, beidellite, kaolinite, or flybon Examples include tight.
- layered clay minerals include pyroferrite, talc, montmorillonite (overlapping with artificial clay), beidellite, nontronite, saponite, vermiculite, sericite, sea green stone, ceradonite, kaolinite, nacrite, dacite, halo.
- An inorganic substance such as site, antigolite, chrysotile, amesite, chroniteite, chamosite, chlorite, alevaldite, corrensite, or tosudite can also be used as a layered compound.
- the extender pigment other inorganic particles (spherical particles), a polycrystalline compound, zirconia, metal oxides such as titania, barium titanate, the general chemical formula, such as strontium titanate and the like MM'O X
- metal oxide containing two or more metal atoms M, M ′, etc.
- FIG. 2 is a cross-sectional view showing the configuration of the laminate according to the second embodiment of the present invention.
- the laminate 1b of the second embodiment is different from the laminate 1a of the first embodiment shown in FIG. 1 in that an undercoat layer (hereinafter, referred to as an undercoat layer) is formed between the substrate 2 and the ALD film 4. (Referred to as UC layer) 3 is interposed.
- the UC layer 3 may contain an inorganic substance or may contain an organic polymer.
- the laminated body 1b includes a base material 2 formed of a polymer material, a film-like or film-like UC layer 3 formed on the surface of the base material 2, and a thickness direction of both sides of the UC layer 3.
- the ALD film 4 is formed on the surface opposite to the surface in contact with the material 2, and the OC layer 5 covers the ALD film 4 with a film having higher mechanical strength than the ALD film 4.
- the OC layer 5 has the same mechanical strength as the ALD film 4 and may cover the ALD film 4 with a film thicker than the ALD film 4.
- the UC layer 3 may contain an inorganic substance and may contain an organic polymer, both will be described.
- the laminate 1 b includes a UC layer 3 in which an inorganic substance is dispersed between the base material 2 and the ALD film 4, and the OC layer 5 is formed on the surface of the ALD film 4.
- the precursor of the ALD film 4 is a gaseous substance and has a characteristic that it easily binds to an inorganic substance exposed on the surface of the UC layer 3.
- the precursors of the ALD film 4 bonded to the inorganic substances are bonded to each other.
- a two-dimensional ALD film 4 growing in the plane direction of the UC layer 3 is generated.
- a gap that allows gas to permeate in the film thickness direction of the laminated body 1b is less likely to be generated, and a laminated body 1b having a high gas barrier property can be realized.
- a UC layer 3 containing an inorganic substance is provided on a polymer base 2.
- a UC layer 3 containing an inorganic substance is provided.
- the inorganic substance adsorption sites at a high density are used. In this way, by providing the UC layer 3 containing the inorganic substance (inorganic compound) on the polymer substrate 2, the gas containing the precursor cannot pass through the inorganic substance of the UC layer 3.
- the laminated body 1b according to the second embodiment includes a base material 2 formed of a polymer material and a film or film shape formed on the surface of the base material 2, as shown in FIG.
- the UC layer 3 includes an ALD film 4 formed on a surface opposite to the surface in contact with the substrate 2 among both surfaces in the thickness direction of the UC layer 3, and an OC layer 5 formed on the ALD film 4. ing.
- the UC layer 3 has a configuration in which an inorganic substance (inorganic material) is added to a binder. That is, the precursor of the ALD film 4 is formed in a film shape so that the ALD film 4 covers the UC layer 3 by being bonded to an inorganic substance contained in the UC layer 3.
- the UC layer 3 is formed of a binder and an inorganic substance (inorganic material).
- an inorganic substance has a small free volume unlike a polymer.
- the inorganic substance does not have glass point transfer like a polymer, the characteristics do not change even in a high temperature process. That is, in the polymer, the non-crystalline part starts the Brownian motion above the glass point transfer, and the gas diffusion rate in the free volume increases, but the inorganic substance does not have such a phenomenon due to the glass point transfer.
- the inorganic substance used for the UC layer 3 is a layered compound. Therefore, the inorganic substance of such a layered compound is oriented almost parallel to the coating surface of the substrate 2. In addition, all gases including the precursor gas in the ALD method cannot diffuse inside the layered compound inorganic substance.
- the surface of the UC layer 3 is etched so that the surface of the inorganic substance of the layered compound is exposed. That is, the surface of the UC layer 3 is etched by performing plasma treatment in order to introduce a desired functional group into the surface of the inorganic substance of the layered compound in the UC layer 3 exposed on the substrate 2. As a result, the precursor of the ALD film 4 is easily bonded to the inorganic material of the UC layer 3.
- the UC layer 3 having the above-described characteristics is provided on the surface of the polymer base material 2, precursor adsorption sites are arranged on the surface of the base material 2 at a high density.
- the inorganic substance of the layered compound in the UC layer 3 is arranged in parallel to the surface of the substrate 2. Therefore, since the UC layer 3 covers the surface area of the substrate 2 almost uniformly, the adsorption sites are two-dimensionally arranged, and the two-dimensional growth of the ALD film 4 is promoted. Further, since the inorganic substance portion of the layered compound in the UC layer 3 does not undergo glass transition unlike a general plastic polymer even when the process temperature of ALD for forming the ALD film 4 is high, stable ALD Film growth of the film 4 is performed.
- the binder of the UC layer 3 may be any of an organic binder, an inorganic binder, and a hybrid binder of an organic / inorganic mixture.
- the precursor of the ALD film 4 is bonded to the outer surface of the inorganic substance.
- the bonding strength with the precursor of the ALD film 4 can be increased by making the inorganic substance into a particulate or layered structure.
- an optimum bonding force is obtained by making the inorganic substance into a sol or gel polymer.
- the laminated body 1b of this embodiment since the surface where the functional groups are arranged at high density is formed, not only the ALD method but also other thin film growth methods (for example, vacuum deposition, sputtering, CVD, etc.) ), It can be expected to form a dense thin film by a growth mode with a high nuclear density.
- the inorganic compound (inorganic substance) used for the UC layer 3 will be described in detail.
- the radio material is selected with the following points in mind. That is, as an element for selecting an inorganic substance composed of inorganic particles, the shape of the inorganic particles includes nearly spherical particles and plate-like particles, and any particle can be used.
- the particle size (particle diameter) of the inorganic particles is 1 ⁇ m or less, preferably 0.1 ⁇ m or less, so that the smoothness of the substrate 2 is not affected.
- the size of the inorganic particles is sufficiently smaller than the wavelength of visible light so as to avoid the influence on the optical characteristics of the UC layer 3 (that is, light transmittance, haze: ratio of diffuse transmitted light to total transmitted light) as much as possible. Particle size is desirable.
- coloring is not preferable from the viewpoint of transparent barrier coating.
- it is necessary to match the refractive index of the binder of the UC layer 3 and the inorganic particles. That is, in the UC layer 3, when the refractive index of the binder and the refractive index of the inorganic particles are significantly different, reflection at the interface of the UC layer 3 is increased. As a result, the light transmittance in the UC layer 3 is reduced and haze (cloudiness) is increased.
- the dispersibility of the inorganic particles secondary agglomeration hardly occurs because of good dispersion in the binder. Further, when the inorganic substance is a layered compound, the affinity (intercalation: chemical bond) with the binder is good.
- the laminate 1b when the laminate 1b is used as a solar cell, a usage period of 20 to 30 years is assumed, so that the laminate 1b is used for a long time at high temperature / high humidity and extremely low temperature. Even inorganic materials need to be chemically stable. In addition, about the safety
- inorganic substances added to the UC layer 3 will be described.
- inorganic substance used for the UC layer 3 is inorganic particles, for example, halloysite, calcium carbonate, silicic anhydride having a particle size larger than that of extender candidates, for example, kaolinite which is a kind of viscosity mineral , Hydrous silicic acid, or alumina.
- artificial clay When the inorganic substance is a layered compound, artificial clay, fluorine phlogopite, fluorine tetrasilicon mica, teniolite, fluorine vermiculite, fluorine hectorite, hectorite, sapolite, stevensite, montmorillonite, beidellite, kaolinite, or flybon Examples include tight.
- layered clay minerals include pyroferrite, talc, montmorillonite (overlapping with artificial clay), beidellite, nontronite, saponite, vermiculite, sericite, sea green stone, ceradonite, kaolinite, nacrite, dacite, halo.
- An inorganic substance such as site, antigolite, chrysotile, amesite, chroniteite, chamosite, chlorite, alevaldite, corrensite, or tosudite can also be used as a layered compound.
- the extender pigment other inorganic particles (spherical particles), a polycrystalline compound, zirconia, metal oxides such as titania, barium titanate, the general chemical formula, such as strontium titanate and the like MM'O X
- metal oxide containing two or more metal atoms M, M ′, etc.
- the laminate 1 b includes a UC layer 3 containing an organic polymer between the base material 2 and the ALD film 4, and the OC layer 5 is formed on the surface of the ALD film 4.
- the UC layer 3 is a layer containing an organic polymer, and this organic polymer has a binding site to which the precursor of the ALD film 4 is bonded. That is, the organic polymer contained in the UC layer 3 has a large number of functional groups as binding sites that are easily bonded to the precursor of the ALD film 4. Accordingly, the precursors bonded to each functional group of the organic polymer are bonded to each other.
- an inorganic substance may be dispersed in the UC layer 3. That is, by adding an inorganic substance to the UC layer 3, the organic polymer and the inorganic substance can be combined to further improve the adsorption density of the precursor of the ALD film 4.
- a UC layer 3 containing an organic polymer may be provided on the polymer substrate 2.
- the UC layer 3 contains an organic polymer material and secures an adsorption site for the precursor of the ALD film 4. That is, the organic polymer contained in the UC layer 3 has a functional group that can easily adsorb the precursor of the ALD film 4. Therefore, when the precursor of the ALD film 4 is bonded to the functional group of the organic polymer contained in the UC layer 3, the ALD film is formed in a film shape so as to cover the UC layer 3.
- the laminated body 1 b includes a base material 2 formed of a polymer material, a film-like or film-like UC layer 3 formed on the surface of the base material 2, and a UC layer 3.
