CN101389166A - Gas barrier film, and display device comprising the same - Google Patents
Gas barrier film, and display device comprising the same Download PDFInfo
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- CN101389166A CN101389166A CNA2008102159731A CN200810215973A CN101389166A CN 101389166 A CN101389166 A CN 101389166A CN A2008102159731 A CNA2008102159731 A CN A2008102159731A CN 200810215973 A CN200810215973 A CN 200810215973A CN 101389166 A CN101389166 A CN 101389166A
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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
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/10—Apparatus or processes specially adapted to the manufacture of electroluminescent light sources
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/724—Permeability to gases, adsorption
- B32B2307/7242—Non-permeable
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
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Abstract
The invention relates to a gas barrier film, and a display device comprising the same. The gas barrier film has can effectively prevent moisture penetration through the other surface thereof not having the gas-barrier layer. Disclosed is a gas barrier film having, on one surface of a substrate film, a gas-barrier layer comprising at least one organic region and at least one inorganic region, and having, as a barrier property-having layer, only a layer comprising a barrier property-having resin as the main ingredient of the layer on the other surface of the substrate film.
Description
Technical field
The display element that the present invention relates to gas barrier film and manufacture method thereof and adopted gas barrier film.
Background technology
The gas barrier film that all in display element such as research organic EL etc., uses of people all the time.Disclose in the TOHKEMY 2007-30451 communique and a kind ofly on a face of base film, be provided with barrier layer for gases, be provided with the gas barrier film that glass transition temperature is the resin bed more than 60 ℃ on another face.In addition, a kind of gas barrier film that is provided with barrier layer for gases on a face of base film, is provided with anti-solvent layer on another face is disclosed in Japanese kokai publication hei 9-254303 communique.But such gas barrier film be not provided with covering property of shortage moisture on the one side of barrier layer for gases.Therefore, in the manufacture process of organic EL etc., can be subjected to influence because of film is taken in moisture etc. or the composition release taken in etc. produces.
On the other hand, a kind of gas barrier film that all has organic-inorganic cascade type barrier layer for gases on the two sides of base film is disclosed in TOHKEMY 2006-35737 communique.But, in TOHKEMY 2006-35737 communique, owing to be equipped with organic-inorganic cascade type barrier layer for gases on the two sides, so it makes comparatively difficulty.
Summary of the invention
The objective of the invention is to solve above-mentioned problem, only on single face, be provided with organic-inorganic cascade type barrier layer for gases and can prevent effectively that also moisture from never establishing the gas barrier film that a side of barrier layer for gases is infiltrated even promptly provide.
Based on above-mentioned problem, the inventor concentrates on studies, found that: the single face by base film is provided with the inorganic cascade type barrier layer for gases of machine, and be the layer that the layer (below be sometimes referred to as " block resin bed ") of main component is used as having barrier properties only being provided with on another face with the resin with barrier properties, can solve above-mentioned problem.Particularly, realize by the following method.
(1) gas barrier film, it has barrier layer for gases on a face of base film, this barrier layer for gases has at least 1 organic zone and at least 1 inorganic zone, and only having with the resin with barrier properties on another face of above-mentioned base film is the layer that the layer of main component is used as having barrier properties.
(2) as (1) described gas barrier film, wherein, barrier layer for gases has at least 1 layer of organic layer and at least 1 layer of inorganic layer.
(3) as (1) or (2) described gas barrier film, wherein, with the resin with barrier properties be main component the layer in resin be polyvinyl alcohol.
(4) as (1) or (2) described gas barrier film, wherein, with the resin with barrier properties be main component the layer in resin be polyfunctional acrylic ester.
(5) as each described gas barrier film in (2)～(4), wherein, organic layer contains by making that at least a kind of composition with bis-phenol skeleton (methyl) acrylate is solidified to form.
(6) as each described gas barrier film in (2)～(5), wherein, with the resin with barrier properties be main component the layer identical with the main component of organic layer.
(7), wherein, be that the layer of main component and the main component of organic layer are (methyl) acrylate derivative with resin with barrier properties as each described gas barrier film in (2), (4)～(6).
(8) as each described gas barrier film in (1)～(7), wherein, with the resin with barrier properties be main component the layer thickness be 0.5～30 μ m.
(9) as each described gas barrier film in (1)～(8), wherein, the thickness of gas barrier film is 10～300 μ m.
(10) as each described gas barrier film in (1)～(9), it is used for display element.
(11) manufacture method of each described gas barrier film is characterized in that in (1)～(10), after on the base film barrier layer for gases being set, is the layer of main component with the resin with barrier properties in the opposition side setting of above-mentioned base film.
(12) display element, it has adopted each described gas barrier film in (1)～(10).
As (12) described display element, it is characterized in that (13) gas barrier film is as the substrate of display element.
As (12) described display element, it is characterized in that (14) gas barrier film is as the sealing film of display element.
(15) as each described display element in (12)～(14), wherein, on display element by with resin be with barrier properties main component the layer be positioned at the outside mode gas barrier film is set.
According to the present invention, even only the single face of gas barrier film is provided with the inorganic cascade type barrier layer for gases of machine, also can suppress the base film absorption or discharge moisture or gas, consequently, when display elements such as making organic EL, can reduce the deterioration of this display element, thereby stably make display element.
Description of drawings
Skeleton diagram when Fig. 1 is expression with existing gas barrier film and gas barrier film of the present invention as the sealing film of organic EL.
Embodiment
Below content of the present invention is elaborated.In addition, "～" is meant that the numerical value that comprises its front and back record is as lower limit and higher limit in this specification.Organic EL among the present invention refers to organic electroluminescent device.
Gas barrier film of the present invention is characterised in that, on a face of base film, be provided with barrier layer for gases, this barrier layer for gases (being sometimes referred to as " organic-inorganic cascade type barrier layer for gases " in this specification) has at least 1 organic zone and at least 1 inorganic zone, and only being provided with the resin with barrier properties on another face of base film is the layer that the layer (block resin bed) of main component is used as having barrier properties.
At this, about the block resin bed, first composition that constitutes this layer is the resin with barrier properties, and it contains the resin that has barrier properties more than the 80 weight % usually.Therefore, in the scope that does not break away from purport of the present invention, do not get rid of the composition that contains other." as the layer with barrier properties " is meant, can only be provided with this block resin bed as the layer with barrier properties, also can be provided with the layer with other functions.That is, the execution mode that is provided with other barrier layer for gases does not belong to scope of the present invention, is used to make the block resin bed and the adhesive linkage of base film applying or the execution mode of other functional layers to belong to scope of the present invention but be provided with.
Below, be that example describes with the situation that gas barrier film of the present invention is used for the sealing film of organic EL.Certainly, the present invention and be not limited to these execution modes.
Skeleton diagram when Fig. 1 is used for the sealing film of organic EL for expression with existing gas barrier film and gas barrier film of the present invention (a) is represented existing gas barrier film, (b) represents gas barrier film of the present invention.Here use respectively: 1 expression base film, 2 expression organic-inorganic cascade type barrier layer for gases, 3 expression block resin beds.In addition, (c) be organic EL, on substrate 4, be provided with pair of electrodes and this electrode and the duplexer 5 of being located at this interelectrode organic compound layer etc.
If adopt existing gas barrier film (a), then moisture infiltrates from base film 1 side, because this is impregnated with gas barrier film and organic EL applying of the state of moisture, thereby the problem that causes the element deterioration because of moisture is arranged.And if adopt gas barrier film of the present invention (b), then organic-inorganic cascade type barrier layer for gases 2 and block resin bed 3 can prevent that moisture from infiltrating.
