WO2004101276A1 - 透明ガスバリア積層フィルム、これを用いたエレクトロルミネッセンス発光素子、エレクトロルミネッセンス表示装置、及び電気泳動式表示パネル - Google Patents
透明ガスバリア積層フィルム、これを用いたエレクトロルミネッセンス発光素子、エレクトロルミネッセンス表示装置、及び電気泳動式表示パネル Download PDFInfo
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- WO2004101276A1 WO2004101276A1 PCT/JP2004/006808 JP2004006808W WO2004101276A1 WO 2004101276 A1 WO2004101276 A1 WO 2004101276A1 JP 2004006808 W JP2004006808 W JP 2004006808W WO 2004101276 A1 WO2004101276 A1 WO 2004101276A1
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- Prior art keywords
- gas barrier
- layer
- film
- transparent gas
- transparent
- Prior art date
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
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- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/165—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on translational movement of particles in a fluid under the influence of an applied field
- G02F1/166—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on translational movement of particles in a fluid under the influence of an applied field characterised by the electro-optical or magneto-optical effect
- G02F1/167—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on translational movement of particles in a fluid under the influence of an applied field characterised by the electro-optical or magneto-optical effect by electrophoresis
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- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/133345—Insulating layers
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- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/165—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on translational movement of particles in a fluid under the influence of an applied field
- G02F1/1675—Constructional details
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
- H10K50/84—Passivation; Containers; Encapsulations
- H10K50/844—Encapsulations
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- B32B2250/00—Layers arrangement
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- B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
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- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/412—Transparent
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/724—Permeability to gases, adsorption
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- G—PHYSICS
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- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F2201/00—Constructional arrangements not provided for in groups G02F1/00 - G02F7/00
- G02F2201/50—Protective arrangements
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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
- Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
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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
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- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/31938—Polymer of monoethylenically unsaturated hydrocarbon
Definitions
- the present invention provides a transparent laminated film having high gas barrier properties against oxygen, water vapor, etc., and which can be used as a packaging material for foods, pharmaceuticals, electronic members, optical members, etc., which require high transparency.
- the present invention relates to an electroluminescence light-emitting element, an electroluminescence display device, and an electrophoretic display panel using the same. Background art
- Packaging materials used for packaging in the non-food fields such as the food field, pharmaceuticals, electronic components, and optical components, use oxygen that penetrates the packaging material to suppress deterioration of the contents and maintain their functions and properties. It is necessary to prevent the effects of water vapor and other gases that alter the contents, and it is required to have a gas barrier property that blocks these effects.
- a metal foil made of a metal such as aluminum, a metal-deposited film, a gas-barrier resin film having a relatively excellent gas-barrier property for example, chloride Resin films such as vinylidene resin films, polyvinyl alcohol and ethylene vinyl copolymer films, polyacrylic resin-triles, etc., or films laminated with these resins are mainly used. It has been used for
- the metal foil / metal deposition film is a gas barrier. Although it is excellent in transparency, its contents cannot be identified due to the loss of transparency, the contents cannot be inspected by a metal detector, and it is considered incombustible when disposed of after use. There was a problem that it had to be processed.
- gas barrier resin films and their laminated films have a large temperature and humidity dependence and cannot maintain a high level of gas barrier properties, and also have a problem of vinyl chloride dendrimer. There was a problem that rilonitrile, etc. could generate harmful substances during disposal and incineration.
- inorganic oxides such as silicon oxide, aluminum oxide, and magnesium oxide as described in Japanese Patent Publication No. 63-28017 are used.
- a gas-barrier laminated film having a vapor-deposited film deposited on a plastic film by a forming method such as a vacuum vapor deposition method or a sputtering method is provided. It is known that these vapor-deposited films have transparency and gas barrier properties against oxygen and water vapor.
- metallized films and gas-barrier laminated films are usually used to enhance these properties or to exhibit the properties of other substrates, or even to the same type of phenolic film or film. It is often used by laminating with different kinds of finolems.
- Japanese Patent Publication No. 58-42027 discloses that the same or different film on which metal or metal compound is deposited is coated on both sides of an adhesive layer having a thickness of 1.5 to 35 / zm.
- a packaging material composed of a metal-deposited film composite in which the metal-deposited surface is laminated on the inside is proposed.
- Various kinds of high Molecular adhesive and dry lamination adhesive are used.
- the dry lamination method using a two-component reactive adhesive consisting of a base material and a curing agent is often used.
- a polyol and a polyisocyanate are used and, if necessary, a catalyst is applied and reacted to obtain a polymer having a degree of polymerization suitable for the intended use.