- An ALD film 4 formed on a surface opposite to the surface in contact with the substrate 2 among both surfaces in the thickness direction, and an OC layer 5 covering the surface of the ALD film 4 are provided.
- the UC layer 3 contains an organic polymer material and secures an adsorption site for the precursor of the ALD film 4.
- the organic polymer contained in the UC layer 3 has a functional group that can easily adsorb the precursor of the ALD film 4. Therefore, when the precursor of the ALD film 4 is bonded to the functional group of the organic polymer contained in the UC layer 3, the ALD film is formed in a film shape so as to cover the UC layer 3.
- the adsorption site on the base material 2 with the organic polymer contained in the UC layer 3 it is necessary to select an organic polymer having a functional group that can easily adsorb the precursor of the ALD film 4. is there. Moreover, it is necessary to select an organic polymer having a high functional group density. Furthermore, it is desirable to modify the surface of the organic polymer to increase the density of functional groups of the organic polymer by subjecting the substrate 2 to surface treatment by plasma treatment or hydrolysis treatment. At this time, the adsorption density of the precursor can be further increased by adding an inorganic compound to the organic polymer.
- the UC layer 3 needs to be selected from those containing an organic polymer having a functional group that can easily adsorb the precursor of the ALD film 4.
- the functional group is an amide group, and the precursor is very easily adsorbed. Therefore, nylon-6 is an organic material used for the UC layer 3. Desirable as a polymer material.
- polypropylene (PP) having a methyl group that is difficult to adsorb the precursor.
- the ALD film precursor when PP having a functional group (methyl group) that is difficult for the precursor of the ALD film 4 to be adsorbed is used for the undercoat, the ALD film precursor has a low adsorptivity to PP, and therefore, the ALD at the boundary with the polymer. The film becomes sparse and the gas barrier property is lowered.
- nylon-6 having a functional group (amide group) that is easily adsorbed by the precursor of the ALD film is used for the undercoat, the adsorbability of the precursor of the ALD film to nylon-6 is high. Since the density of the ALD film at the boundary is increased, the gas barrier property is improved.
- the organic polymer material having a functional group on which the precursor of the ALD film 4 is easily adsorbed includes a urethane resin having an isocyanate group, a polyimide resin having an imide group, and a polyether sulfone having a sulfone group (PES). And polyethylene terephthalate (PET) having an ester group.
- the functional group of the organic polymer contained in the UC layer 3 preferably has an O atom or an N atom.
- the functional group having an O atom include OH group, COOH group, COOR group, COR group, NCO group, and SO 3 group.
- the functional group having an N atom is an NH x group (X is an integer).
- the organic polymer used for the UC layer 3 is classified into an aqueous type and a solvent type depending on the solvent used.
- Examples of the water-based organic polymer include polyvinyl alcohol and polyethyleneimine.
- Examples of the solvent-based organic polymer include acrylic ester, urethane acrylic, polyester acrylic, and polyether acrylic.
- Organic Polymer of O Atom-Containing Resin Preferred materials for the organic polymer of O atom-containing resin are as follows.
- the hydroxyl group (OH) -containing resin include polyvinyl alcohol, phenol resin, and polysaccharides.
- the polysaccharide includes cellulose derivatives such as cellulose, hydroxymethylcellulose, hydroxyethylcellulose, and carboxymethylcellulose, chitin, chitosan, and the like.
- COOH carbonyl group
- a carboxyvinyl polymer is also a preferable material.
- O atom-containing resins include polyketone, polyetherketone, polyetheretherketone, aliphatic polyketone and the like of ketone group (CO) -containing resins.
- ester group (COO) -containing resins such as polyester resin, polycarbonate resin, liquid crystal polymer, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), boribylene naphthalate (PBN), polytrile Methylene terephthalate (PTT) or the like can also be used.
- an epoxy resin or an acrylic resin containing the above functional group may be used.
- organic polymer of N atom-containing resin Preferred materials for the organic polymer of N atom-containing resin are as follows.
- the imide group (CONHCO) -containing resin include polyimide, polyetherimide, polyamideimide, alicyclic polyimide, and solvent-soluble polyimide.
- alicyclic polyimides aromatic polyimides are usually obtained from aromatic tetracarboxylic acid anhydrides and aromatic diamines, but since they are not transparent, acid dianhydrides or diamines are used to make polyimides transparent. It is also possible to substitute an aliphatic group or an alicyclic group.
- Examples of the alicyclic carboxylic acid include 1,2,4,5-cyclohexanetetracarboxylic acid and 1,2,4,5-cyclopentanetetracarboxylic dianhydride.
- examples of the solvent-soluble polyimide include ⁇ -ptyrolactone, N, N-dimethylacetamide, and N-methyl-2-pyrrolidone.
- amide group (NHCO) -containing resin such as nylon-6, nylon-6,6, metaxylenediamine-adipic acid condensation polymer, polymethylmethacrylamide, etc.
- urethane resins such as isocyanate group (NHCOO) -containing resins.
- Urethane resin can also be used as an adhesion layer.
- amino group (NH) -containing resins can also be used.
- Organic Polymer of S Atom-Containing Resin Materials that can be used as the organic polymer of S atom-containing resin include the following. That is, examples thereof include polyethersulfone (PES), polysulfone (PSF), polyphenylsulfone (PPS), and the like, which are sulfonyl group (SO 2 ) -containing resins. Among these, PES and PSF are materials having high heat resistance.
- polymer alloys, polybutylene terephthalate polymer alloys, polyphenylene sulfide polymer alloys, and the like can also be used as the organic polymer. In the polymer alloy, the above polymer may be combined with a polymer (alloy, blend, or composite) as necessary.
- Example Next, specific examples of the laminate including the overcoat layer realized based on the above embodiment will be described.
- a general film forming method of a gas barrier layer made of an ALD film will be described.
- a method for forming an ALD film when a UC layer is formed on the surface of a substrate will be described.
- the upper surface having a UC layer on or polymer substrate of the polymer substrate was formed an Al 2 O 3 film by atomic layer deposition (ALD) method.
- the source gas was trimethylaluminum (TMA).
- TMA trimethylaluminum
- the treatment pressure at that time was 10 to 50 Pa.
- a plasma gas excitation power source was a 13.56 MHz power source, and plasma discharge was performed in an ICP (Inductively Couple Plasma) mode.
- the supply time of each gas was set to 60 msec for TMA and process gas, 10 sec for purge gas, and 5 sec for reactive gas / discharge gas.
- plasma discharge was generated in the ICP mode.
- the output power of the plasma discharge at this time was 250 watts.
- purge gases O 2 and N 2 were supplied for 10 seconds.
- the film forming temperature at this time was 90 ° C.
- the deposition rate of Al 2 O 3 under the above cycle conditions was as follows. That is, since the unit film formation rate is 1.4 to 1.5 liters / cycle, when the film formation process of 70 cycles is performed to form a film with a film thickness of 10 nm, the total film formation time is about 30 min. It became.
- the raw material gas was titanium tetrachloride (TiCl 4 ).
- the treatment pressure at that time was 10 to 50 Pa.
- the plasma gas excitation power source was a 13.56 MHz power source, and plasma discharge was performed in the ICP mode.
- the supply time of each gas was 60 msec for TiCl 4 and the process gas, 10 sec for the purge gas, and 3 sec for the reactive gas / discharge gas. Then, plasma discharge was generated in the ICP mode at the same time as the reaction gas and discharge gas were supplied. The output power of the plasma discharge at this time was 250 watts. Further, as gas purge after plasma discharge, purge gases O 2 and N 2 were supplied for 10 seconds. The film forming temperature at this time was 90 ° C.
- the film formation rate of TiO 2 under the above cycle conditions was as follows. That is, since the unit film forming speed is about 0.9 mm / cycle, when the film forming process of 110 cycles was performed to form a film with a film thickness of 10 nm, the total time of the film forming process was about 43 min. .
- FIG. 3 is a diagram comparing the water vapor transmission rate (WVTR) of the laminate of this example having an OC layer and the laminate of a comparative example without an OC layer. Therefore, the superiority of each embodiment will be described with reference to FIG.
- Example 1 As shown in FIG. 3, in Example 1, an AlO x thin film was directly formed as an ALD film on a 100 ⁇ m thick polyethylene terephthalate (PET) polymer substrate without forming a UC layer.
- the AlO x thin film (ALD film) was formed with a thickness of 10 nm by plasma treatment using TMA (trimethylaluminum) as a raw material.
- an OC layer was formed on the surface of the ALD film by an organic / inorganic composite coating film.
- the raw materials for the OC layer (organic-inorganic composite coating film) at this time are hydrolyzed TEOS (tetraethoxysilane) and PAV (polyvinyl alcohol).
- the composition ratio of SiO 2 and PVA is 70% to 30%.
- a 5% solids solution was prepared as a coating agent, and a film thickness of 0.5 ⁇ m was formed by bar coating under processing conditions of 120 ° C. for 1 min.
- the gas barrier property was measured.
- the initial measured value of the water vapor transmission rate (WVTR) is 7.5 ⁇ 10 ⁇ 3 [g / m 2 / day]
- the WVTR after the cooling test is 9.8 ⁇ 10 ⁇ 3 [g / m 2 / day]. That is, when the laminated body of Example 1 was subjected to a thermal test, the WVTR increased by about 30%.
- the thermal test was a thermal shock test (conforming to JIS C 0025), and was performed under the conditions of ⁇ 30 ° C. (30 min) / 85 ° C. (30 min) and 50 cycles.
- the cold test of the Example and comparative example which are mentioned later was done on the same conditions.
- Example 2 As shown in FIG. 3, in Example 2, a UC layer was formed on a 100 ⁇ m thick PET polymer substrate using a urethane coating agent.
- the urethane coating agent for this UC layer is a commercially available acrylic polyol, HEMA (2-hydroxymethyl methacrylate) / MMA (methyl methacrylate) copolymer, HAMA 30 mol% molecular weight 10,000, TDI (toluene diisocyanate) adduct curing.
- the agent was used as a raw material.