In addition, in Fig. 1, the sealing film that gas barrier film of the present invention is used as organic EL uses, but also can be used as the substrate use of organic EL, also can be used as both and uses.And, also can in other display element, use.In these cases, preferably the block resin bed is located at the outside of display element.
The thickness of gas barrier film of the present invention is preferably 10～300 μ m, more preferably 25～250 μ m.
(is the layer of main component with the resin with barrier properties)
Of the present invention is that the resin with barrier properties of layer in (block resin bed) of main component is meant with the resin with barrier properties, for example suppresses the material to gas componant diffusions such as the oxygen of the material production influence that constitutes organic EL or moisture.Particularly, can list the polyfunctional acrylic ester that uses in the organic layer of polyvinyl alcohol, Vingon analog copolymer, ethylene-vinyl alcohol copolymer, the resin bed that contains synthetic mica, organic-inorganic cascade type barrier layer for gases, the pure and mild polyfunctional acrylic ester of preferably polyethylene.
The main component of the block resin bed preferably main component with the organic layer that constitutes barrier layer for gases is identical.Adopt such formation to have the advantage of easy film forming.
About the gas barrier of block resin bed, when measuring under 25 ℃, the condition of relative humidity 50%, preferred moisture-vapor transmission is 0.001～10g/m
2My god.
The thickness of block resin bed is preferably 0.5～30 μ m, more preferably 1～20 μ m.
The block resin bed preferably is provided with by coating resin composition on base film, also can adopt methods such as stickup resin film such as using bonding agent.
(barrier layer for gases)
Barrier layer for gases of the present invention is the layer with function of oxygen in the blocking blocking-up atmosphere, moisture, is the organic-inorganic cascade type that organic zone and inorganic zone or organic layer and inorganic layer are laminated.
Organic zone and inorganic zone or organic layer and inorganic layer are alternately laminated usually.When constituting, can be that each zone is along the so-called inclination material layer of film thickness direction continually varying by organic zone and inorganic zone.As above-mentioned inclination examples of material, can list disclosed organic layer and inorganic layer in the material, U.S. publication 2004-46497 specification of record in Kimura's the paper " vacuum science and technology journal A the 23rd volume; 971 pages～977 pages (distribution in 2005, U.S. vacuum association) (Journal of VacuumScience and Technology A Vol.23 p971-977 (2005 American VacuumSociety)) " and be continuous layer of no interface etc.Below, for the purpose of simplifying, organic layer and organic zone note are made " organic layer ", inorganic layer and inorganic zone note are made " inorganic layer ".
The number of plies that constitutes barrier layer for gases there is not particular restriction, typical preferred 2 layers～30 layers, more preferably 3 layers～20 layers.
The thickness of barrier layer for gases is not subjected to particular restriction, for example is 0.2～30 μ m, is preferably 0.5～15 μ m.
(inorganic layer)
The thin layer that inorganic layer is normally formed by metallic compound.About the formation method of inorganic layer, all can use so long as can form any method of aimed thin film.For example rubbing method, sputtering method, vacuum vapour deposition, ion plating method, plasma CVD method etc. all are suitable for, the formation method of particularly, can adopt Japan special permission No. 3400324, TOHKEMY 2002-322561 number, the record of TOHKEMY 2002-361774 communique.
As long as the composition that contains in the above-mentioned inorganic layer can satisfy above-mentioned performance, do not have particular restriction, for example can use and contain the oxide that is selected from the metal more than a kind among Si, Al, In, Sn, Zn, Ti, Cu, Ce or the Ta etc., nitride, carbide, oxynitride, oxycarbide, nitrogen carbide, oxygen nitrogen carbide etc.Wherein, be preferably selected from oxide, nitride or the oxynitride of the metal of Si, Al, In, Sn, Zn, Ti, metal oxide, nitride or the oxynitride of preferred especially Si or Al.They can also contain other elements as submember.
Thickness to above-mentioned inorganic layer does not have particular restriction, preferably in the scope of 5nm～500nm, and more preferably 10nm～200nm.In addition, also can stacked inorganic layer more than 2 layers.At this moment, each layer can be same composition, also can be different the composition.In addition, also can be that disclosed and interface organic layer are not obvious and form continually varying layer on film thickness direction in the U.S. publication 2004-46497 specification.
(organic layer)
Organic layer of the present invention is by forming as preferred free-radical polymerised compound of polymer and/or polymer with cationically polymerizable compound of this functional group of ether.
(polymerizable compound)
The polymerizable compound that the present invention uses is that end or side chain have the compound that the compound of ethylenic unsaturated bond and/or end or side chain have epoxy radicals or oxetanes.Wherein, preferred end or side chain have the compound of ethylenic unsaturated bond.Have the example of the compound of ethylenic unsaturated bond as end or side chain, can list (methyl) acrylic ester compound (acrylate and methacrylate combined statement are shown (methyl) acrylate), acrylamides, styrene compound, maleic anhydride etc.
As (methyl) acrylic ester compound, preferred (methyl) acrylate, carbamate (methyl) acrylate or polyester (methyl) acrylate, epoxy (methyl) acrylate etc.
As styrene compound, optimization styrene, AMS, 4-methyl styrene, divinylbenzene, 4-hydroxy styrenes, 4-carboxyl styrene etc.
Below, enumerate the object lesson of (methyl) acrylic ester compound, but the invention is not restricted to these.
(polymerization initiator)
Organic layer of the present invention generally solidifies it by the coating polymerizable composition, polymerizable composition and obtains, and this polymerizable composition, polymerizable composition can contain polymerization initiator.Using under the situation of Photoepolymerizationinitiater initiater, its content is preferably 0.1 mole of polymerizable compound total amount more than the %, more preferably 0.5～2 mole of %.Adopt such composition can suitably control the polymerization reaction of going through the active component reaction of formation.Example as Photoepolymerizationinitiater initiater, can list Irgacure series (for example Irgacure 651, Irgacure 754, Irgacure 184, Irgacure 2959, Irgacure 907, Irgacure369, Irgacure 379, Irgacure 819 etc.), Darocure series (for example Darocure TPO, Darocure 1173 etc.), Quantacure PDO that Ciba Specialty Chemicals sells, the Ezacure series (for example Ezacure TZM, Ezacure TZT etc.) that Sartomer company sells.
(the formation method of organic layer)
Formation method as organic layer does not have particular restriction, for example can adopt solution coat method or vacuum film formation method to form.As the solution coat method, for example can adopt the extrusion coated method of the use hopper of putting down in writing in dip coated method, airblade coating method, curtain formula rubbing method, rolling method, coiling rod rubbing method, intaglio plate rubbing method, slope stream rubbing method or No. 2681294 specification of United States Patent (USP) to be coated with.As the vacuum film formation method, there is not particular restriction, film build methods such as preferred evaporation, plasma CVD.In the present invention, polymer can be carried out solution coat, also can as disclosed in TOHKEMY 2000-323273 communique, the TOHKEMY 2004-25732 communique, adopt the hydridization rubbing method that contains organic/inorganic substance.
(cross-linking method of polymerizable compound)
In the present invention, above-mentioned polymerizable compound being heated or shining various energy-rays and carry out polymerization, crosslinked, is the organic layer of main component thereby form with the macromolecule.As the example of energy-ray, can list ultraviolet ray, visible light, infrared ray, electron ray, X ray, gamma-rays etc.At this moment, if carrying out polymerization with heat then adopts thermal polymerization,, then adopt Photoepolymerizationinitiater initiater and sensitizer if carry out polymerization with visible light if carrying out polymerization with ultraviolet ray then adopts Photoepolymerizationinitiater initiater.Wherein, preferably make the polymerizable compound polymerization that contains Photoepolymerizationinitiater initiater also crosslinked with ultraviolet ray.