- Polyols or polyesters with two functions are used as polyols, and polyisocyanates such as tolylene diisocyanate (TDI) and diphenylmethane diisocyanate (MDI). Kisamethylene range asso- ciate (XDI), iso-holi- range asso- ciate (IPDI), etc. are mainly used.
- the present invention has been made in order to solve the above-mentioned problems of the prior art, and has a high gas barrier property against gases such as oxygen and water vapor, and has a high transparency.
- the purpose is to provide rum.
- Another object of the present invention is to seal using a gas-parallel laminated film having high gas barrier properties against gases such as oxygen and water vapor and having high transparency. It is an object of the present invention to provide an electroluminescent light emitting element, an electroluminescent display device, and an electrophoretic display panel.
- the present invention provides, firstly, a first transparent gas barrier film, an adhesive layer having a thickness of 1 to 30 ⁇ m provided on the first transparent gas layer film, and the adhesive layer.
- a transparent gas barrier laminate film comprising: a second transparent gas barrier film provided on the layer.
- the present invention provides a transparent electrode layer, an electroluminescence luminescent layer provided on the transparent electrode layer, and a dielectric luminescent layer provided on the electroluminescence luminescent layer.
- a laminate including one of the body layer and the insulating layer, and a back electrode layer provided thereon; a first transparent gas barrier film sealed over the laminate;
- a transparent gas including an adhesive layer having a thickness of l to 30 m provided on a first transparent gas film, and a second transparent gas barrier film provided on the adhesive layer
- a third aspect of the present invention is to provide an electroluminescent light-emitting device having a laminated film and a color filter layer provided on the color filter layer.
- Transparent electrode layer provided on the transparent electrode
- a laminate including an electrode layer;
- the present invention provides an electronic luminescence display device comprising: a transparent gas layer laminated film including a second transparent gas layer film provided on a layer ′. 4, a transparent electrode layer, a display region provided on the transparent electrode layer, the display region including electrophoretic particles and an insulating fluid for dispersing the electrophoretic particles, and a back electrode provided on the display region A display unit,
- An electrophoretic display panel comprising: a transparent gas barrier laminated film including a second transparent gas / rear film provided on the adhesive layer.
- FIG. 1 is a cross-sectional view showing a first example of the transparent gas barrier laminated film of the present invention.
- FIG. 2 is a sectional view showing a second example of the transparent gas barrier laminated film of the present invention.
- FIG. 3 is a cross-sectional view illustrating a third example of the transparent gas barrier laminated film of the present invention.
- FIG. 4 shows a fourth example of the transparent gas-noise laminated film of the present invention.
- FIG. 5 is a cross-sectional view showing a fifth example of the transparent gas barrier laminated film of the present invention.
- FIG. 6 is a cross-sectional view showing a sixth example of the transparent gas barrier laminated film of the present invention.
- FIG. 7 is a sectional view showing a seventh example of the transparent gas barrier laminated film of the present invention.
- FIG. 8 is a sectional view showing an eighth example of the transparent gas barrier laminated film of the present invention.
- FIG. 9 is a cross-sectional view illustrating a configuration of an example of the electroluminescence light emitting device of the present invention.
- FIG. 10 is a cross-sectional view illustrating a configuration of an example of the electronic aperture luminescence display device of the present invention.
- FIG. 11 is a cross-sectional view illustrating a configuration of an example of the electrophoretic display panel of the present invention.
- the transparent gas barrier laminated film of the present invention is provided at least in at least two transparent gas norm films and at least one between the transparent gas norm films. And an adhesive layer having a thickness of 1 to 30 ⁇ m.
- the adhesive layer is formed using an adhesive (self-adhesive).
- This pressure-sensitive adhesive is also called a pressure-sensitive adhesive, has cohesive strength and elasticity, has long-lasting tackiness at room temperature, and requires only a slight pressure without the need for heat or solvent. in Idei intends cohesion come this c Ru can adhere to the object corresponds to the force adhesive to withstand internal fracture.
- Elasticity is equivalent to the property of an object that changes its shape or volume when an external force is applied to it, and then recovers its original state when the force is removed.
- FIG. 1 is a sectional view showing a typical example of the transparent gas barrier laminated film of the present invention.
- the transparent gas barrier laminated film 10 has a configuration in which two transparent gas barrier films 1 are laminated via an adhesive layer 2.
- the present invention by bonding two transparent gas barrier films using this adhesive layer, it is possible to remove air bubbles which have been a problem in the conventional dry lamination.
- a transparent gas barrier laminated film without any generation can be easily obtained.
- the adhesive layer since the adhesive layer has elasticity, the obtained gas barrier laminated film is much stronger than the gas-parallel laminated film formed by dry lamination. Cracks due to external stress are less likely to occur and handling is easier.