- a 3% solid content solution was prepared as a coating agent, and a film thickness of 0.1 ⁇ m was formed by bar coating under processing conditions of 120 ° C. for 1 min.
- AlO x thin film was formed as an ALD film on the UC layer.
- the AlO x thin film was formed with a thickness of 10 nm by plasma treatment using TMA as a raw material.
- an OC layer was formed on the surface of the ALD film by an organic / inorganic composite coating film.
- the raw materials of the OC layer (organic / inorganic composite coating film) at this time are hydrolysis TEOS, silane compound, and PAV, and the composition ratio of SiO 2 and PVA is 85% to 15%.
- a 5% solids solution was prepared as a coating agent, and a film thickness of 0.5 ⁇ m was formed by bar coating under processing conditions of 120 ° C. for 1 min.
- the gas barrier property was measured.
- the initial measured value of WVTR was 3.1 ⁇ 10 ⁇ 3 [g / m 2 / day]
- the WVTR after the cooling test was 6.4 ⁇ 10 ⁇ 3 [g / m 2 / day]. It was. That is, when the laminated body of Example 2 was subjected to a cooling test, the WVTR increased about twice.
- Example 3 As shown in FIG. 3, in Example 3, a UC layer was formed on a 100 ⁇ m thick PET polymer substrate using an inorganic-containing urethane coating agent.
- the urethane-based coating agent for the UC layer was made from commercially available acrylic polyol, HEMA / MMA copolymer, HAMA 30 mol% molecular weight 10,000, TDI adduct curing agent, and organic bentonite.
- a 3% solids solution was prepared as a coating agent, and a film thickness of 1 ⁇ m was formed by bar coating under processing conditions of 120 ° C. for 1 min.
- AlO x thin film was formed as an ALD film on the UC layer.
- the AlO x thin film was formed to a thickness of 10 nm by plasma treatment using TMA as a raw material.
- an OC layer was formed on the surface of the ALD film with an organic-inorganic composite coating film.
- the raw materials of the OC layer (organic-inorganic composite coating film) at this time are hydrolysis TEOS, silane compound, PAV, and organic bentonite having an average particle size of 0.5 ⁇ m, and the composition ratio of SiO 2 and PVA is 85% to 15%. %.
- a 5% solids solution was prepared as a coating agent, and a film thickness of 0.5 ⁇ m was formed by bar coating under processing conditions of 120 ° C. for 1 min.
- the gas barrier property was measured.
- the initial measured value of WVTR was 0.8 ⁇ 10 ⁇ 3 [g / m 2 / day]
- the WVTR after the thermal test was 2.1 ⁇ 10 ⁇ 3 [g / m 2 / day]. It was. That is, when the laminated body of Example 3 was subjected to a cooling test, the WVTR increased by about 2.5 times.
- Example 4 As shown in Example 4 of FIG. 3, in Example 4, a UC layer was formed on a PET polymer substrate having a thickness of 100 ⁇ m using an inorganic-containing urethane-based coating agent.
- the inorganic-containing urethane-based coating agent for the UC layer was made from commercially available acrylic polyol, HEMA / MMA copolymer, HAMA 30 mol% molecular weight 10,000, TDI adduct curing agent, and TiO 2 ultrafine particle sol.
- a 3% solid content solution was prepared as a coating agent, and a film thickness of 0.1 ⁇ m was formed by bar coating under processing conditions of 120 ° C. for 1 min.
- a TiO x thin film was formed as an ALD film on the UC layer.
- the TiO x thin film was formed by using a TiCl 4 raw material and having a thickness of 10 nm by plasma treatment.
- an OC layer was formed on the surface of the ALD film by an organic / inorganic composite coating film.
- the raw materials of the OC layer (organic-inorganic composite coating film) at this time are hydrolyzed TEOS, silane compound, PAV, and TiO 2 fine particles having an average particle diameter of 20 nm, and the composition ratio of SiO 2 and PVA is 85% 15%.
- a 5% solids solution was prepared as a coating agent, and a film thickness of 0.5 ⁇ m was formed by bar coating under processing conditions of 120 ° C. for 1 min.
- the gas barrier property was measured.
- the initial measured value of WVTR was 1.9 ⁇ 10 ⁇ 3 [g / m 2 / day]
- the WVTR after the thermal test was 2.1 ⁇ 10 ⁇ 3 [g / m 2 / day]. It was. That is, when the laminated body of Example 4 was subjected to a cooling test, the WVTR increased by about 10%.
- Comparative example 1 As shown in FIG. 3, in Comparative Example 1, a stretched PET film (100 ⁇ m thick) was prepared as a polymer substrate. Then, an AlO x film was formed as an ALD film without providing a UC layer on the surface of the substrate. The AlO x thin film was formed to a thickness of 10 nm by plasma treatment using TMA as a raw material. An OC layer is not provided on the surface of the ALD film.
- the gas barrier property was measured.
- the initial measured value of WVTR was 8.5 ⁇ 10 ⁇ 3 [g / m 2 / day]
- the WVTR after the cooling test was 120.2 ⁇ 10 ⁇ 3 [g / m 2 / day]. It was. That is, when the laminated body of Comparative Example 1 was subjected to a cooling test, the WVTR increased by 14 times or more.
- Comparative Example 2 As shown in Comparative Example 2 in FIG. 3, in Comparative Example 2, a stretched PET film (100 ⁇ m thick) was prepared as a polymer substrate. Then, a UC layer was formed on a PET substrate having a thickness of 100 ⁇ m using a urethane coating agent in the same manner as in Example 2.
- a 3% solid content solution was prepared as a coating agent, and a film thickness of 0.1 ⁇ m was formed by bar coating under processing conditions of 120 ° C. for 1 min.
- a TiO x thin film was formed as an ALD film on the UC layer.
- the TiO x thin film was formed by using a TiCl 4 raw material and having a thickness of 10 nm by plasma treatment. Further, no OC layer is formed on the surface of the ALD film.
- the gas barrier property was measured.
- the initial measured value of WVTR was 4.1 ⁇ 10 ⁇ 3 [g / m 2 / day]
- the WVTR after the cooling test was 80.4 ⁇ 10 ⁇ 3 [g / m 2 / day]. It was. That is, when the laminated body of Comparative Example 2 was subjected to a cooling test, the WVTR increased by about 20 times.
- Comparative Example 1 and Comparative Example 2 do not have an OC layer on the surface of the ALD film, so that through holes are formed in the ALD film due to thermal stress and the like, and the gas barrier property is remarkably lowered. Conceivable.
- the samples of the laminates of Examples 1 to 4 were provided with an OC layer on the surface of the ALD film to protect against external stress, the ALD film was not damaged by thermal stress or the like. It is considered that the property does not decrease.
- the laminate of the present invention by providing an OC layer on the surface of an ALD film formed on a polymer substrate, the OC layer can be subjected to stress or mechanical external force due to environmental changes or the like. Therefore, the gas barrier property of the laminate can be increased. In addition, even if a thin ALD film is used, since the OC layer prevents damage due to external force, the desired performance can be achieved even with a thin ALD film.
- Embodiment of Manufacturing Method of Laminate The manufacturing method of the laminated body which concerns on embodiment of this invention forms a thin-film-like atomic layer deposition film along the outer surface of a base material at the first process. Then, in an inline next step, before the atomic layer deposition film contacts a rigid body such as a roller, an overcoat layer is formed on the surface of the atomic layer deposition film. Specifically, normally, the substrate on which the atomic layer deposition film is formed is wound into a roll and transported to the next process. In this embodiment, the substrate on which the atomic layer deposition film is formed is used.
- An overcoat layer is formed on the surface of the atomic layer deposited film before the roller for changing the traveling direction for changing the traveling direction of the substrate in order to make a roll shape contacts the atomic layer deposited film.
- an overcoat layer is formed on the surface of the atomic layer deposition film. Form.
- the overcoat layer needs to be a film having higher mechanical strength than the atomic layer deposition film.
- the overcoat layer has a mechanical strength equivalent to that of the atomic layer deposition film
- the overcoat layer needs to be a layer formed with a thickness larger than that of the atomic layer deposition film. The reason is that even if the atomic layer deposition film is damaged by external force and a through-hole is formed in the film thickness direction, the overcoat layer does not generate a through-hole in the film thickness direction with such external force. This is because the property can be maintained well.
- an undercoat layer may be formed between the base material and the atomic layer deposition film, or the undercoat layer may not be formed.
- the method for manufacturing a laminate according to an embodiment of the present invention is realized by a laminate manufacturing apparatus including an inline overcoat forming unit that forms the ALD film 4 and the OC layer 5 in an inline serial process.
- the manufacturing method of the laminated body according to the present embodiment is such that the laminated body 1b in which the UC layer 3 as shown in FIG. 2 is formed even in the laminated body 1a in which the UC layer is not formed as shown in FIG. But it can be applied. That is, when the ALD film 4 and the OC layer (protective coat) 5 are formed in-line regardless of the presence or absence of the UC layer, the ALD is performed in a roll-to-roll manner with respect to the wound (film-like) base material.
- the present invention can be applied to the manufacturing process of the laminated bodies 1a and 1b on which the thin film 4 is deposited.
- the ALD film 4 formed (deposited) on the base material 2 is a dense thin film, and can exhibit excellent gas barrier properties even with a very thin film thickness (for example, 10 nm).
- a very thin film thickness for example, 10 nm.
- the ALD film 4 is thin, when a thin film is deposited (film formation) using the roll-to-roll method using the ALD method, the stacked body 1 (1a, 1b) after the ALD film 4 is formed is The ALD film 4 may be scratched or pinholed due to contact with a transport guide roller or the like, or contact between substrates during winding. When scratches or pinholes are generated in the ALD film 4 in this manner, the gas barrier performance of the laminate 1 is degraded.
- the minute defects generated in the ALD film 4 are practical problems in the case of the laminated body 1 having a low gas barrier property requirement (for example, when the water vapor transmission rate (WVTR) is about 1.0 g / m 2 / day). Must not. However, in the case of the laminated body 1 that requires a high gas barrier property such that the WVTR is 1 ⁇ 10 ⁇ 3 g / m 2 / day or less, a problem arises in airtightness.