In the present invention, usually the composition that contains polymerizable compound is carried out rayed it is solidified, the light of irradiation is generally the ultraviolet ray of high-pressure mercury lamp or low pressure mercury lamp generation.Irradiation energy is preferably 0.5J/cm
2More than, 2J/cm more preferably
2More than.(if methyl) acrylic ester compound, because of airborne oxygen can hinder its polymerization, oxygen concentration or partial pressure of oxygen when therefore preferably reducing polymerization.During oxygen concentration when reducing polymerization with the nitrogen displacement method, oxygen concentration is preferably below 2%, more preferably below 0.5%.During partial pressure of oxygen when reducing polymerization with the decompression method, total gas pressure is preferably below 1000Pa, more preferably below 100Pa.In addition, particularly preferably in shining 2J/cm under the reduced pressure below the 100Pa
2Above energy carries out polymerizable ultraviolet.
Organic layer of the present invention is with level and smooth and film hardness is high is advisable.The square mean roughness (Ra value) of the preferred 1 μ m of the flatness of organic layer more preferably is lower than 0.5nm for being lower than 1nm.The aggregate rate of monomer is preferably more than 85%, more preferably more than 88%, further preferably more than 90%, particularly preferably in more than 92%.Here so-called aggregate rate is meant the ratio of the polymerizable group that has reacted in the polymerizable group total in the monomer mixture (acryloyl group and methacryl).Aggregate rate can be measured by infrared absorption.
Thickness to organic layer does not have particular restriction, if thin excessively, then is difficult to obtain the thickness of homogeneous, if blocked up, then can produce the crack under the effect of external force and reduces block.Based on this viewpoint, the thickness of organic layer is preferably 50nm～2000nm, more preferably 200nm～1500nm.
As mentioned above, organic layer is smoothly to be advisable.The square mean roughness (Ra value) of the preferred 1 μ m of the flatness of organic layer more preferably is lower than 0.5nm for being lower than 1nm.Require the surface of organic layer not have foreign matter, projections such as particle.Therefore, preferably in the clean room, carry out the film forming of organic layer.Cleanliness factor is preferably below 10000 grades, more preferably below 1000 grades.
The hardness of organic layer is high more good more.If the hardness height of organic layer, then inorganic layer forms level and smooth film and improves blocking capability.The hardness of organic layer can be expressed as the small hardness based on the nano impress method.The small hardness of organic layer is preferably more than 150N/mm, more preferably more than 180N/mm, more than 200N/mm.
Organic layer is preferred stacked more than 2 layers.At this moment, at least 1 layer is that above-mentioned organic layer gets final product, and other organic layers can be above-mentioned organic layers, also can be the organic layers of other compositions.As 1 layer of organic layer, also can be not obvious and form continually varying layer on film thickness direction as disclosed and interface inorganic layer in the U.S. publication 2004-46497 specification.
(base film)
Gas barrier film of the present invention uses plastic film as base film usually.Employed plastic film does not have particular restriction to material, thickness etc. so long as can keep the film of duplexers such as organic layer, inorganic layer to get final product, and can wait suitably according to application target and select.As above-mentioned plastic film, specifically can list mylar; methacrylic resin; methacrylic acid-maleic acid; polystyrene resin; transparent fluororesin; polyimides; the fluorinated polyimide resin; polyamide; polyamide-imide resin; polyetherimide resin; the cellulose acylate resin; polyurethane resin; polyether-ether-ketone resin; polycarbonate resin; the ester ring type vistanex; polyarylate; polyethersulfone resin; polysulfone resin; cyclic olefine copolymer; fluorenes ring modified polycarbonate resin; alicyclic modified polycarbonate resin; fluorenes ring modified polyester resin; thermoplastic resins such as acryloyl compound.Wherein, preferred polyester resin (for example PETG (PET)), PEN (PEN).
When gas barrier film of the present invention was used as the substrate of components and parts such as organic EL described later, plastic film preferably formed by having stable on heating material.Particularly, be more than 100 ℃ by glass transition temperature (Tg) preferably and/or coefficient of linear thermal expansion is that high-fire resistance transparent material below 40ppm/ ℃ forms.Tg and coefficient of linear thermal expansion useful additives wait regulates.As such thermoplastic resin, can list PEN (PEN:120 ℃); Merlon (PC:140 ℃); ester ring type polyolefin (1,600 160 ℃ of the ZEONOR of for example Japanese Zeon Co., Ltd. system); polyarylate (PAr:210 ℃); polyether sulfone (PES:220 ℃); polysulfones (PSF:190 ℃); cyclic olefine copolymer (COC: the compound of TOHKEMY 2001-150584 communique: 162 ℃); polyimides (for example the ネ オ of Mitsubishi's aerochemistry Co., Ltd. プ リ system: 260 ℃); fluorenes ring modified polycarbonate (BCF-PC: the compound of TOHKEMY 2000-227603 communique: 225 ℃); alicyclic modified Merlon (IP-PC: the compound of TOHKEMY 2000-227603 communique: 205 ℃); acryloyl compound (compound of TOHKEMY 2002-80616 communique: more than 300 ℃) (expression Tg in the bracket).Particularly under the situation that requires to have the transparency, preferably use ester ring type polyolefin etc.
During with gas barrier film of the present invention and polarizer combination use, preferably make the barrier laminated dignity of gas barrier film gas barrier film is configured in the most inboard (adjacent with element) to the inboard of unit.At this moment, owing to compare the inboard that gas barrier film is configured in the unit with polarizer, so the length of delay of gas barrier film becomes very important.It is gas barrier film and the stacked use of circular polarizing disk (1/4 wavelength sheet+(1/2 wavelength sheet)+straight line polarizer) of the following base film of 10nm that the occupation mode of the gas barrier film under this kind execution mode preferably will adopt length of delay, or be to make up the straight line polarizer on the gas barrier film of base film of 100nm～180nm to use adopting the length of delay that can be used as 1/4 wavelength sheet.
Base film as postponing below 10nm can list cellulosic triacetate (Fuji Photo Film Co., Ltd.: the of Fuji Star Network), Merlon (Teijin Chemicals, Ltd.: Pure-ace, Kaneka Co., Ltd.: Elmec), cyclic olefin polymer (JSR Corp.: Arton, Japan Zeon Co., Ltd.: Zeonor), cyclic olefine copolymer (Mitsui Chemicals, Inc: Apel (pellet), Polyplastic Co., Ltd.: Topas (pellet)), polyacrylate (Unitika Co., Ltd.: U100 (pellet)), clear polyimides (aerochemistry Co., Ltd. of Mitsubishi: ネ オ プ リ system) etc.
As 1/4 wavelength sheet, can adopt by above-mentioned film is suitably extended the film that is adjusted to required length of delay.
Because gas barrier film of the present invention uses as components and parts such as organic ELs, so plastic film is transparent, and promptly light transmittance is generally more than 80%, and is preferred more than 85%, more preferably more than 90%.Light transmittance can be obtained with the method for putting down in writing among the JIS-K7105, promptly measures total light transmittance and amount of scattered light with integrating sphere type determination of light transmittance device, and deducting the diffusion transmitance from total light transmittance can obtain.
Even gas barrier film of the present invention is used for display applications, not necessarily the transparency to be arranged when observing side etc. when not being arranged on.Therefore, under these circumstances, plastic film also can use opaque material.As opaque material, can list for example polyimides, polyacrylonitrile, known liquid crystal polymer etc.