- the transparent gas barrier laminated film having good transparency and strong stiffness is used as a packaging material for foods, pharmaceuticals, electronic parts, etc., or as an optical member for optical parts. It is preferably used for preventing water or oxygen from entering from the outside and preventing deterioration or defects caused by oxygen or moisture inside.
- the pressure-sensitive adhesive layer used in the present invention one having excellent transparency is used.
- the constituents of the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer include acryl-based, rubber-based, urethane-based, and vinyl ether-based.
- the form such as a silicone type include a solvent type, an emulsion type, a hot methylate type, and an ultraviolet curable type.
- acrylic-based premonomers or acrylic-based resins mainly containing acrylic-based monomers are preferred in terms of transparency, weather resistance, and the like.
- the acryl-based resin examples include a vinyl monomer having an acryl group, a virmonomer having an epoxy group, a virmonomer having an alkoxyl group, a vinyl monomer having an ethyleneoxide group, and a vinyl monomer having an ethylene oxide group.
- additives for example, natural resins such as rosin, modified rosin, derivatives of rosin and modified rosin, polyterpene resins, modified terpene, and fats, in order to improve the adhesive properties of the acrylic resin
- Natural resins such as rosin, modified rosin, derivatives of rosin and modified rosin, polyterpene resins, modified terpene, and fats
- Aromatic hydrocarbon resin, cyclopentadiene resin, aromatic petroleum resin, phenolic resin, alkyl-phenol-acetylene resin, coumarone-indene Tackifiers such as vinyl resins, vinyl toluene methyl styrene copolymers, aging inhibitors, stabilizers, and softeners can be added as necessary.
- an organic ultraviolet absorber such as benzophenone-based or benzotriazole-based can be added to the pressure-sensitive adhesive in order to increase light resistance.
- an adhesive can be applied to the lamination surface of any of the substrates to be laminated, and dried if necessary to form an adhesive layer.
- Applicators for this adhesive include a reverse roll coater, a knife coater, a no coater, a slot tie coater, a kanaif coater, a linoleous gravure coater, and a variogravure coater. Is used. The amount of adhesive applied is the thickness
- a range of 1 to 30 ⁇ is desirable.
- the other transparent gas barrier film is disposed, and pressure is optionally applied to the transparent gas barrier film.
- a laminated film can be formed.
- the transparent gas barrier film has a water vapor permeability of 0 to 50 g Zm 2 'day, or an oxygen permeability of SO or 50 cc / m 2 ⁇ day. ⁇ Atm is preferred.
- the water vapor permeability used here was measured at a temperature of 40 ° C using a water vapor transmission rate measuring device (PER MATRAN 3/31 manufactured by Modern Control Co., Ltd.) according to the JISK 7129B method. It can be measured under the conditions of ° C and 90% RH.
- the oxygen permeability used here is based on an oxygen permeability measuring device (modern control) according to the JISK 7126 method. It can be measured using OXTRAN 2/20) manufactured under the conditions of a temperature of 30 ° C and a humidity of 70 ° / oRH.
- the transparent gas film has a thickness of 9 ⁇ m to 50 ⁇ . If the thickness is less than 9 m, film formation becomes difficult and a film defect tends to occur. If the thickness exceeds 50 ⁇ m, processing efficiency such as vapor deposition or lamination tends to decrease.
- At least one of the two transparent gas films is an inorganic oxide vapor-deposited film including a substrate and an inorganic oxide vapor-deposited layer deposited on the substrate. be able to.
- FIG. 2 is a cross-sectional view showing a modified example of the transparent gas barrier laminated film of FIG.
- this transparent gas barrier laminated film 20 is composed of two transparent gas layers, each having a base material 3 and an inorganic oxide deposition layer 4 deposited on the base material 3.
- the base material of the inorganic oxide vapor-deposited film used in the present invention includes a polyethylene terephthalate (PET) film and a polyethylene terephthalate (PEN) film.
- PET polyethylene terephthalate
- PEN polyethylene terephthalate
- PBT polybutylene terephthalate
- PET polyethylene terephthalate
- various known additives and stabilizers can be added to the substrate. Additives and Examples of stabilizers and stabilizers include antistatic agents, plasticizers, and lubricants.
- a pretreatment can be performed on the lamination surface side of the substrate.
- a corona treatment any of a corona treatment, a low-temperature plasma treatment, an ion bombardment treatment, a chemical treatment, and a solvent treatment may be applied.
- the thickness of the substrate is preferably 9 to 50 m.