- WVTR water vapor transmission rate
- the WVTR may increase by 1 ⁇ 10 ⁇ 3 g / m 2 / day or more.
- an overcoat layer (OC layer) 5 is formed as a protective coat before the laminate 1 contacts the guide roller.
- the material of the OC layer 5 at this time is preferably an organic polymer, and examples thereof include acrylic ester monomers and mixtures of acrylic monomers and acrylic ester oligomers.
- the thickness of the OC layer 5 serving as a protective coat is preferably 1 ⁇ m or more. Note that a method for forming a protective coat on the surface of the ALD film 4 with the OC layer 5 is performed by a method in which the mechanical component does not directly contact the surface of the ALD film 4.
- the film formation process of the protective coat by the OC layer 5 is performed in-line with the film formation of the ALD film 4, and therefore the appropriate coating speed and the appropriate range of the degree of vacuum must be the same. Further, when the protective coating is performed by the OC layer 5, it is not desirable that the coating surface of the ALD film 4 is in contact because it causes pinholes and scratches, and the protective coating of the OC layer 5 can be performed without contact. The method is desirable.
- the process for protective coating the OC layer 5 must not generate a large amount of gas in order to maintain a desired degree of vacuum.
- the deposition process of the protective coat using the OC layer 5 is a vacuum process, non-contact, and a flash vapor deposition method that does not use a solvent as a coating agent (that is, generates less volatile gas). ing.
- Embodiment demonstrates the manufacturing method of the laminated body which forms an OC layer by flash vapor deposition.
- the flash vapor deposition method is a means for coating monomers, oligomers, etc. in a desired thickness in a vacuum, is non-contact, does not generate a large amount of volatile components such as a solvent, and is applied to a substrate in a vacuum with a low heat load.
- An acrylic layer can be deposited. At this time, an acrylic monomer, an acrylic oligomer, or the like that is liquid at room temperature and does not contain a solvent is used.
- FIG. 4 is a schematic configuration diagram of a laminate manufacturing apparatus 10a that forms an OC layer by a flash vapor deposition method, which is applied to the third embodiment of the present invention.
- This laminated body manufacturing apparatus 10 a includes an ALD film forming mechanism 11 for forming an ALD film 4 and an overcoat formation that is provided on the downstream side of the ALD film forming mechanism 11 and forms an OC layer 5 on the surface of the ALD film 4.
- the unit 21 is constituted by the drum 13 and various rollers (feeding roller 14a, winding roller 18b, etc.).
- the configuration of the elements including the ALD film forming mechanism 11, the drum 13, and various rollers is as follows. That is, a drum (support) 13 that supports one surface in the thickness direction of a thin plate, a film, or a strip-like base material 12 formed in a film shape, and the base material 12 in one direction along the drum 13.
- the base material 12 is inserted between the transport mechanism 14 including the feeding roller 14 a and the small roller 14 b to be transported, the plasma pretreatment unit 16 that performs plasma pretreatment on the base material 12, and the surface of the drum 13.
- ALD film forming portions 17a, 17b, and 17c that adhere the precursor of the ALD film to the other surface in the thickness direction of the base material 12, and provided downstream of the overcoat forming portion 21 in the transport direction of the base material 12.
- a winding mechanism 18 including a dancer roller 18a and a winding roller 18b that winds the base material 12 on which the ALD film 4 and the OC layer 5 are formed in a roll shape.
- the dancer roller 18a of the winding mechanism 18 has a function of applying a predetermined tension when the substrate 12 is wound around the winding roller 18b.
- FIG. 4 three ALD film forming portions 17 a, 17 b, and 17 c are displayed.
- the number corresponding to the film forming cycle of the ALD method capable of realizing a desired film thickness on the ALD film 4 is shown. It is necessary to provide it. For example, if the ALD film 4 has a thickness of 10 nm and 70 ALD film forming cycles are required, 70 ALD film forming portions must be provided.
- the rotation direction of the feeding roller 14a, the drum 13, and the winding roller 18b is the arrow direction (counterclockwise direction) in FIG.
- the overcoat forming unit 21 for forming (coating) the OC layer 5 on the surface of the ALD film 4 includes a raw material tank 22, a raw material pipe 23, a raw material transfer pump 24, an atomizer (atomizer) 25, a vaporizer (evaporator) 26, A gas pipe 27, a coating nozzle 28, and an irradiation unit 29 that irradiates an electron beam or UV (ultraviolet light) to crosslink and cure the OC layer 5 (acrylic layer) coated on the surface of the ALD film 4. ing.
- the drum (support) 13 supports the base material 12 so that the base material 12 is maintained in a certain shape between the ALD film forming portions 17a, 17b, and 17c and the winding mechanism 18. .
- the OC layer 5 is uniformly coated on the surface of the ALD film 4.
- the ALD film 4 is formed on the substrate 2 by a normal ALD method.
- a case will be described in which a thin film of an ALD film 4 made of aluminum oxide (Al 2 O 3 ) is formed on a polymer base 2 by a roll-up type ALD method.
- Step 1 a stretched film of polyethylene terephthalate (PET) having a thickness of 100 ⁇ m is wound up as a film-like polymer base material 2, and this is attached to a feeding roller 14 a of the transport mechanism 14 in the laminate manufacturing apparatus 10.
- PET polyethylene terephthalate
- step 2 the film-like base material 12 fed out from the small roller 14 b that is the unwinding shaft of the transport mechanism 14 is oxygenated by the plasma pretreatment unit 16 while the back surface is supported by the drum (support) 13. Surface modification is performed by exposure to a plasma atmosphere.
- the plasma treatment conditions at this time are appropriately selected according to the detailed characteristics of the substrate 12.
- Step 3 the base material 12 moves to the purge region 17a1 of the ALD film forming portion 17a of the ALD film forming mechanism 11 in the atmosphere of an inert gas (nitrogen gas) after the plasma processing is completed.
- an inert gas nitrogen gas
- Step 4 after the base material 12 enters the zone of the ALD film forming portion 17a and passes through the purge region 17a1, trimethylaluminum is adsorbed in the atmosphere of the first precursor region 17a2.
- the first precursor region 17a2 is maintained in an atmosphere of nitrogen gas and trimethylaluminum, a pressure of about 10 to 50 Pa, and an inner wall temperature of about 70 ° C.
- Step 5 the base material 12 moves to the purge area 17a1 of the next section, and excess first precursor is removed in the atmosphere.
- step 6 the base material 12 moves from the purge region 17a1 to the second precursor region 17a3.
- the second precursor region 17a3 is maintained at a pressure of about 10 to 50 Pa and an inner wall temperature of about 70 ° C. in an atmosphere of nitrogen gas and water.
- water reacts with trimethylaluminum adsorbed on the base material 12.
- step 7 the base material 12 passes through a slit (not shown) provided in the partition plate between the second precursor region 17a3 and the purge region 17a1, and is conveyed to the next purge region 17a1. Excess second precursor is removed in the purge region 17a1.
- the film forming process of the ALD film 4 in steps 1 to 7 as described above is one cycle, and the laminated ALD film 4 for one layer is formed on the surface of the substrate 12.
- FIG. 4 three cycles by three ALD film forming units 17a, 17b, and 17c are shown.
- 70 ALD film forming units 17 perform film forming processing of 70 cycles.
- a 10 nm thin film of aluminum oxide (Al 2 O 3 ) is formed as an ALD film 4 on the surface of the substrate 12.
- the base material 12 on which the ALD film 4 is formed by a thin film of aluminum oxide (Al 2 O 3 ) in the ALD film forming sections 17a, 17b, and 17c is transported to the overcoat forming section 21 that forms the OC layer 5 serving as a protective coat. Is done.
- the coating material (acrylic monomer or the like) sent from the raw material tank 22 to the raw material pipe 23 by the raw material transport pump 24 is dropped onto an atomizer (atomizer) 25.
- the coating material (acrylic monomer or the like) dropped onto the atomizer (sprayer) 25 becomes gaseous at the same time as it contacts the wall surface of the vaporizer (evaporator) 26.
- the coating material that has become gaseous (gaseous) in the vaporizer 26 is diffused to the coating nozzle 28 through the gas pipe 27 kept at a high temperature. Further, the gaseous coating material that has flowed out of the coating nozzle 28 in the form of spray is aggregated on the surface of the substrate 12.
- the OC layer 5 formed of the coating material aggregated on the surface of the substrate 12 is crosslinked and cured by an electron beam or UV light irradiated from the irradiation unit 29. Note that the coating section (overcoat forming portion 21) of the OC layer 5 is usually kept in an atmosphere of an inert gas such as nitrogen gas so as not to inhibit the crosslinking of the coating material.
- the coating thickness of the OC layer 5 can be arbitrarily adjusted by adjusting the amount of the coating material dropped on the vaporizer 26 per unit time. For example, when it is desired to increase the coating thickness of the OC layer 5, the amount of the coating material dropped onto the vaporizer 26 is increased. When the coating thickness of the OC layer 5 is desired to decrease, the coating material is dropped onto the vaporizer 26. Reduce the amount. In this way, the uniformity of the coating film thickness of the OC layer 5 can be controlled by keeping the amount of material dropped per unit time constant.
- the base material 12 on which the thin film of the ALD film 4 made of aluminum oxide (Al 2 O 3 ) is formed in the ALD film forming mechanism 11 has a protective coat (OC layer 5) without being in contact with the mechanical parts on the way. It is conveyed to the overcoat formation part 21 to form.
- an acrylic coating agent for example, an acrylic monomer, an oligomer, a photoinitiator, etc.
- the OC layer 5 is aggregated.
- the base film (laminate 1) in which the OC layer 5 of the acrylic coating agent is deposited on the surface of the aluminum oxide (Al 2 O 3 ) thin film (ALD film 4) is irradiated with a UV lamp or an electron beam To the irradiation zone (irradiation unit 29).
- the acrylic coating agent is cured to form an OC layer 5 of about 1 ⁇ m.