The thickness of the plastic film that uses in gas barrier film of the present invention can suitably be selected according to purposes, does not therefore have particular restriction, is typically 1～800 μ m, is preferably 10～200 μ m.These plastic films also can have functional layers such as transparency conducting layer, prime coat.About functional layer, in the paragraph numbering 0036～0038 of TOHKEMY 2006-289627 communique, be documented.As the example of the functional layer beyond the above-mentioned functions layer, can list delustering agent layer, protective layer, antistatic backing, smoothing layer, antistatic backing, adhesion improvement layer, light shield layer, anti-reflection layer, hard conating, stress relaxation layer, anti-fog layer, stain-proofing layer, be printed layer, easy adhesive linkage etc.
(display element)
As the display element among the present invention, can list liquid crystal display cells, touch panel, organic EL, thin-film transistor (TFT) image-displaying member, Electronic Paper etc.
Liquid crystal display cells
The structure of reflection-type liquid-crystal display device is for being followed successively by infrabasal plate, reflecting electrode, following alignment films, liquid crystal layer from top to bottom, going up alignment films, transparency electrode, upper substrate, λ/4 plates and polarizing coating.If colored the demonstration is then preferably further between reflecting electrode and following alignment films or between last alignment films and transparency electrode color-filter layer is set.
The structure of transmissive liquid crystal display device is backlight for being followed successively by from top to bottom, polarizer, λ/4 plates, down transparency electrode, down alignment films, liquid crystal layer, go up alignment films, go up transparency electrode, upper substrate, λ/4 plates and polarizing coating.If colored the demonstration, then preferably further descending between transparency electrode and the following alignment films or between last alignment films and transparency electrode, colour filter be set.
The kind of liquid crystal cells is not subjected to particular restriction, preferred TN (twisted-nematic) type, STN (supertwist is to row) type or HAN (hybrid orientation is to row) type, VA (vertical orientated) type, ECB type (electrically conerolled birefringence), OCB type (optical compensation curved), IPS type (switching in the face), CPA type (ContinuousPinwheel Alignment: the fireworks shape is arranged continuously).
Touch panel
Use in the device that touch panel can be put down in writing in Japanese kokai publication hei 5-127822 communique, TOHKEMY 2002-48913 communique etc.
Organic EL
Organic EL is meant organic electroluminescent device.Organic EL has negative electrode and anode on substrate, have the organic compound layer that contains luminescent layer between two electrodes.Light-emitting component in nature, the electrode of at least one in anode and the negative electrode is transparent.
As the stacked execution mode of organic compound layer of the present invention, preferably stack gradually the mode of hole transporting layer, luminescent layer, electron supplying layer from anode-side.Can also have electron screening layer etc. between hole transporting layer and the luminescent layer or between luminescent layer and electron supplying layer.Between anode and hole transporting layer, can have hole injection layer, between negative electrode and electron supplying layer, can have electron injecting layer.As luminescent layer, can only be one deck, also luminescent layer can be divided into first luminescent layer, second luminescent layer, the 3rd luminescent layer etc.In addition, each layer also can be divided into the multilayer secondary layer.
Below, each key element that constitutes organic EL is elaborated.
Substrate
The substrate that uses in the organic EL of the present invention can be a gas barrier film of the present invention, also can be the known substrate that uses in organic EL.When adopting known substrate, can be resin film, also can be gas barrier film.If adopt gas barrier film, then can preferably use the gas barrier film of record in TOHKEMY 2004-136466 communique, TOHKEMY 2004-148566 communique, TOHKEMY 2005-246716 communique, the TOHKEMY 2005-262529 communique etc.
When adopting known substrate, its thickness is not subjected to particular restriction, preferred 30 μ m～700 μ m, more preferably 40 μ m～200 μ m, further preferred 50 μ m～150 μ m.In addition, no matter under which kind of situation, mist degree is all preferably below 3%, and more preferably below 2%, further preferably below 1%, total light transmittance is preferably more than 70%, more preferably more than 80%, further preferably more than 90%.
Anode
Usually,, its shape, structure, size etc. are not had particular restriction, can from known electrode material, suitably select according to purposes, the purpose of light-emitting component as long as anode has as the function that the electrode in hole is provided to organic compound layer.As mentioned above, anode is established as transparent anode usually.About transparent anode, at＜＜new development of ELD〉〉 CMC of swamp Tian Feng chief editor distribution (1999) (swamp Tian Feng
Repair " transparent Electricity Very film Xin Zhan Open " シ-エ system シ-periodical (1999)) in be documented.When with the low plastic basis material of thermal endurance during, preferably use ITO or IZO, film forming obtains under the low temperature below 150 ℃ transparent anode as substrate.
Negative electrode
Usually,, its shape, structure, size etc. are not had particular restriction, can from known electrode material, suitably select according to purposes, the purpose of light-emitting component as long as negative electrode has as function from the electrode of electronics to organic compound layer that inject.
As the material that constitutes negative electrode, can list metal for example, alloy, metal oxide, conductive compound, their mixture etc.As object lesson, can list rare earth metals such as group II metal (for example Mg, Ca etc.), gold, silver, lead, aluminium, lithium-aluminium alloy, magnesium-silver alloy, Yin, Yb etc.They can a kind use separately, but from taking into account the viewpoint of stability and electronics injection, also can be preferred more than 2 kinds and usefulness.
Wherein, as the material that constitutes negative electrode, preferably based on the material of aluminium.
Based on the material of aluminium be meant aluminium separately, aluminium and the alkali metal of 0.01～10 quality % or the alloy (for example lithium-aluminium alloy, magnesium-aluminum alloy etc.) of group II metal.In addition, about the material of negative electrode, in Japanese kokai publication hei 2-15595 communique, Japanese kokai publication hei 5-121172 communique, be documented.And, the dielectric layer that fluoride by alkali metal or group II metal, oxide that can also insert thick 0.1～5nm between negative electrode and above-mentioned organic compound layer etc. forms.This dielectric layer also can be considered a kind of electron injecting layer.
The thickness of negative electrode can suitably be selected according to the material that constitutes negative electrode, can't stipulate in the lump, is generally about 10nm～5 μ m, preferred 50nm～1 μ m.
Negative electrode can be transparent, also can be opaque.In addition, transparent negative electrode can form behind the film of thick 1～10nm transparent conductivity materials such as stacked ITO or IZO by the material with negative electrode and forms.
Luminescent layer
Organic EL has the organic compound layer that one deck at least contains luminescent layer, other organic compound layer as beyond the organic luminous layer can list each layers such as hole transporting layer, electron supplying layer, electron screening layer, hole injection layer, electron injecting layer as mentioned above.
-organic luminous layer-
Organic luminous layer is the layer with following function, promptly when applying electric field, receive the hole from anode, hole injection layer or hole transporting layer, receive electronics, the place that hole and electronics combine again is provided and makes it luminous from negative electrode, electron injecting layer or electron supplying layer.Luminescent layer can only be made of luminescent material, also can be the mixed layer of host material and luminescent material.Luminescent material can be a fluorescence luminescent material, also can be phosphorescent light-emitting materials, and alloy can be a kind, also can be more than 2 kinds.Host material is preferably charge transport material.Host material can be a kind, also can be more than 2 kinds, can list the structure that the host material of the host material of electron transport for example and hole (ホ-Le) conveying property mixes.In addition, can also contain in the luminescent layer and do not have charge-transporting, non-luminous material.Luminescent layer can be 1 layer, also can be more than 2 layers, and each layer can be undertaken luminous by different illuminant colours.