- the deposition layer made of the inorganic oxide includes aluminum oxide, silicon oxide, tin oxide, magnesium oxide, or a mixture thereof. It is desired that the inorganic oxide deposition layer has transparency and has a gas barrier property against oxygen or water vapor. More preferably, one or more of aluminum oxide, silicon oxide, and magnesium oxide can be used.
- the optimum thickness of the inorganic oxide vapor-deposited layer varies depending on the type of the inorganic compound used and the structure of the vapor-deposited layer, but is preferably in the range of 5 to 300 nm. If the thickness is less than 5 nm, a uniform film cannot be obtained, and the gas barrier property tends to decrease.If the thickness exceeds 300 nm, an inorganic oxide vapor deposition film is formed. Film flexibility is degraded, and the film tends to crack due to external factors such as bending and stretching after film formation.
- the thickness of the inorganic oxide deposited layer is preferably in the range of 10 to 150 nm.
- a usual vacuum vapor deposition method is used. It can. It is also possible to use other thin film forming methods such as a sputtering method, an ion plating method, and a plasma vapor deposition (CVD) method. In consideration of productivity, a vacuum deposition method can be preferably used.
- a heating means of the vacuum evaporation method any of an electron beam heating method, a resistance heating method, and an induction heating method is preferable.
- the deposition in order to improve the adhesion between the deposited layer and the base material and the denseness of the deposited layer, the deposition can be performed by using a plasma assist method or an ion beam assist method.
- reactive deposition in which an oxygen gas or the like is blown can be performed during the deposition.
- one of the transparent gas barrier films is an inorganic oxide vapor-deposited film
- another gas barrier film for example, a transparent gas barrier resin layer can be laminated on the other.
- FIG. 3 is a cross-sectional view showing a modified example of the transparent gas barrier laminated film of FIG.
- the transparent gas layer laminated film 30 is composed of a base material 3 and an inorganic oxide vapor deposited layer 4 deposited on the base material 3.
- the other transparent gas layer is composed of the transparent gas barrier resin layer 5
- the transparent gas barrier resin layer 5 and the inorganic oxide vapor deposition film are composed of the transparent gas barrier resin layer 5.
- It has a configuration in which an inorganic oxide vapor-deposited layer 4 and a vapor-deposited film are laminated via an adhesive layer 2.
- the gas barrier resin applied to the transparent gas barrier film include a polyvinyl alcohol copolymer (PVOH), an ethylene / vinyl alcohol copolymer (EVOH), and a vinylidene chloride film. (PVDC).
- each of the transparent gaseous films has a thickness of 9 to 50 ⁇ m. If the thickness is less than 9 / m, film formation becomes difficult, and the film is difficult to form. There is a tendency for defects to occur, and when it exceeds 50 m, processing efficiency such as lamination processing tends to decrease.
- the transparent gas barrier laminated film the transparent gas barrier resin layer, the inorganic oxide vapor-deposited film, or the like can be used alone or in a laminated state.
- the lamination include a multilayer body composed of a plurality of transparent gas barrier resin layers, a multilayer body composed of a plurality of inorganic oxide vapor-deposited films, or a transparent gas barrier resin layer and an inorganic oxide vapor deposition
- the film include a film laminate, a laminate of a transparent gas barrier resin layer or an inorganic oxide vapor-deposited film and another resin layer, and a multilayer thereof.
- a gas barrier coating layer can be preferably used.
- FIG. 4 is a cross-sectional view showing a modified example of the transparent gas barrier laminated film of FIG.
- this transparent gas-norm laminated film 40 is composed of two transparent gas-norm films each having a base material 3 and an inorganic oxide vapor-deposited layer formed on the base material 3. 4, Formed on inorganic oxide deposited layer 4
- the composite film 8 includes a first gas barrier coating layer 6 formed, and the two composite films 8 are laminated via the adhesive layer 2.
- the gas barrier coating layer includes, for example, a water-soluble polymer and at least one of (a) one or more metal alkoxides or Z and a hydrolyzate thereof, and (b) tin chloride.
- a layer formed by applying a coating agent mainly composed of an aqueous solution or a mixed solution of water and alcohol and heating and drying the coating agent can be used.
- a solution prepared by dissolving a water-soluble polymer and tin chloride in an aqueous (water or water / alcohol mixture) solvent, or a solution obtained by directly or preliminarily hydrolyzing a metal alkoxide thereto is used.
- a mixed solution and use it as a coating agent is coated on the inorganic oxide deposited layer 4 and then dried by heating.
- Each component contained in this coating agent will be described in more detail.
- the water-soluble polymer used in the coating agent of the present invention includes polyvinyl alcohol, polyvinylpyrrolidone, starch, methinoresenolose, casreboxime cinnoresorenolose and sodium anoreginate. And the like.