- the base film (laminated body 1) on which the OC layer 5 is formed in this way by flash vapor deposition is conveyed to the winding mechanism 18 and wound around the winding roller 18b while being applied with a certain tension by the dancer roller 18a.
- the thin film (ALD film 4) of aluminum oxide (Al 2 O 3 ) does not directly contact the winding mechanism 18 (dancer roller 18a or winding roller 18b). Further, even after the base film (laminate 1) is wound around the winding roller 18b, there is no possibility that the aluminum oxide (Al 2 O 3 ) thin films (ALD films 4) are in direct contact with each other.
- FIG. 5 is a schematic configuration diagram of a laminate manufacturing apparatus 10b that forms an OC layer by CVD, which is applied to the fourth embodiment of the present invention. Since the configuration including the ALD film forming mechanism 11 for forming the ALD film 4 on the substrate 12, the drum 13, and various rollers is the same as that in FIG. 4, the description thereof is omitted.
- the overcoat forming unit 31 performs chemical vapor deposition, for example, an RF (Radio Frequency) power supply 32 that supplies high-frequency power for plasma of 13.56 MHz, a matching box 33 that performs frequency matching of high-frequency power for plasma, and the like.
- RF Radio Frequency
- the ambient gas flow meter 36 for measuring the supply amount of the atmospheric gas, such as ozone or O 2
- HMDSO for CVD A raw material tank 37 for supplying a fluorocarbon gas such as Hexamethyldisiloxane (hexamethyldisiloxane) and a raw material gas flow meter 38 for measuring the supply amount of a fluorocarbon gas such as HMDSO are provided.
- an Al 2 O 3 film having a thickness of 10 nm is formed on the surface of the polymer substrate 12 by a normal ALD method in the ALD film forming mechanism 11 by a method similar to the case of the flash vapor deposition described in the third embodiment.
- An ALD film 4 is formed.
- the base material 12 on which the Al 2 O 3 thin film (ALD film 4) is formed by the ALD film forming portions 17a, 17b, and 17c moves to the overcoat forming portion 31 as in the case of the third embodiment. .
- Al 2 O substrate 12 on which a thin film is formed is of 3, when passing through the overcoat forming unit 31, a thin film of SiO 2 is formed to a thickness of 1 ⁇ m by conventional CVD method.
- a high frequency power of 1.0 kW with a frequency of 13.56 MHz is applied from the RF power source 32 to the CVD electrode.
- hexamethyldisiloxane (HMDSO) having a film forming pressure of 10 Pa is supplied from the raw material tank 37.
- the amount of HMDSO introduced at this time is 100 sccm.
- the amount of ozone gas introduced from the gas tank 35 is 100 sccm.
- the distance between the electrodes in the CVD electrode 34 is 30 mm.
- the base material 12 made the polyethylene terephthalate (PET) 100 micrometers in thickness.
- the base film (laminated body 1) on which the OC layer 5 is thus formed by CVD is conveyed to the winding mechanism 18 and is wound around the winding roller 18b while being applied with a certain tension by the dancer roller 18a. It is done. Therefore, the Al 2 O 3 thin film (ALD film 4) does not directly contact the winding mechanism 18 (dancer roller 18a or winding roller 18b). Further, even after the base film (laminate 1) is wound around the winding roller 18b, there is no possibility that the Al 2 O 3 thin films (ALD films 4) are in direct contact with each other.
- FIG. 6 is a flowchart summarizing the manufacturing process of the laminate in the case where the UC layer is not provided in the embodiment of the present invention.
- FIG. 7 is a flow chart summarizing the manufacturing process of the laminate when the UC layer is provided in the embodiment of the present invention.
- a thin ALD film 4 is formed along the outer surface of the polymer substrate 2 (step S1).
- an OC layer 5 having a mechanical strength higher than that of the ALD film 4 is formed along the outer surface of the ALD film 4 in-line in the process in series with the formation of the ALD film 4 to generate a laminated body 1a.
- the OC layer 5 is formed of a film having a mechanical strength equivalent to that of the ALD film 4 and a thickness greater than that of the ALD film 4 along the outer surface of the ALD film 4 to form a laminate. It may be generated.
- the OC layer 5 is brought into contact with the take-up roller 18b to take up and store the laminate 1a (step S3).
- the OC layer 5 having higher mechanical strength than the ALD film 4 comes into contact with the dancer roller 18a and the take-up roller 18b, and the ALD film 4 does not come into direct contact with the dancer roller 18a and the take-up roller 18b. There is no possibility that the ALD film 4 is damaged. As a result, the laminate 1a can be wound around the take-up roller 18b while maintaining good gas barrier properties of the laminate 1a. Even if the OC layer 5 has the same mechanical strength as that of the ALD film 4, if the OC layer 5 is thicker than the ALD film 4, the OC layer 5 is not affected even if an external force is applied to the extent that the ALD film 4 is slightly damaged. There is no possibility that a through-hole is formed in the layer 5. As a result, the gas barrier property of the laminated body 1a can be maintained satisfactorily.
- the manufacturing process of the laminated body 1b when the UC layer is provided will be described with reference to FIG.
- the UC layer 3 containing at least one of an inorganic substance and an organic polymer is formed along the outer surface of the polymer substrate 2 (step S11).
- a thin ALD film 4 is formed on the surface of the UC layer 3 so as to be bonded to at least one of an inorganic substance or an organic polymer exposed on the surface of the UC layer 3 (step S2).
- an OC layer 5 having a mechanical strength higher than that of the ALD film 4 is formed along the outer surface of the ALD film 4 in-line in a process in series with the formation of the ALD film 4 to generate the stacked body 1b. (Step S3).
- step S3 the OC layer 5 is formed of a film having a mechanical strength equal to that of the ALD film 4 and thicker than the ALD film 4 along the outer surface of the ALD film 4 to form the laminate 1b. May be generated.
- the OC layer 5 is brought into contact with the take-up roller 18b to take up and store the laminated body 1b (step S4).
- the OC layer 5 having higher mechanical strength than the ALD film 4 comes into contact with the dancer roller 18a and the take-up roller 18b, and the ALD film 4 does not come into direct contact with the dancer roller 18a and the take-up roller 18b. There is no possibility that the ALD film 4 is damaged. As a result, the gas barrier property of the laminate 1b can be maintained satisfactorily. Even if the OC layer 5 has the same mechanical strength as that of the ALD film 4, if the OC layer 5 is thicker than the ALD film 4, the OC layer 5 is not affected even if an external force is applied to the extent that the ALD film 4 is slightly damaged. There is no possibility that a through-hole is formed in the layer 5. As a result, the gas barrier property of the laminate 1b can be maintained satisfactorily.
- Example 1 the OC layer was formed by flash vapor deposition using the laminate manufacturing apparatus 10a of FIG. That is, as shown in FIG. 8, in Example 1, a stretched film of 100 ⁇ m-thick polyethylene terephthalate (PET) wound as a polymer base film was attached to the feeding roller 14a of the laminate manufacturing apparatus 10a. . Then, the film (base material 12) fed out from the small roller 14b was exposed to an O 2 plasma atmosphere by the plasma processing unit 16 under conditions of 300 W and 180 seconds to modify the surface. Further, after the plasma treatment, the film was moved by the drum 13 to the ALD film forming unit 11 in an N 2 gas atmosphere.
- PET polyethylene terephthalate
- the film was introduced into the ALD film forming unit 17a and passed through the purge region 17a1 which was a mixed atmosphere of O 2 gas and N 2 gas, and then the inner wall temperature was maintained at about 70 ° C.
- TMA was adsorbed on the surface of the film in the first precursor region 17a2 in an atmosphere of N 2 gas and trimethylaluminum (TMA).
- the film was moved to the next purge region 17a1, where excess first precursor was removed. Then, the film is moved from the purge region 17a1 to the second precursor region 17a3, and the second precursor which is a mixed atmosphere of N 2 gas and H 2 O gas of 10 to 50 Pa with the inner wall temperature maintained at about 70 ° C. H 2 O was adsorbed on the film in the region 17a3. At this time, H 2 O and TMA reacted to produce aluminum oxide (Al 2 O 3 ) on the surface of the film.
- the second precursor which is a mixed atmosphere of N 2 gas and H 2 O gas of 10 to 50 Pa with the inner wall temperature maintained at about 70 ° C.
- H 2 O was adsorbed on the film in the region 17a3. At this time, H 2 O and TMA reacted to produce aluminum oxide (Al 2 O 3 ) on the surface of the film.
- the film is conveyed to a next purge region 17a1 through a slit provided in a partition plate between the second precursor region 17a3 and the purge region 17a1, and an excessive second film is passed through the purge region 17a1.
- the precursor was removed.
- the film on which the thin film of aluminum oxide (Al 2 O 3 ) was formed by the ALD film forming mechanism 11 was conveyed to the overcoat forming unit 21.
- the overcoat forming part 21 90/10 (wt%) of 2-hydroxy-3-phenoxypropyl acrylate and propoxylated neopentyl glycol diacrylate is formed on aluminum oxide (Al 2 O 3 ) on the surface of the film.
- the film layer formed by the uncured flash vapor deposition having a thickness of 1 ⁇ m was laminated.
- the coating layer formed by flash deposition was irradiated with an electron beam from the irradiation unit 29 to cure the coating layer, and an acrylic coating layer (acrylic resin) having a thickness of 1 ⁇ m was formed as an overcoat layer (OC layer).
- an acrylic coating layer (acrylic resin) having a thickness of 1 ⁇ m was formed as an overcoat layer (OC layer).
- the film on which the OC layer was formed by flash vapor deposition was transported to the winding mechanism 18, and the film on which the OC layer was formed was wound on the winding roller 18b with a constant tension by the dancer roller 18a.
- the gas barrier property was measured.
- the measured value of water vapor transmission rate (WVTR) was 1.5 ⁇ 10 ⁇ 3 [g / m 2 / day].
- Example 2 the OC layer was formed by CVD using the laminate manufacturing apparatus 10b of FIG. That is, as shown in FIG. 8, in Example 2, a thin film (barrier layer) of about 5 nm of aluminum oxide (Al 2 O 3 ) is formed to 100 ⁇ m by the ALD film forming mechanism 11 in the same manner as in Example 1. It was formed on a stretched film of thick polyethylene terephthalate (PET).