As the example of above-mentioned fluorescence luminescent material, can list for example benzoxazole derivative, benzimidizole derivatives, benzothiazole derivant, the styryl benzene derivative, the polyphenyl derivative, the diphenyl diethylene derivative, the tetraphenylbutadiene derivative, Naphthalamide derivatives, coumarin derivative, the condensation aromatic compound, purple cyclic ketone derivative oxadiazole derivative oxazine derivative, the aldazine derivative, Pyraridine (ピ ラ リ ジ Application) derivative, cyclopentadiene derivant, the bisstyryl anthracene derivant, quinoline a word used for translation ketone derivatives, Pyrrolopyridine derivatives, the thiadiazoles pyridine derivate, cyclopentadiene derivant, the styrylamine derivative, diketopyrrolopyrrolederivatives derivatives, aromatic series two methylidyne compounds, with the metal complex of oxine derivative or the metal complex of methylene pyrrole derivative is various metal complexes of representative etc., polythiophene, polyphenylene, polymer compounds such as polyphenylene vinylene, compounds such as organic silane derivative etc.
Above-mentioned phosphorescent light-emitting materials can list the complex that for example contains transition metal atoms or group of the lanthanides atom.As above-mentioned transition metal atoms, there is not particular restriction, preferred ruthenium, rhodium, palladium, tungsten, rhenium, osmium, iridium and platinum, more preferably rhenium, iridium and platinum.
As above-mentioned group of the lanthanides atom, can list lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium.Preferred neodymium, europium and gadolinium in these group of the lanthanides atoms.
As the ligand of complex, for example can list works such as G.Wilkinson, Comprehensive Coordination Chemistry, the distribution in 1987 of Pergamon Press company; The H.Yersin work, the distribution in 1987 of " Photochemistry and Photophysics of Coordination Compounds " Springer-verlag company; The bright husband's work in Yamamoto " organometallic chemistry-basis and application-" skirt China room society nineteen eighty-two (Yamamoto bright husband's work “ You Machine metal
Learn-Ji Foundation と ying usefulness-" Shang room society nineteen eighty-two) ligand put down in writing in the distribution etc. etc.
As the host material that contains in the luminescent layer, can list material, material, the material, the material that for example have the carbazole skeleton, have the material of triazine skeleton and have the material of aryl-silane skeleton or illustrative material under the item of hole injection layer described later, hole transporting layer, electron injecting layer, electron supplying layer with pyrazine skeleton with pyridine skeleton with diaryl amine skeleton.
-hole injection layer, hole transporting layer-
Hole injection layer, hole transporting layer are the layers that has from anode or anode-side reception hole and be transported to the function of cathode side.Hole injection layer, hole transporting layer specifically preferably contains carbazole derivates, triazole derivative oxazole derivative oxadiazole derivative, imdazole derivatives, poly-aryl alkane derivatives, pyrazoline derivative, pyrazolone derivative, phenylenediamine derivative, aryl amine derivatives, the amino chalcone derivative that replaces, the styryl anthracene derivant, fluorenone derivatives, hydazone derivative, stilbene derivative, the silazane derivative, aromatic uncle amine compound, the styrylamine compound, aromatic series two methine compounds, porphyrins, organic silane derivative, the layer of carbon etc.
-electron injecting layer, electron supplying layer-
Electron injecting layer, electron supplying layer are to have from negative electrode or cathode side to receive electronics and be transported to the layer of the function of anode-side.Electron injecting layer, electron supplying layer specifically preferably contains triazole derivative oxazole derivative oxadiazole derivative, imdazole derivatives, fluorenone derivatives, anthraquinone bismethane derivative, anthracyclinone derivatives, the diphenyl benzene quinone derivative, the thiapyran dioxide derivative, the carbodiimide derivative, the fluorenylidene methane Derivatives, the talan based piperazine derivative, aromatic rings tetracarboxylic anhydrides such as naphthalene perylene, phthalocyanine derivates, the metal complex that is metal phthalocyanine benzoxazole or benzothiazole with the metal complex or the ligand of oxine derivative is the various metal complexes of representative, the layer of organic silane derivative etc.
-hole screen-
The hole screen is to have to prevent to be delivered to the layer of the hole of luminescent layer by the function of cathode side from anode-side.In the present invention, the organic compound layer as in cathode side and luminescent layer adjacency can be provided with the hole screen.In addition, the electron supplying layer electron injecting layer also can have the function of hole screen concurrently.
As the example of the organic compound that constitutes the hole screen, can list phenanthroline derivatives such as aluminium complex, triazole derivative, BCP such as BAlq etc.
In addition, also can be located on anode-side and the luminescent layer adjoining position having the electronics that prevents to be delivered to luminescent layer from cathode side layer by the function of anode-side.The hole transporting layer hole injection layer also can have this function concurrently.
(solar cell)
The sealing film that gas barrier film of the present invention can be used as solar battery element uses.Here, gas barrier film of the present invention preferably is positioned near the mode of solar battery element side with adhesive linkage and carries out sealing.Solar battery element as preferred use gas barrier film of the present invention, do not have particular restriction, can list monocrystalline silicon class solar battery element, polysilicon class solar battery element, non-crystalline type silicon class solar battery element with formations such as single connecting-type (シ Application グ Le maqting type) or tandem junction configurations ( Application デ system Agencies moulding), gallium arsenic (GaAs) or indium phosphorus III-V compound semiconductor solar battery elements such as (InP), cadmium tellurium II-VI compound semiconductor solar battery elements such as (CdTe), copper/indium/selenium class (so-called CIS class), copper/indium/gallium/selenium class (so-called CIGS class), copper/indium/gallium/selenium/sulphur class I-III-VI compound semiconductor solar battery elements such as (so-called CIGSS classes), the dye-sensitized solar cell element, organic photovoltaic cell element etc.Wherein, the above-mentioned solar battery element preferably copper/indium/selenium class among the present invention (so-called CIS class), copper/indium/gallium/selenium class (so-called CIGS class), copper/indium/gallium/selenium/sulphur class I-III-VI compound semiconductor solar battery elements such as (so-called CIGSS classes).
Embodiment
Below, enumerate embodiment and be described more specifically the present invention.Material shown in the following embodiment, consumption, ratio, contents processing, processing sequence etc. only otherwise break away from purport of the present invention all can suitably change.Therefore, scope of the present invention is not limited to object lesson shown below.
Making of [embodiment 1] gas barrier film and evaluation (1)
On base film, be provided with the gas barrier film (sample No.101～115) that inorganic layer and organic layer form by following sequentially built.The detailed structure of each gas barrier film is as described in Table 1.Base film adopts PEN (PEN, thick 100 μ m, Supreme Being people Dupont Kabushiki Kaisha system, Q65A) film.
[1] formation of inorganic layer (*)
Form the inorganic layer of aluminium oxide with the reactive sputtering device.Concrete membrance casting condition is as follows.
The vacuum chamber of reactive sputtering device is decompressed to limiting pressure 5 * 10 with oil rotary pump and turbomolecular pump
-4Pa.Import argon gas then as plasma gas, apply 2000W electric power by plasma electrical source.To indoor importing high-purity oxygen, will become film pressure to be adjusted to 0.3Pa and carry out the film forming of certain hour, form the inorganic layer of aluminium oxide.The thickness of the pellumina that obtains is 40nm, and film density is 3.01g/cm
3
[2] formation of organic layer (Y, W, Z, V, U)
Organic layer adopts the film build method (organic layer Y, W, V, U) of solvent coating under the normal pressure and these 5 kinds of methods of film build method (organic layer Z) of decompression glitter down vapour deposition method to form.Shown in concrete film forming thes contents are as follows.