- poly-vinyl alcohol hereinafter referred to as PVA
- Gas barrier properties are particularly excellent when PVA is used.
- the PVA used here is generally obtained by saponifying polyacetic acid butyl. For example, only a few percent of the so-called partially saponified PVA and acetic acid groups in which tens of percent of acetic acid groups remain remain. Not include complete PVA etc.
- tin chloride used in Koti ring agent stannous chloride (S n C 1 2), stannic chloride (S n C l 4), or a mixture thereof. These tin chlorides may be anhydrous or hydrated.
- Et al is a metal alkoxy de the general formula, M (OR) n (M : S i, T i, A 1, metals such as Z r, R: CH 3, C 2 H 5 or the like alkyl group)
- M (OR) n M : S i, T i, A 1, metals such as Z r, R: CH 3, C 2 H 5 or the like alkyl group
- Is a compound represented by Specific examples include tetraethoxysilane (Si (OC 2 H 5 ) 4), trisiso-porous aluminum (A 1 (0-2, -C 3 H 7 ) 3), etc. those mentioned force s alone or with the Ki that Calling mixed and used. These are relatively stable in aqueous solvents after hydrolysis
- additives such as an isocyanate compound, a silane coupling agent, or a dispersant stabilizer, viscosity modifier, or colorant as necessary, as long as the gas barrier properties of the coating agent are not impaired. be able to.
- an isocyanate compound to be added to the coating agent a compound having two or more isocyanate groups in its molecule is preferable.
- monomers such as tolylene diisocyanate, triphenylmethanthrene lysocyanate, tetramethyl xylendigen socyanate, and polymers and derivatives thereof.
- the coating agent may be applied by a conventionally known method such as a diving method, a roll coating method, a screen printing method, a spray method, or a gravure printing method which is generally used. But it can.
- the thickness of the gas barrier coating layer varies depending on the type of coating agent, processing machine and processing conditions, but is preferably in the range of 0.01 to 50 ⁇ m. And more preferably in the range of 1 to 15 ⁇ m.
- the thickness of the gas barrier coating layer after drying is less than 0.01 / m, there is a tendency that a uniform coating film cannot be obtained and sufficient gas barrier properties cannot be obtained. On the other hand, when the thickness force exceeds S50 / im, cracks tend to occur in the gas barrier coating layer.
- FIG. 5 is a cross-sectional view showing a modified example of the transparent gas barrier laminated film of FIG.
- the transparent gas barrier laminated film 50 is composed of a base material 3 and a first inorganic oxide deposition layer formed by depositing one of the transparent gas barrier films on the base material 3. 4, a composite film including a gas-parallel coating layer 6 formed on the first inorganic oxide vapor-deposited layer 4; a composite film 8; and the other transparent gas barrier film is a transparent gas barrier. It has a configuration in which a transparent resin layer 5 and a gas barrier coating layer 6 are laminated via an adhesive layer 2.
- a first inorganic oxide vapor-deposited layer was formed on a substrate, and a first gas barrier coating layer was formed thereon. Thereafter, a second inorganic oxide deposition layer can be further deposited. Furthermore, a second gas barrier coating layer can be formed on the second inorganic oxide vapor-deposited layer.
- the composite film obtained by laminating the inorganic oxide deposition layer and the gas barrier coating layer on the base material has a better film quality. It has sublimation properties.
- FIG. 6 is a cross-sectional view showing a modified example of the transparent gas barrier laminated film of FIG.
- this transparent gas barrier laminated film 60 has a first inorganic oxide vapor deposition film in which two transparent gas film films are deposited on the substrate 3 and the substrate 3, respectively.
- Layer 4 first gas barrier coating layer 6 formed on first inorganic oxide vapor deposition layer 4, second inorganic coating layer 6 formed on first gas barrier coating layer 6
- a composite film 8 ′ including a deposited oxide layer 4 ′ and a second gas barrier coating layer 6 ′ formed on the deposited second inorganic oxide layer 4 ′, 2 has a configuration in which a gas barrier coating layer 6 ′ is laminated via an adhesive layer 2.
- FIG. 7 is a cross-sectional view showing a modified example of the transparent gas barrier laminated film of FIG.
- this transparent gas barrier laminated film 70 is composed of a base material 3, a first inorganic oxide deposition layer 4 on which one transparent gas barrier film is deposited on the base material 3.
- Is composed of a transparent gas barrier resin layer 5, and the transparent gas barrier resin layer 5 and the second gas barrier coating layer 6 ′ are laminated via the adhesive layer 2.
- a heat seal layer can be formed on one main surface.