- PET polyethylene terephthalate
- the film in which the thin film of aluminum oxide (Al 2 O 3 ) was formed by the ALD film forming unit mechanism 11 was conveyed to the overcoat forming unit 31.
- a mixed gas of 100 sccm of hexamethyldisiloxane (HMDSO) and 100 sccm of ozone is introduced between the CVD electrodes 34, and high frequency power 1.0 kW with a frequency of 13.56 MHz is supplied between the electrodes 34 from the RF power source 32.
- HMDSO hexamethyldisiloxane
- ozone 100 sccm of ozone
- high frequency power 1.0 kW with a frequency of 13.56 MHz is supplied between the electrodes 34 from the RF power source 32.
- a silicon oxide film (SIO 2 film) of about 1 ⁇ m was formed as an OC layer on aluminum oxide (Al 2 O 3 ) on the surface of the film.
- the film on which the OC layer was formed by CVD was conveyed to the take-up mechanism 18, and the film on which the OC layer was formed was wound on the take-up roller 18b with a constant tension by the dancer roller 18a.
- a thin film (barrier layer) of about 5 nm of aluminum oxide (Al 2 O 3 ) was formed to a thickness of 100 ⁇ m by the ALD film forming mechanism 11 in the same manner as in Example 1. It was formed on a stretched film of polyethylene terephthalate (PET). Next, the film was conveyed to the winding mechanism 18 in a state where the OC layer was not formed. And the film in which the OC layer was not formed was made into the fixed tension
- PTT polyethylene terephthalate
- the gas barrier property was measured.
- the measured value of water vapor transmission rate (WVTR) was 3.0 ⁇ 10 ⁇ 2 [g / m 2 / day]. That is, when a film (laminated body) not provided with an OC layer as in Comparative Example 1 is wound up by the winding mechanism 18, a film (laminated body) provided with an OC layer as shown in Example 1 and Example 2 ) Is reduced by an order of magnitude as compared to the case where it is taken up by the take-up mechanism 18. In other words, when a film (laminate) not provided with an OC layer is wound by the winding mechanism 18, the gas barrier property is remarkably deteriorated.
- ⁇ Summary> As described above, according to the present invention, by providing an OC layer on the surface of an ALD film formed on a polymer substrate, mechanical external force (stress) by a roll-to-roll laminate manufacturing apparatus is provided. As a result, no scratches or pinholes are generated in the OC layer, so that the gas barrier property of the laminate can be increased. As a result, a high-quality ALD film-coated film can be produced at high speed by a winding method.
- the concrete structure of this invention is not limited to the content of embodiment mentioned above, The meaning of this invention Even if there is a design change or the like without departing from the scope, it is included in the present invention.
- the laminate manufacturing method and the laminate manufacturing apparatus have been described.
- the present invention is not limited thereto, and the manufacturing of the gas barrier film in which the laminate realized by the present invention is formed into a film shape.
- the present invention can also be applied to a method and a manufacturing apparatus.
- the laminate of the present invention can be used for electronic parts such as electroluminescence elements (EL elements), liquid crystal displays, and semiconductor wafers, as well as packaging films for pharmaceuticals and foods, packaging films for precision parts, etc. It can also be used effectively.
- the present invention provides a semiconductor manufacturing apparatus for manufacturing semiconductor parts such as electroluminescence elements (EL elements), liquid crystal displays, and semiconductor wafers, and a packaging film manufacturing for manufacturing packaging films for pharmaceuticals, foodstuffs, precision parts and the like. It can be used effectively for devices.
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Abstract
Description
本願は、2011年7月28日に、日本に出願された特願2011-165903号、特願2011-165904号に基づき優先権を主張し、その内容をここに援用する。
本発明の実施形態に係る積層体は、基本的には、基材の表面に原子層堆積膜が形成され、さらに、その原子層堆積膜の表面を覆うようにオーバーコート層が形成された構成となっている。このオーバーコート層は、基材やALD膜の特性を阻害しないものであれば、どのような特性を有する層であっても構わない。なお、膜厚方向に延びる貫通孔をオーバーコート層に生じさせるために要する外力の大きさが、膜厚方向に延びる貫通孔を原子層堆積膜に生じさせるために要する外力の大きさよりも大きいことが必要である。言い換えると、オーバーコート層は、原子層堆積膜よりも機械的強度が高い膜である必要がある。あるいは、オーバーコート層は、原子層堆積膜と同等の機械的強度を有している場合は、原子層堆積膜の膜厚よりも厚い膜厚で形成された層である必要がある。
図1は、本発明の第1実施形態にかかる積層体の構成を示す断面図である。図1に示すように、第1実施形態の積層体1aは、高分子材料で形成された基材2と、基材2の表面に膜状に形成された原子層堆積膜(以下、ALD膜という)4と、ALD膜4よりも機械的強度の高い膜で該ALD膜4を覆うオーバーコート層(以下、OC層という)5とを備えて構成されている。なお、OC層5は、ALD膜4と同等の機械的強度を有していて、ALD膜4よりも膜厚の厚い膜で該ALD膜4を覆ってもよい。
図2は、本発明の第2実施形態にかかる積層体の構成を示す断面図である。図2に示すように、第2実施形態の積層体1bが図1に示す第1実施形態の積層体1aと異なるところは、基材2とALD膜4との間にアンダーコート層(以下、UC層という)3が介在されている点である。なお、UC層3は、無機物質を含有していてもよいし、有機高分子を含有していてもよい。
図2に示すように、積層体1bは、基材2とALD膜4との間に、無機物質が分散されたUC層3を備えていて、ALD膜4の表面にOC層5が形成されている。ALD膜4の前駆体はガス状の物質であり、UC層3の表面に露出された無機物質に結合しやすい特性を有している。さらに、UC層3の表面には、多数の無機物質が露出しているので、各無機物質に結合したALD膜4の前駆体同士が、互いに結合する。これにより、UC層3の面方向に成長する二次元状のALD膜4が生じる。その結果、積層体1bの膜厚方向にガスが透過するような隙間が生じ難くなり、ガスバリア性の高い積層体1bを実現することができる。
図2に示すように、積層体1bは、基材2とALD膜4との間に有機高分子を含有するUC層3を備えていて、ALD膜4の表面にOC層5が形成されている。UC層3は有機高分子を含有する層であり、この有機高分子はALD膜4の前駆体が結合する結合部位を有している。すなわち、UC層3に含有されている有機高分子は、ALD膜4の前駆体と結合しやすい結合部位として、多数の官能基を有している。したがって、有機高分子の各官能基に結合した前駆体同士は、互いに結合する。これによって、UC層3の面方向に成長する二次元状のALD膜4が生じる。その結果、積層体1bの膜厚方向にガスが透過するような隙間が生じ難くなり、ガスバリア性の高い積層体1bを実現することができる。なお、UC層3には、有機高分子の他に無機物質が分散されていてもよい。すなわち、UC層3に無機物質が添加されていることにより、有機高分子と無機物質とが相俟って、ALD膜4の前駆体の吸着密度をさらに向上させることができる。