[2-1] utilizes the film forming of solvent coating carrying out organic layer (Y) under normal pressure
To be dissolved in methylethylketone 190g as tripropylene glycol diacrylate (TPGDA, the ダ イ セ Le サ イ テ Star Network system) 9g and Photoepolymerizationinitiater initiater (Ciba Specialty Chemicals, the Irgacure 907) 0.1g of optical polymerism acrylate, make coating fluid.With the coiling rod this coating fluid is coated on the base film, with the air-cooled metal Halogen lamp LED (EyeGraphics Co., Ltd. system) of 160W/cm, irradiation illumination is 350mW/cm under the nitrogen of oxygen concentration below 0.1% purges
2, exposure is 500mJ/cm
2Ultraviolet ray, form organic layer (Y).Thickness is about 500nm.
[2-2] utilizes the film forming of solvent coating carrying out organic layer (W) under normal pressure
Except (DPHA: Xin Zhong village chemical industry system) replace tripropylene glycol diacrylate (TPGDA) as the optical polymerism acrylate, other is all according to the membrance casting condition of organic layer Y with dipentaerythritol acrylate.Thickness is about 500nm.
[2-3] under reduced pressure utilizes the flash of light vapour deposition method to carry out the film forming of organic layer (Z)
To mix as butyl ethyl propane diol diacrylate (BEPGA, the common prosperity society chemistry system) 9.7g and Photoepolymerizationinitiater initiater (Lamberti spa system, the EZACURE-TZT) 0.3g of optical polymerism acrylate, make evaporation liquid.In the interior pressure of vacuum chamber be under the condition of 3Pa with the flash of light vapour deposition method with this evaporation liquid evaporation in substrate.Then, under the condition of same vacuum degree, the irradiation exposure is 2J/cm
2Ultraviolet ray, form organic layer Z.Thickness is about 1200nm.In the formation of organic layer Z, adopt organic-inorganic layer film formation device Guardian200 (Vitex Systems corporate system) to implement.
[2-4] utilizes the film forming of solvent coating carrying out organic layer (V) under normal pressure
To be dissolved in methylethylketone 190g as bisphenol-a epoxy acrylate (Xin Zhong village chemistry system, the NK オ リ go EA-1020) 9g and Photoepolymerizationinitiater initiater (Ciba Specialty Chemicals, the Irgacure 907) 0.1g of optical polymerism acrylate, make coating fluid.With the coiling rod this coating fluid is coated on the base film, with the air-cooled metal Halogen lamp LED (Eye Graphics Co., Ltd. system) of 160W/cm, irradiation illumination is 350mW/cm under the nitrogen of oxygen concentration below 0.1% purges
2, exposure is 500mJ/cm
2Ultraviolet ray, form organic layer (V).Thickness is about 500nm.
[2-5] utilizes the film forming of solvent coating carrying out organic layer (U) under normal pressure
Except replacing bisphenol-a epoxy acrylate (Xin Zhong village chemistry system, NK オ リ go EA-1020) as the optical polymerism acrylate with epoxy acrylate (ダ イ セ Le サ イ テ Star Network system, EB3702), other is all according to the membrance casting condition of organic layer V.Thickness is about 500nm.
[3] formation of block resin bed (P)
The block resin bed forms with following 6 kinds of methods.Shown in concrete film forming thes contents are as follows.
The film forming of [3-1] block resin bed (P-1)
Polyvinyl alcohol (PVA117H, Network ラ レ system) is dissolved in the pure water with 2 weight %, makes coating fluid.With the coiling rod this coating fluid is coated on the base film, dry under 80 ℃, form block resin bed (P-1).Thickness is about 700nm.
The film forming of [3-2] block resin bed (P-2)
Vinylidene chloride analog copolymer (サ ラ Application レ ジ Application F216, Asahi Chemical Industry industry system) is dissolved in the mixed solvent of toluene/oxolane=1/2 (weight ratio) and is 15 weight %, make coating fluid.With the coiling rod this coating fluid is coated on the base film, dry under 105 ℃, form block resin bed (P-2).Thickness is about 2.5 μ m.
The film forming of [3-3] block resin bed (P-3)
Ethylene-vinyl alcohol copolymer (ソ ア ノ-Le 30L, Japanese synthetic chemical industry system) is dissolved in the mixed solvent of pure water/isopropyl alcohol=1/1 (weight ratio) and is 12 weight %, make coating fluid.With the coiling rod this coating fluid is coated on the base film, dry under 110 ℃, form block resin bed (P-3).The about 2 μ m of thickness.
The film forming of [3-4] block resin bed (P-4)
Synthetic mica (テ ト ラ シ リ リ Star Network マ イ カ (Na-Ts), TOPY industry system) is dispersed in the pure water and the dispersion liquid (1) of the 0.65 weight % that obtains and polyvinyl alcohol (PVA210, Network ラ レ system) are dissolved in the pure water and the solution (2) of the 0.325 weight % that obtains, according to the solid constituent of dispersion liquid (1) and solution (2) mixed, make coating fluid than (volume ratio) (1)/(2)=3/7.With the coiling rod this coating fluid is coated on the base film, formed block resin bed (P-4).Thickness is about 1 μ m.
The film forming of [3-5] block resin bed (P-5)
Except replacing the polyvinyl alcohol of above-mentioned solution (2) with hydroxyethylcellulose (with the pure medicine system of light), other is all according to the membrance casting condition of block resin bed (P-4).Thickness is about 1 μ m.
The film forming of [3-6] block resin bed (P-6)
To be dissolved in methylethylketone 190g as dipentaerythritol acrylate (DPAH, the Xin Zhong village chemical industry system) 9g and Photoepolymerizationinitiater initiater (Ciba Specialty Chemicals, the Irgacure 907) 0.1g of optical polymerism acrylate, make coating fluid.With the coiling rod this coating fluid is coated on the base film, with the air-cooled metal Halogen lamp LED (EyeGraphics Co., Ltd. system) of 160W/cm, irradiation illumination is 350mW/cm under the nitrogen of oxygen concentration below 0.1% purges
2, exposure is 1J/cm
2Ultraviolet ray, form block resin bed (P-6).Thickness is about 1 μ m.
[4] making of gas barrier film
Gas barrier film is by forming above-mentioned inorganic layer successively according to the formation of described each sample of table 1 and organic layer forms on base film.Manufacture method is undertaken by following 3 kinds of methods.
[4-1] utilizes the solvent coating to form organic layer repeatedly and under reduced pressure forms the method (stacked A) of inorganic layer
On substrate, alternately be laminated with machine layer and inorganic layer.When stacked inorganic layer on organic layer, be coated with film forming to form organic layer with solvent after, place in the vacuum chamber and reduce pressure, be 10 in vacuum degree
-3The following state of Pa keeps certain hour to come the film forming inorganic layer down.When stacked organic layer on inorganic layer, behind the film forming inorganic layer, be coated with the film forming organic layer by solvent immediately.
[4-2] be the method (stacked B) of continuous film forming organic layer and inorganic layer under reduced pressure
Be laminated into film device Guardian 200 with above-mentioned organic-inorganic, stacked organic layer and inorganic layer.This device carries out the film forming of organic layer and inorganic layer under reduced pressure atmosphere, and the film forming room of organic layer and inorganic layer links to each other, therefore can be at continuous film forming under the reduced pressure atmosphere.Therefore, before forming the barrier layer, do not need to atmosphere opening.
[4-3] only ground floor is coated with solvent and forms and the equal method of continuous film forming (stacked C) under reduced pressure of all the other organic layers
On substrate, form the 1st organic layer with the solvent rubbing method.Then, the substrate that will have the 1st organic layer places in the vacuum chamber, and decompression is 10 in vacuum degree
-3Following state replaces film forming inorganic layer and organic layer after keeping certain hour down.
[5] evaluation of physical property of gas barrier film
Estimate the various rerum naturas of gas barrier film with following apparatus.