- This heat seal layer can be provided as a heat bonding layer when the transparent vapor-deposited film laminate is practically used as a package such as a bag or an optical component.
- FIG. 8 is a cross-sectional view showing a modified example of the transparent gas barrier laminated film of FIG.
- the transparent gas barrier laminated film 80 is composed of two transparent gas barrier films 1 laminated through an adhesive layer 2, and one of the transparent gas barrier films 1. Has a configuration in which a heat seal layer 9 is further formed on a surface opposite to the surface on which the adhesive layer 2 is laminated.
- the transparent gas nori film 1 in FIG. 8 the inorganic oxide vapor-deposited film 7, the transparent gas barrier resin layer 5, and the composite films 8, 8 'as described above are used. One or more may be applied.
- the heat seal layer examples include, for example, polyethylene, polypropylene, ethylene-butyl acetate copolymer, ethylene-methacrylic acid copolymer, ethylene- Resins such as a methacrylic acid ester copolymer, an ethylene-acrylic acid copolymer, an ethylene-acrylic acid ester copolymer, and a metal crosslinked product thereof are used.
- the thickness is determined according to the purpose, but is generally in the range of 15 to 200 / xm.
- the method for forming the heat seal layer is preferably extrusion extrusion.
- a lamination method or the like can be used, but lamination can be performed by other known methods.
- Examples of the adhesive resin used in the above-mentioned extrusion sand lamination method include, for example, an ethylene-butyl acetate copolymer, an ethylene-methacrylic acid copolymer, and an ethylene-acrylyl.
- Polyester film base material is not coated with anchor coat, and extruded laminated resin melt film is not subjected to ozone treatment.
- Ethylene-methyl methacrylate acid copolymer (for example, Mitsui 'Dupont Polychemical Co., Ltd. Cranle AN 4 228 C ”) is preferably used.
- the transparent gas barrier laminated film of the present invention can be suitably used for packaging materials, optical components and the like.
- the electroluminescence light-emitting device of the present invention is one of examples in which the transparent gas barrier laminated film of the present invention is used as an optical component.
- Thickness provided on the first transparent gas barrier film and the first transparent gas barrier film sealed over the laminate And a transparent gas barrier laminated film including a second transparent gas barrier film provided on the adhesive layer, having a thickness of 1 to 30 ⁇ .
- Each of the electrode layer, the insulating layer, the dielectric layer, and the electroluminescent light emitting layer can be formed by using a known method, for example, a vapor deposition and sputtering method.
- FIG. 9 is a cross-sectional view illustrating a configuration of an example of the electroluminescence light emitting device of the present invention.
- the emission luminescent element 90 is provided on a transparent electrode layer 11 made of, for example, indium lead oxide and a transparent electrode layer 11 connected to electrodes (not shown).
- a transparent electrode layer 11 made of, for example, indium lead oxide and a transparent electrode layer 11 connected to electrodes (not shown).
- the laminated body includes a back electrode layer 14 made of a metal, and a sealing film 10 as shown in FIG. 8, for example, which is sealed to cover the laminated body.
- an electroluminescence display device is an example of a display device using the above-described electroluminescence light emitting element.
- First transparent gas barrier fill sealed over the stack A transparent layer including an adhesive layer having a thickness of 1 to 30 ⁇ m provided on the first transparent gas barrier film, and a second transparent gas barrier film provided on the adhesive layer.
- a gas barrier laminated film is provided.
- the color final letter can be formed by a known method such as a photolithographic method.
- Each of the electrode layer, the insulating layer, the dielectric layer, and the electroluminescent luminescent layer can be formed by using a well-known method such as a vapor deposition method and a sputtering method.
- FIG. 10 is a cross-sectional view illustrating a configuration of an example of the electroluminescence display device of the present invention.
- the electroluminescence display device 100 is provided on the color filter layer 15 and the color filter layer 15 and connected to an electrode (not shown).
- FIG. 8 shows an example in which a laminated body provided on the dielectric layer 13 and including a back electrode layer 14 made of, for example, a metal connected to an electrode (not shown) and the laminated body is sealed.
- a sealing film 10 as shown in FIG.
- electrophoretic display panel of the present invention is another one of the examples in which the transparent gas barrier laminated film of the present invention is used as an optical component
- the display unit may include, for example, a capsule enclosing an insulating fluid in which electrophoretic particles are dispersed.
- an insulating fluid in which electrophoretic particles are dispersed can be sealed in a region partitioned by the partition.
- a plurality of such capsules and partitioned areas are provided and can be arranged in a predetermined pattern.
- FIG. 11 is a cross-sectional view illustrating a configuration of an example of the electrophoretic display panel of the present invention.