1.O原子含有樹脂の有機高分子
O原子含有樹脂の有機高分子として好ましい材料は、次のようなものである。水酸基(OH)含有樹脂として、ポリビニルアルコール、フェノール樹脂、多糖類などである。なお、多糖類は、セルロース、ヒドロキシメチルセルロース、ヒドロキシエチルセルロース、カルポキシメチルセルローズなどのセルロース誘導体、キチン、キトサンなどである。また、カルボニル基(COOH)含有樹脂として、カルボキシビニルポリマーなども好ましい材料である。
N原子含有樹脂の有機高分子として好ましい材料は、次のようなものである。イミド基(CONHCO)含有樹脂の、ポリイミド、ポリエーテルイミド、ポリアミドイミド、脂環族ポリイミド、溶剤可溶型ポリイミドなどである。なお、脂環族ポリイミドについては、通常は、芳香族ポリイミドは芳香族テトラカルボン酸無水物と芳香族ジアミンから得られるが、透明性がないため、ポリイミドの透明化として酸二無水物あるいはジアミンを脂肪族または脂環族に置き換えることも可能である。また、脂環族カルボン酸は、1,2,4,5-シクロへキサンテトラカルボン酸、1,2,4,5-シクロペンタンテトラカルボン酸二無水物などがある。さらに、溶剤可溶型ポリイミドとしては、γ-プチロラクトン、N,N-ジメチルアセトアミド、N-メチル-2-ピロリドンなどがある。
S原子含有樹脂の有機高分子として使用できる材料は、次のようなものがある。すなわち、スルホニル基(SO2)含有樹脂の、ポリエーテルスルフォン(PES)、ポリスルフォン(PSF)、ポリフェニルスルフォン(PPS)などである。このうち、PESとPSFは耐熱性が高い材料である。さらに、ポリマーアロイ、ポリブチレンテレフタレート系ポリマーアロイ、ポリフェニレンスルフイド系ポリマーアロイなども有機高分子として使用できる。なお、ポリマーアロイは、上記の高分子を必要に応じてポリマーの複合化(アロイ、ブレンド、コンボジット)してもよい。
次に、上記の実施形態に基づいて実現したオーバーコート層を備えた積層体の具体的な実施例について説明する。最初に、ALD膜からなるガスバリア層の一般的な成膜方法について説明する。なお、ここでは、基材の表面にUC層を形成したときのALD膜の成膜方法について説明する。
1.Al2O3の成膜
先ず、高分子基板の上面または高分子基板にUC層を設けた上面に、原子層堆積法(ALD法)によってAl2O3膜を成膜した。このとき、原料ガスはトリメチルアルミニウム(TMA)とした。また、原料ガスと同時に、プロセスガスとしてO2とN2を、パージガスとしてO2とN2を、反応ガス兼プラズマ放電ガスとしてO2を、それぞれ、成膜室へ供給した。その際の処理圧力は10~50Paとした。さらに、プラズマガス励起用電源は13.56MHzの電源を用い、ICP(Inductively Couple Plasma)モードによってプラズマ放電を実施した。
先ず、高分子基板の上面または高分子の基材の表面にUC層を設けた上面に、ALD法によってTiO2膜を成膜した。このとき、原料ガスは四塩化チタン(TiCl4)とした。また、原料ガスと同時に、プロセスガスとしてN2を、パージガスとしてN2を、反応ガス兼プラズマ放電ガスとしてO2を、それぞれ、成膜室へ供給した。その際の処理圧力は10~50Paとした。さらに、プラズマガス励起用電源は13.56MHzの電源を用い、ICPモードにてプラズマ放電を実施した。
次に、上記の実施形態に基づいて実現したオーバーコート層(OC層)を備えた積層体の水蒸気透過率の実験結果について、幾つかの実施例を説明する。なお、ここで行った各実施例の実験結果は、上記の実施形態で実現した積層体のガスバリア性について、水蒸気透過度測定装置(モダンコントロール社製 MOCON Aquatran(登録商標))を用いて、40℃/90%RHの雰囲気で水蒸気透過率を測定したものである。図3は、OC層を有する本実施例の積層体と、OC層を設けない比較例の積層体とについて、水蒸気透過率(WVTR)を比較した図である。したがって、図3を参照しながら各実施例の優位性について説明する。
図3に示すように、実施例1では、100μm厚のポリエチレンテレフタレート(PET)の高分子基材上に、UC層を形成しないで、直接、ALD膜としてAlOx薄膜を形成した。なお、AlOx薄膜(ALD膜)は、原材料をTMA(トリメチルアルミニウム)として、プラズマ処理によって10nmの膜厚を形成した。
図3に示すように、実施例2では、100μm厚のPETの高分子基材上に、ウレタン系コート剤を用いてUC層を形成した。このUC層のウレタン系コート剤は、市販のアクリルポリオール、HEMA(メタクリル酸2-ヒドロキシメチル)/MMA(メタクリル酸メチル)系共重合ポリマー、HAMA30mol%分子量1万、TDI(トルエンジイソシアネート)アダクト系硬化剤を原材料とした。なお、原材料の組成比は、NCO/OH=0.5である。UC層は、コート剤として固形分3%溶液を調整し、120℃-1minの加工条件で、バーコートにて膜厚0.1μmを形成した。
図3に示すように、実施例3では、100μm厚のPETの高分子基材上に、無機含有ウレタン系コート剤を用いてUC層を形成した。UC層のウレタン系コート剤は、市販のアクリルポリオール、HEMA/MMA系共重合ポリマー、HAMA30mol%分子量1万、TDIアダクト系硬化剤、及び有機ベントナイトを原材料とした。なお、原材料の組成比は、NCO/OH=0.5であり、無機物質は15wt%である。UC層は、コート剤として固形分3%溶液を調整し、120℃-1minの加工条件で、バーコートにて膜厚1μmを形成した。
図3の実施例4に示すように、実施例4では、100μm厚のPETの高分子基材上に、無機含有ウレタン系コート剤を用いてUC層を形成した。UC層の無機含有ウレタン系コート剤は、市販のアクリルポリオール、HEMA/MMA系共重合ポリマー、HAMA30mol%分子量1万、TDIアダクト系硬化剤、及びTiO2超微粒子ゾルを原材料とした。なお、原材料の組成比は、NCO/OH=0.5であり、無機物質は30wt%である。UC層は、コート剤として固形分3%溶液を調整し、120℃-1minの加工条件で、バーコートにて膜厚0.1μmを形成した。
次に、本実施例に係るOC層を備えた積層体にける水蒸気透過率の優位性を示すために、図3に示すような比較例と対比してみる。
図3に示すように、比較例1では、高分子の基材としてPETの延伸フィルム(100μm厚)を用意した。そして、この基材の表面にはUC層を設けないで、ALD膜としてAlOx膜を成膜した。AlOx薄膜は、原材料をTMAとして、プラズマ処理によって10nmの膜厚を形成した。なお、ALD膜の表面にはOC層は設けない。
図3の比較例2に示すように、比較例2では、高分子の基材としてPETの延伸フィルム(100μm厚)を用意した。そして、100μm厚のPETの基材上には、実施例2と同様に、ウレタン系コート剤を用いてUC層を形成した。UC層のウレタン系コート剤は、市販のアクリルポリオール、HEMA/MMA系共重合ポリマー、HAMA30mol%分子量1万、TDIアダクト系硬化剤を原材料とした。なお、原材料の組成比は、NCO/OH=0.5である。UC層は、コート剤として固形分3%溶液を調整し、120℃-1minの加工条件で、バーコートにて膜厚0.1μmを形成した。
すなわち、実施例1乃至実施例4のようにOC層を設けた場合の積層体のガスバリア特性は、水蒸気透過率(WVTR)の初期値に比べて、冷熱試験後のWVTRの値はそれほど増加していない。一方、比較例1、比較例2のようにOC層を設けない場合のガスバリア特性は、WVTRの初期値に比べて冷熱試験後のWVTRの値が1桁以上(10倍以上)増加している。この原因は、比較例1、比較例2の積層体の試料はALD膜の表面にOC層を設けないために、熱ストレスなどによってALD膜に貫通孔が生じてガスバリア性が著しく低下したものと考えられる。一方、実施例1乃至実施例4の積層体の試料は、ALD膜の表面にOC層を設けて外部ストレスに対する保護を行ったので、熱ストレスなどによってALD膜が損傷しないために積層体のガスバリア性が低下しないものと考えられる。
以上述べたように、本発明の積層体によれば、高分子の基材上に形成したALD膜の表面にOC層を設けることにより、環境変化等などによるストレスや機械的な外力によってOC層が傷つかないために、積層体のガスバリア性を高くすることができる。また、薄いALD膜であってもOC層が外力による損傷を防止するために、薄いALD膜の膜厚でも所望の性能を実現することができる。
本発明の実施形態に係る積層体の製造方法は、最初の工程で、基材の外面に沿って薄膜状の原子層堆積膜を形成する。そして、インラインの次工程で、原子層堆積膜がローラ等の剛体に接触する前に、その原子層堆積膜の表面にオーバーコート層を形成する。具体的には、通常は、原子層堆積膜が形成された基材はロール状に巻かれて次工程へと搬送されるが、本実施形態では、原子層堆積膜が形成された基材をロール状にするために基材の進行方向を変えるための進行方向変更用のローラが原子層堆積膜に接触する前に、原子層堆積膜の表面にオーバーコート層を形成する。望ましくは、積層体の製造工程中において、原子層堆積膜が形成された基材の形状が、原子層堆積膜の形成時の形状から変化する前に、原子層堆積膜の表面にオーバーコート層を形成する。これによって、基材の変形に起因する原子層堆積膜の傷を防いで、良好なガスバリア性を維持することができる。
第3実施形態では、フラッシュ蒸着法によってOC層を形成する積層体の製造方法について説明する。フラッシュ蒸着法は、真空中でモノマー、オリゴマー等を所望の厚みでコーティングする手段であり、非接触で、溶媒などの多量の揮発成分を発生させることなく、かつ低熱負荷によって真空中において基材にアクリル層を堆積させることができる。このとき、常温において液体であり、溶媒を含まないアクリルモノマー、アクリルオリゴマー等が使用される。
第4実施形態では、CVD、すなわち化学蒸着法によってOC層を形成する積層体の製造方法について説明する。図5は、本発明の4実施形態に適用される、CVDによってOC層を形成する積層体製造装置10bの概略構成図である。基材12にALD膜4を成膜するALD成膜機構11とドラム13及び各種ローラを含めた構成については図4と同じであるので、それらの構成については説明は省略する。
以上説明した内容に基づき、図4または図5に示す積層体製造装置10a,10bによる積層体1の製造工程について説明する。図6は、本発明の実施形態において、UC層を設けない場合の積層体の製造工程を要約したフローチャートである。また、図7は、本発明の実施形態において、UC層を設けた場合の積層体の製造工程を要約したフローチャートである。
〈実施例1〉
実施例1では、図4の積層体製造装置10aを用いてフラッシュ蒸着によってOC層を形成した。すなわち、図8に示すように、実施例1では、高分子基材のフィルムとして巻き取られた100μm厚のポリエチレンテレフタレート(PET)の延伸フィルムを、積層体製造装置10aの繰出しローラ14aに取り付けた。そして、小ローラ14bから繰り出されたフィルム(基材12)をプラズマ処理部16で300W、180secの条件でO2プラズマの雰囲気に暴露して表面の改質を行った。さらに、プラズマ処理の後、ドラム13によって同フィルムをN2ガス雰囲気のALD成膜形成部11へ移動した。
実施例2では、図5の積層体製造装置10bを用いてCVDによってOC層を形成した。すなわち、図8に示すように、実施例2では、実施例1と全く同様な方法で、ALD成膜機構11にて約5nmの酸化アルミニウム(Al2O3)の薄膜(バリア層)を100μm厚のポリエチレンテレフタレート(PET)の延伸フィルム上に形成した。
次に、本実施例に係るOC層を備えた積層体にける水蒸気透過率の優位性を示すために、図8に示すような比較例と対比してみる。