[layer structure (thickness)]
With the ultra-thin section of scanning electron microscope " S-900 type " viewing film sample of Hitachi, Ltd.'s system and measure.
[moisture-vapor transmission (g/m
2/ day)]
" PERMATRAN-W3/31 " (condition: 40 ℃, relative humidity 90%) with film health (MOCON) corporate system measured.The mensuration boundary of above-mentioned film health device is 0.01g/m
2/ day following value is supplied in order to following method.At first, direct evaporation metal Ca on gas barrier film is positioned at inboard mode with this film and glass substrate sealing with material for sealing with evaporation Ca with commercially available organic EL, makes working sample.Then, under above-mentioned temperature and humidity conditions, keep this working sample, change (because of hydroxide or oxidation reduce metallic luster) by the optical concentration of the metal Ca on the gas barrier film and obtain moisture-vapor transmission.Detailed content is measured referring to the method for putting down in writing in the following list of references.
＜list of references 〉
SID ConferenceRecord of the International Display Research Conference 1435-1438 pages or leaves such as G.NISATO, P.C.P.BOUTEN, P.J.SLIKKERVEER
[the X ray reflection rate is measured (film density of inorganic layer)]
Adopt the evaluation sample of film forming inorganic layer on the Si wafer, measure with electric system ATX-G of science.Calculate the film density of inorganic layer film by measurement result.
Table 1
| Sample No. | Layer structure | Laminating method | Barrier resin layer | Moisture-vapor transmission (g/m 2My god) |
| 101 | PEN/Y/X/Y/X | Stacked A | — | 0.01 |
| 102 | P-1/PEN/Y/X/Y/X | Stacked A | P-1 | 0.01 |
| 103 | P-2/PEN/Y/X/Y/X | Stacked A | P-2 | 0.01 |
| 104 | P-3/PEN/Y/X/Y/X | Stacked A | P-3 | 0.01 |
| 105 | PEN/Z/X/Z/X | Stacked B | — | 0.005 |
| 106 | P-1/PEN/Z/X/Z/X | Stacked B | P-1 | 0.005 |
| 107 | P-2/PEN/Z/X/Z/X | Stacked B | P-2 | 0.005 |
| 108 | P-3/PEN/Z/X/Z/X | Stacked B | P-3 | 0.005 |
| 109 | P-4/PEN/Z/X/Z/X | Stacked B | P-4 | 0.005 |
| 110 | P-5/PEN/Z/X/Z/X | Stacked B | P-5 | 0.005 |
| 111 | PEN/Y/X/Z/X | Stacked C | — | 0.007 |
| 112 | P-4/PEN/Y/X/Z/X | Stacked C | P-4 | 0.007 |
| 113 | P-5/PEN/Y/X/Z/X | Stacked C | P-5 | 0.007 |
| 114 | PEN/W/X/W/X | Stacked A | 0.008 | |
| 115 | P-6/PEN/W/X/W/X | Stacked A | P-6 | 0.008 |
| 116 | P-1/PEN/V/X/V/X | Stacked A | P-1 | 0.007 |
| 117 | P-1/PEN/U/X/U/X | Stacked A | P-1 | 0.007 |
Making of [embodiment 2] gas barrier film and evaluation (2)
Except (PET, thick 100 μ m, Toray Co., Ltd., Le ミ ラ-T60) as the base film, operate similarly to Example 1 make gas barrier film (sample No.201～208) according to table 2 with PETG.
Table 2
| Sample No. | Layer structure | Laminating method | Barrier resin layer | Moisture-vapor transmission (g/m 2My god) |
| 201 | PET/Y/X/Y/X | Stacked A | — | 0.011 |
| 202 | P-1/PET/Y/X/Y/X | Stacked A | P-1 | 0.011 |
| 203 | P-2/PET/Y/X/Y/X | Stacked A | P-2 | 0.011 |
| 204 | P-3/PET/Y/X/Y/X | Stacked A | P-3 | 0.011 |
| 205 | PET/Z/X/Z/X | Stacked B | — | 0.006 |
| 206 | P-1/PET/Z/X/Z/X | Stacked B | P-1 | 0.006 |
| 207 | P-2/PET/Z/X/Z/X | Stacked B | P-2 | 0.006 |
| 208 | P-3/PET/Z/X/Z/X | Stacked B | P-3 | 0.006 |
| 209 | P-1/PET/V/X/V/X | Stacked A | P-1 | 0.008 |
| 210 | P-1/PET/U/X/U/X | Stacked A | P-1 | 0.008 |
Making of [embodiment 3] organic EL and evaluation (1)
[1] making of organic EL substrate
Conductive glass substrate (sheet resistance value 10 Ω/, carry out 10 minutes UV-ozone treatment that will have the ITO film) with after the washing of 2-propyl alcohol.Go up with the vacuum vapour deposition organic compound below the evaporation successively at this substrate (anode).
(the 1st hole transporting layer)
Copper phthalocyanine: thickness 10nm
(the 2nd hole transporting layer)
N, N '-diphenyl-N, N '-dinaphthyl benzidine: thickness 40nm
(luminescent layer hold concurrently electron supplying layer)
Three (oxine) aluminium: thickness 60nm
Evaporation lithium fluoride 1nm, metallic aluminium 100nm successively make negative electrode at last, use the silicon nitride film of thick 3 μ m on the parallel flat CVD choice specimen of calligraphy thereon, make organic EL.
[2] setting of the barrier layer for gases on the organic EL
With heat curing-type bonding agent (エ Port テ Star Network 310, ダ イ ゾ-ニ チ モ リ Co., Ltd.), block film and the organic EL substrate made in the foregoing description 1 are fitted in the mode that the barrier layer is positioned at the organic EL side, and heating made bonding agent solidify in 3 hours under 65 ℃.Each makes the organic EL (sample No.301～315) that 20 sealing according to said method obtain.
[3] evaluation of organic EL light-emitting area situation (1)
With source measuring unit (SMU2400 type, Keithley corporate system) organic EL (sample No.301～315) that has just made being applied 7V voltage makes it luminous.With confirming after the microscopic examination light-emitting area situation: each element all sends the even light of no dim spot.
After then each element being left standstill 24 hours in 60 ℃, the darkroom of relative humidity 90%, observe the light-emitting area situation.Be defined as failure rate with observing the ratio of diameter greater than the element of the dim spot of 300 μ m, the failure rate of each element is as shown in table 3.
Making of [embodiment 4] organic EL and evaluation (2)
, make as the sealing film of the gas barrier film making among the embodiment 2 by the organic EL of sealing (sample No.401～408).When on organic EL, barrier layer for gases being set, with ultraviolet hardening bonding agent (XNR5516HV, length
Ciba Co., Ltd. system) replaces the heat curing-type bonding agent, make its curing, bonding with the glove box internal radiation ultraviolet ray after the argon replaces.Similarly to Example 3, estimate the failure rate of each element at 60 ℃, relative humidity 90%, after leaving standstill in 24 hours.The result is as shown in table 4.
[embodiment 5] are with the making (1) of gas barrier film as the organic EL of substrate
The gas barrier film of making among the embodiment 1 is imported in the vacuum chamber, use the ITO target, by the DC magnetron sputtering, the transparency electrode that formation is formed by the ito thin film of thick 0.2 μ m.The gas barrier film that will have the ITO film places clean container, carries out ultrasonic washing in the 2-propyl alcohol, carries out 30 minutes UV-ozone treatment then.Adopt this substrate, make organic EL (sample No.501～508) similarly to Example 3.Therefore the substrate of this element and sealing film have flexible all based on resin.Estimate the failure rate of each element similarly to Example 3 at 60 ℃, relative humidity 90%, after leaving standstill in 24 hours.The result is as shown in table 5.