- this electrophoretic display panel is composed of a transparent glass substrate 25, pixels formed of a predetermined pattern on the transparent glass substrate 25, and made of, for example, lead oxide of indium oxide.
- a sealing film 10 having the following configuration.
- This microcapsule 23 can be created, for example, as follows.
- titanium oxide having an average particle diameter of 3 ⁇ m was coated in 100 parts of tetrachloroethylene solvent as white particles and coated with a polyethylene resin that is negatively charged in the solution. And 40 parts of carbon black with an average particle size of 4.0 ⁇ m, which was surface-treated as a black particle and treated with an alkyl trimethylammonium To make a dispersion.
- the obtained P-W emulsion was mixed with 80 parts of water adjusted to 40 ° C. and 10 parts of aromatic rubber by mixing with a disperser. While maintaining the temperature of the solution at 40 ° C, ) Prepare H to 4 and form a microcapsule capsule wall by coacervation.
- the temperature of the solution is lowered to 5 ° C, and 1.9 parts of a 37% by weight formalin solution is applied to harden the microcapsules.
- a microcapsule enclosing the white particles, the black particles, and the insulating solution for dispersing these particles is obtained.
- a transparent electrode of, for example, indium lead oxide on one of the transparent glass substrates by, for example, sputtering, etc.
- the coating liquid containing the capsule and binder is coated and dried, and a transparent electrode such as indium lead oxide is formed on the other transparent glass substrate by, for example, sputtering.
- the electrophoretic display panel of the present invention can be formed by laminating the transparent electrode and the microcapsule on the inside.
- an adhesive may be used, and another resin film may be further laminated.
- resin films include, for example, polyethylene terephthalate (PET) and polyethylene terephthalate (PEN), and the like.
- PET polyethylene terephthalate
- PEN polyethylene terephthalate
- Polyolefins such as polyethylene and polypropylene, polystyrene, polystyrene, polyamide, polycarbonate, polyacrylonitrile and polyolefin
- a transparent film such as a polyimide film can be used. These may be stretched or unstretched as long as they have mechanical strength and dimensional stability.
- a polyethylene terephthalate film stretched arbitrarily in the biaxial direction is preferably used from the viewpoint of heat resistance and the like.
- the lamination side of the substrate is pretreated as a corona treatment, low-temperature plasma treatment, ion bombardment treatment, chemical treatment, solvent treatment, etc. Processing may be performed.
- a biaxially stretched PET film having a thickness of 12 im was provided as the substrate.
- This PET film was placed in a vacuum evaporation system using the electron beam heating method, metal aluminum was evaporated, and oxygen gas was introduced into the PET film.
- An aluminum oxide layer having a thickness of 3 mm was deposited to obtain a first deposited layer.
- the obtained intermediate layer coating solution was applied by a gravure coating method, and then dried at 120 ° C. for 1 minute to form a first gas barrier coating layer having a thickness of 5 m. Formed.
- the substrate on which the first vapor deposition layer and the first gas barrier coating layer are formed is placed in a vacuum vapor deposition device using an electron beam heating method, and the metal aluminum is evaporated.
- the aluminum oxide layer having a thickness of 15 nm was vaporized while introducing oxygen gas into the To form a second deposited layer.
- a transparent laminate was obtained by forming a second gas barrier coating layer on the second vapor deposition layer in the same manner as described above.
- the water vapor permeability of this inorganic oxide vapor-deposited film is 7 at 0.04 g / ⁇ ⁇ day.
- BXX5134 manufactured by Toyo Ink Mfg. Co., Ltd.
- Toyo Ink Mfg. Co., Ltd. The second gas barrier coating layer surface of the other inorganic oxide vapor-deposited film was overlaid on the obtained adhesive layer, and pressure-bonded to obtain a transparent gas barrier laminated film.
- the obtained transparent gas barrier laminated film had good transparency, and no unevenness was observed in the transparency.
- the waist strength of the film was measured as follows.
- a strip-shaped test piece (horizontal) measuring 200 mm in the width direction and 15 mm in the length direction, and 20 O in the length direction 3 mm long and 15 mm long strip-shaped test pieces (vertical) in the width direction were cut out.
- Both sides of Toyo Seiki Mfg. Co., Ltd. Attach the fixed fixtures of both sides to the center by mounting the fixed fixtures at a distance of 150 ram between the two fixed fixtures, and bring the test pieces into contact with the movable fixtures of both sides. After making the loop shape, tilt it toward the sensor at 90 °, approach it until it comes into contact with the sensor, measure the strength at the time of this contact, and calculate the average of the measured values of the three test pieces as the waist strength. did.