図8に示すように、比較例1では、実施例1と全く同様な方法で、ALD成膜機構11にて約5nmの酸化アルミニウム(Al2O3)の薄膜(バリア層)を、100μm厚みのポリエチレンテレフタレート(PET)の延伸フィルム上に形成した。次に、OC層を形成しない状態で、同フィルムを巻取り機構18へ搬送した。そして、OC層が形成されていないフィルムをダンサーローラ18aによって一定のテンションにして、同フィルムを巻取りローラ18bに巻き上げた。
以上述べたように、本発明によれば、高分子の基材上に形成したALD膜の表面にOC層を設けることにより、ロールツーロール方式の積層体製造装置による機械的な外力(ストレス)によってOC層に傷やピンホールが生じないため、積層体のガスバリア性を高くすることができる。その結果、高品質なALD膜コートのフィルムを巻取り方式によって高速生産することができる。
また、本発明は、エレクトロルミネッセンス素子(EL素子)、液晶ディスプレイ、半導体ウェハなどの半導体部品を製造する半導体製造装置や、医薬品、食料品、精密部品などの包装用フィルムを製造する包装用フィルム製造装置などに有効に利用することができる。
2,12 基材
3 アンダーコート層(UC層)
4 原子層堆積膜(ALD膜)
5 オーバーコート層(OC層)
10a,10b 積層体製造装置
11 ALD成膜機構
13 ドラム(支持体)
14 搬送機構
14a 繰出しローラ
14b 小ローラ
16 プラズマ前処理部
17a,17b,17c ALD成膜部
17a1 パージ領域
17a2 第一前駆体領域
17a3 第二前駆体領域
18 巻取り機構
18a ダンサーローラ
18b 巻取りローラ
21、31 オーバーコート形成部
22 原料タンク
23 原料配管
24 原料搬送ポンプ
25 アトマイザー
26 気化器
27 気体配管
28 コーティングノズル
29 照射部
32 RF電源
33 マッチングボックス
34 電極
35 ガスタンク
36 雰囲気ガスフローメータ
37 原料タンク
38 原料ガスフローメータ
Claims (15)
- 基材と、
前記基材の外面に沿って形成された原子層堆積膜と、
前記原子層堆積膜よりも機械的強度の高い膜で該原子層堆積膜を覆うオーバーコート層と、
を備えることを特徴とする積層体。 - 基材と、
前記基材の外面に沿って形成された原子層堆積膜と、
前記原子層堆積膜と同等の機械的強度を有するとともに、前記原子層堆積膜よりも膜厚の厚い膜で該原子層堆積膜を覆うオーバーコート層と、
を備えることを特徴とする積層体。 - 請求項1または請求項2に記載の積層体であって、
前記オーバーコート層は水系バリアコートで形成されており、前記水系バリアコートは、OH基とCOOH基の少なくとも何れかを有することを特徴とする積層体。 - 請求項1から請求項3のいずれか一項に記載の積層体であって、
前記オーバーコート層は、無機物質を含有していることを特徴とする積層体。 - 請求項1から請求項4のいずれか一項に記載の積層体であって、
前記基材と前記原子層堆積膜との間に、前記原子層堆積膜と結合する無機物質が分散されたアンダーコート層または前記原子層堆積膜と結合する有機高分子が含有されたアンダーコート層をさらに備えることを特徴とする積層体。 - 請求項1から請求項5のいずれか一項に記載の積層体を有し、
前記積層体がフィルム状に形成されていることを特徴とするガスバリアフィルム。 - 基材の外面に沿って薄膜状の原子層堆積膜を形成する第1の工程と、
前記第1の工程と直列の工程内にあるインラインにおいて、前記原子層堆積膜の外面に沿って、該原子層堆積膜よりも機械的強度の高いオーバーコート層を形成し、積層体を生成する第2の工程と、
前記第2の工程で形成されたオーバーコート層が剛体に接触するように、前記積層体を収納する第3の工程と、
を含むことを特徴とする積層体の製造方法。 - 基材の外面に沿って薄膜状の原子層堆積膜を形成する第1の工程と、
前記第1の工程と直列の工程内にあるインラインにおいて、前記原子層堆積膜の外面に沿って、前記原子層堆積膜と同等の機械的強度を有すると共に該原子層堆積膜よりも膜厚の厚い膜でオーバーコート層を形成し、積層体を生成する第2の工程と、
前記第2の工程で形成されたオーバーコート層が剛体に接触するように、前記積層体を収納する第3の工程と、
を含むことを特徴とする積層体の製造方法。 - 基材の外面に沿って、無機物質または有機高分子の少なくとも一方を含有するアンダーコート層を形成する第1の工程と、
前記第1の工程で形成されたアンダーコート層の表面に露出した無機物質または有機高分子の少なくとも一方と結合するように、前記アンダーコート層の外面に薄膜状の原子層堆積膜を形成する第2の工程と、
前記第2の工程と直列の工程内にあるインラインにおいて、前記原子層堆積膜の外面に沿って、該原子層堆積膜よりも機械的強度の高いオーバーコート層を形成し、積層体を生成する第3の工程と、
前記第3の工程で形成されたオーバーコート層が剛体に接触するように、前記積層体を収納する第4の工程と、
を含むことを特徴とする積層体の製造方法。 - 基材の外面に沿って、無機物質または有機高分子の少なくとも一方を含有するアンダーコート層を形成する第1の工程と、
前記第1の工程で形成されたアンダーコート層の表面に露出した無機物質または有機高分子の少なくとも一方と結合するように、前記アンダーコート層の外面に薄膜状の原子層堆積膜を形成する第2の工程と、
前記第2の工程と直列の工程内にあるインラインにおいて、前記原子層堆積膜の外面に沿って、前記原子層堆積膜と同等の機械的強度を有すると共に該原子層堆積膜よりも膜厚の厚い膜でオーバーコート層を形成し、積層体を生成する第3の工程と、
前記第3の工程で形成されたオーバーコート層が剛体に接触するように、前記積層体を収納する第4の工程と、
を含むことを特徴とする積層体の製造方法。 - 請求項7から請求項10のいずれか一項に記載の積層体の製造方法であって、
前記剛体は巻取りローラであり、前記第3の工程または前記第3の工程より後において、前記積層体は、前記巻取りローラにロール状に接触して巻き取られ、収納されることを特徴とする積層体の製造方法。 - 請求項7から請求項11のいずれか一項に記載の積層体の製造方法であって、
前記オーバーコート層は、フラッシュ蒸着法により、前記原子層堆積膜の外面にアクリルを成膜したものであるか、または、化学蒸着法によって形成されたものであることを特徴とする積層体の製造方法。 - 薄板、フィルム、若しくは膜状に形成された帯状の基材に原子層堆積膜が成膜された積層体を、インラインの工程内でロールツーロール方式によって搬送する積層体の製造装置であって、
前記基材の厚み方向の一方の面を支持する支持体と、
前記支持体の外面に沿って前記基材を一方向へ搬送する搬送機構と、
前記支持体の外面との間に前記基材が挿入されるように配置され、該基材の厚み方向の他方の面に前記原子層堆積膜を成膜させるALD成膜部と、
前記基材の搬送方向において前記ALD成膜部の下流に設けられ、前記原子層堆積膜の表面に、前記原子層堆積膜より機械的強度の強い、または該原子層堆積膜より膜厚の厚いオーバーコート層を形成させるオーバーコート形成部と、
前記基材の搬送方向において前記オーバーコート形成部の下流に設けられ、前記オーバーコート層を接触面として前記積層体をロール状に巻き取る巻取り機構と、
を備えることを特徴とする積層体製造装置。 - 請求項13に記載の積層体製造装置であって、
前記オーバーコート形成部は、フラッシュ蒸着若しくは化学蒸着により前記オーバーコート層を形成することを特徴とする積層体製造装置。 - 請求項13または請求項14に記載の積層体製造装置であって、
前記基材の搬送方向において前記ALD成膜部よりも上流に配置されたアンダーコート形成部をさらに備え、
前記アンダーコート形成部は、
前記原子層堆積膜に結合する結合部位を有するアンダーコート層を前記基材の外面に形成することを特徴とする積層体製造装置。
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EP12817195.6A EP2740593A4 (en) | 2011-07-28 | 2012-07-27 | LAMINATE, GAS BARRIER FILM, PRODUCTION METHOD FOR LAMINATE AND DEVICE FOR PRODUCING LAMINATE |
JP2013525782A JP6123672B2 (ja) | 2011-07-28 | 2012-07-27 | 積層体の製造方法及び積層体製造装置 |
KR1020147001358A KR102081210B1 (ko) | 2011-07-28 | 2012-07-27 | 적층체, 가스 배리어 필름, 적층체의 제조 방법 및 적층체 제조 장치 |
CN201280037062.9A CN103732393B (zh) | 2011-07-28 | 2012-07-27 | 层叠体、阻气膜、层叠体的制造方法及层叠体制造装置 |
US14/164,766 US20140141218A1 (en) | 2011-07-28 | 2014-01-27 | Laminate body, gas barrier film, method of manufacturing laminate body, and laminate body manufacturing apparatus |
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JP2018020540A (ja) * | 2016-08-05 | 2018-02-08 | 大日本印刷株式会社 | バリア性フィルム |
JP2021073116A (ja) * | 2016-08-05 | 2021-05-13 | 大日本印刷株式会社 | バリア性フィルム |
WO2018056401A1 (ja) * | 2016-09-23 | 2018-03-29 | 凸版印刷株式会社 | ガスバリア性光学フィルム及び有機elディスプレイ |
WO2019151495A1 (ja) * | 2018-02-02 | 2019-08-08 | 凸版印刷株式会社 | ガスバリア性フィルム及びその製造方法 |
JPWO2019151495A1 (ja) * | 2018-02-02 | 2021-02-12 | 凸版印刷株式会社 | ガスバリア性フィルム及びその製造方法 |
JP7287284B2 (ja) | 2018-02-02 | 2023-06-06 | 凸版印刷株式会社 | ガスバリア性フィルム及びその製造方法 |
JP2020158860A (ja) * | 2019-03-28 | 2020-10-01 | 東レエンジニアリング株式会社 | 成膜装置、及び成膜方法 |
JP7221758B2 (ja) | 2019-03-28 | 2023-02-14 | 東レエンジニアリング株式会社 | 成膜装置、及び成膜方法 |
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CN103732393B (zh) | 2016-10-05 |
TWI590951B (zh) | 2017-07-11 |
CN103732393A (zh) | 2014-04-16 |
JP6123672B2 (ja) | 2017-05-10 |
KR102081210B1 (ko) | 2020-02-25 |
JP2017124633A (ja) | 2017-07-20 |
TW201323226A (zh) | 2013-06-16 |
JP6508245B2 (ja) | 2019-05-08 |
EP2740593A4 (en) | 2015-04-15 |
US20140141218A1 (en) | 2014-05-22 |
EP2740593A1 (en) | 2014-06-11 |
KR20140043787A (ko) | 2014-04-10 |
JPWO2013015417A1 (ja) | 2015-02-23 |
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