- the waist strength of the test piece (vertical) was 1.29 g
- the waist strength of the test piece (horizontal) was 1.22 g.
- the obtained transparent gas channel laminated film is used as a sealing film to form an electrifying film having the same configuration as that shown in FIGS. 9, 10, and 11, respectively.
- the transparency was good and the laminated film did not crack.
- an adhesive using polycarbonate and polyisocyanate instead of an adhesive on the second gas barrier coating layer (main agent: Takeda Mitsui Chemicals, Inc.) A5 15 hardening agent: A50) manufactured by Mitsui Takeda Chemical Co., Ltd. is applied, and the gas barrier of the other inorganic oxide vapor-deposited film is applied using a dry laminating machine.
- the gas coating layer side was overlaid and laminated to obtain a gas-barrier laminated finolem.
- the obtained gas-barrier laminated film had transparency but was uneven, and a plurality of striped patterns could be visually confirmed.
- the obtained gas barrier laminated film was When the waist strength was measured in the same manner as in Example 1, the waist strength of the test piece (longitudinal) was 0.556 g, and the waist strength of the test piece (horizontal) was 0.55 g. The waist strength was far inferior to 1. It was hard when picked up.
- the gas barrier laminate film of Example 1 has significantly higher transparency and waist strength than the gas barrier laminate film of Comparative Example 1. Was.
- the transparent gas barrier laminated film of the present invention has a high gas barrier property against oxygen, water vapor and the like, and is excellent in transparency. For this reason, it is suitably used as an optical film or packaging material used in the fields of foods, pharmaceuticals, electronic members, optical members, etc., which require high gas barrier properties and high transparency.
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Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
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EP20040732807 EP1634697B1 (en) | 2003-05-16 | 2004-05-13 | Transparent gas barrier multilayer film, electroluminescent light-emitting device using same, electroluminescent display, and electrophoretic display panel |
CN2004800132537A CN1791510B (zh) | 2003-05-16 | 2004-05-13 | 透明的气体屏蔽性层合薄膜、电致发光元件、电致发光显示装置以及电泳显示板 |
JP2005506247A JP4654911B2 (ja) | 2003-05-16 | 2004-05-13 | 透明ガスバリア積層フィルム、これを用いたエレクトロルミネッセンス発光素子、エレクトロルミネッセンス表示装置、及び電気泳動式表示パネル |
CA 2525622 CA2525622C (en) | 2003-05-16 | 2004-05-13 | Transparent gas barrier laminated film, and electroluminescent light-emiiting element, electroluminescent display device, and electrophoretic display panel using the same |
US11/272,809 US20060062995A1 (en) | 2003-05-16 | 2005-11-15 | Transparent gas barrier laminated film, and electroluminescent light-emitting element, electroluminescent display device, and electrophoretic display panel using the same |
Applications Claiming Priority (2)
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JP2003138316 | 2003-05-16 | ||
JP2003-138316 | 2003-05-16 |
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US11/272,809 Continuation US20060062995A1 (en) | 2003-05-16 | 2005-11-15 | Transparent gas barrier laminated film, and electroluminescent light-emitting element, electroluminescent display device, and electrophoretic display panel using the same |
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WO2004101276A1 true WO2004101276A1 (ja) | 2004-11-25 |
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US (1) | US20060062995A1 (ja) |
EP (1) | EP1634697B1 (ja) |
JP (1) | JP4654911B2 (ja) |
KR (1) | KR100704269B1 (ja) |
CN (1) | CN1791510B (ja) |
CA (1) | CA2525622C (ja) |
TW (1) | TWI294827B (ja) |
WO (1) | WO2004101276A1 (ja) |
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JP2007169519A (ja) * | 2005-12-22 | 2007-07-05 | Mitsubishi Plastics Ind Ltd | 粘着シート |
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Also Published As
Publication number | Publication date |
---|---|
TW200510177A (en) | 2005-03-16 |
CA2525622C (en) | 2010-10-26 |
KR100704269B1 (ko) | 2007-04-09 |
CN1791510A (zh) | 2006-06-21 |
EP1634697A1 (en) | 2006-03-15 |
EP1634697B1 (en) | 2014-08-27 |
EP1634697A4 (en) | 2011-07-06 |
TWI294827B (en) | 2008-03-21 |
KR20060008999A (ko) | 2006-01-27 |
CA2525622A1 (en) | 2004-11-25 |
JPWO2004101276A1 (ja) | 2006-07-13 |
JP4654911B2 (ja) | 2011-03-23 |
US20060062995A1 (en) | 2006-03-23 |
CN1791510B (zh) | 2010-10-13 |
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