Table 3
| Sample No. | The sample No. of gas barrier film | The failure rate of organic EL (%) | Remarks |
| 301 | 101 | 20 | Comparative example |
| 302 | 102 | 11 | The present invention |
| 303 | 103 | 5 | The present invention |
| 304 | 104 | 9 | The present invention |
| 305 | 105 | 11 | Comparative example |
| 306 | 106 | 4 | The wood invention |
| 307 | 107 | 1 | The present invention |
| 308 | 108 | 3 | The present invention |
| 309 | 109 | 6 | The present invention |
| 310 | 110 | 9 | The present invention |
| 311 | 111 | 16 | Comparative example |
| 312 | 112 | 11 | The present invention |
| 313 | 113 | 14 | The present invention |
| 314 | 114 | 18 | Comparative example |
| 315 | 115 | 17 | The present invention |
| 316 | 116 | 8 | The present invention |
| 317 | 117 | 8 | The present invention |
Table 4
| Sample No. | The sample No. of gas barrier film | The failure rate of organic EL (%) | Remarks |
| 401 | 201 | 22 | Comparative example |
| 402 | 202 | 14 | The present invention |
| 403 | 203 | 8 | The present invention |
| 404 | 204 | 13 | The present invention |
| 405 | 205 | 12 | Comparative example |
| 406 | 206 | 6 | The present invention |
| 407 | 207 | 3 | The present invention |
| 408 | 208 | 5 | The present invention |
| 409 | 209 | 10 | The present invention |
| 410 | 210 | 10 | The present invention |
Table 5
| Sample No. | The sample No. of gas barrier film | The failure rate of organic EL (%) | Remarks |
| 501 | 101 | 30 | Comparative example |
| 502 | 102 | 16 | The present invention |
| 503 | 103 | 9 | The present invention |
| 504 | 105 | 17 | Comparative example |
| 505 | 106 | 7 | The present invention |
| 506 | 107 | 3 | The present invention |
| 507 | 109 | 10 | The present invention |
| 508 | 110 | 11 | The present invention |
| 509 | 116 | 14 | The present invention |
| 510 | 117 | 14 | The present invention |
By the result of table 3～5 as can be known, the block film with block resin bed of the present invention is better than the block film of unobstructed property resin bed, and the failure rate of organic EL is low.In addition, block film of the present invention is no matter be as the sealing film, and is still as the substrate of organic EL, all very effective.
Claims (15)
1, a kind of gas barrier film, it has barrier layer for gases on a face of base film, this barrier layer for gases has at least 1 organic zone and at least 1 inorganic zone, and only having with the resin with barrier properties on another face of described base film is the layer that the layer of main component is used as having barrier properties.
2, a kind of gas barrier film, it has barrier layer for gases on a face of base film, this barrier layer for gases has at least 1 layer of organic layer and at least 1 layer of inorganic layer, and only having with the resin with barrier properties on another face of described base film is the layer that the layer of main component is used as having barrier properties.
3, gas barrier film as claimed in claim 2, wherein, with the resin with barrier properties be main component the layer in resin be polyvinyl alcohol.
4, gas barrier film as claimed in claim 2, wherein, with the resin with barrier properties be main component the layer in resin be polyfunctional acrylic ester.
5, gas barrier film as claimed in claim 2, wherein, organic layer contains by making that at least a kind of composition with bis-phenol skeleton (methyl) acrylate is solidified to form.
6, as each described gas barrier film in the claim 2～5, wherein, with the resin with barrier properties be main component the layer identical with the main component of organic layer.
7,, wherein, be that the layer of main component and the main component of organic layer are (methyl) acrylate derivative with resin with barrier properties as each described gas barrier film in the claim 2,4,5.
8, as each described gas barrier film in the claim 1～5, wherein, with the resin with barrier properties be main component the layer thickness be 0.5～30 μ m.
9, as each described gas barrier film in the claim 1～5, wherein, the thickness of gas barrier film is 10～300 μ m.
10, as each described gas barrier film in the claim 1～5, it is used for display element.
11, the manufacture method of each described gas barrier film in the claim 1～10 is characterized in that, after on the base film barrier layer for gases being set, is the layer of main component with the resin with barrier properties in the opposition side setting of described base film.
12, display element, it has adopted each described gas barrier film in the claim 1～10.
13, display element as claimed in claim 12 is characterized in that, gas barrier film is as the substrate of display element.
14, display element as claimed in claim 12 is characterized in that, gas barrier film is as the sealing film of display element.
15, as each described display element in the claim 12～14, wherein, on display element by with resin be with barrier properties main component the layer be positioned at the outside mode gas barrier film is set.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007238857 | 2007-09-14 | ||
| JP238857/2007 | 2007-09-14 | ||
| JP140980/2008 | 2008-05-29 |
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| Publication Number | Publication Date |
|---|---|
| CN101389166A true CN101389166A (en) | 2009-03-18 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2008102159731A Pending CN101389166A (en) | 2007-09-14 | 2008-09-12 | Gas barrier film, and display device comprising the same |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP2009083465A (en) |
| KR (1) | KR101502167B1 (en) |
| CN (1) | CN101389166A (en) |
Cited By (4)
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| CN102001201A (en) * | 2009-08-26 | 2011-04-06 | 富士胶片株式会社 | Laminate film and composite film |
| CN102343699A (en) * | 2010-07-30 | 2012-02-08 | 埃姆斯·帕特恩特股份有限公司 | Multilayer backsheet for photovoltaic modules, and its production and use in the production of photovoltaic modules |
| CN103476579A (en) * | 2011-04-05 | 2013-12-25 | 东丽株式会社 | Gas barrier film |
| CN104203560A (en) * | 2012-03-29 | 2014-12-10 | 琳得科株式会社 | Gas barrier laminate, method for producing same, member for electronic devices, and electronic device |
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| JP5216724B2 (en) * | 2009-09-01 | 2013-06-19 | 富士フイルム株式会社 | Gas barrier film and device |
| JP5485624B2 (en) * | 2009-09-14 | 2014-05-07 | 富士フイルム株式会社 | Barrier laminate and gas barrier film using the same |
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| JP3403882B2 (en) * | 1995-12-25 | 2003-05-06 | 帝人株式会社 | Transparent conductive film |
| JP4437735B2 (en) * | 2004-10-28 | 2010-03-24 | 大日本印刷株式会社 | Gas barrier film, and display substrate and display using the same |
| JP4569336B2 (en) * | 2005-03-22 | 2010-10-27 | 住友ベークライト株式会社 | Transparent barrier sheet |
-
2008
- 2008-05-29 JP JP2008140980A patent/JP2009083465A/en active Pending
- 2008-09-11 KR KR1020080089992A patent/KR101502167B1/en active IP Right Grant
- 2008-09-12 CN CNA2008102159731A patent/CN101389166A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102001201A (en) * | 2009-08-26 | 2011-04-06 | 富士胶片株式会社 | Laminate film and composite film |
| CN102001201B (en) * | 2009-08-26 | 2015-03-18 | 富士胶片株式会社 | Laminate film and composite film |
| CN102343699A (en) * | 2010-07-30 | 2012-02-08 | 埃姆斯·帕特恩特股份有限公司 | Multilayer backsheet for photovoltaic modules, and its production and use in the production of photovoltaic modules |
| CN103476579A (en) * | 2011-04-05 | 2013-12-25 | 东丽株式会社 | Gas barrier film |
| CN103476579B (en) * | 2011-04-05 | 2015-11-25 | 东丽株式会社 | Gas barrier film |
| CN104203560A (en) * | 2012-03-29 | 2014-12-10 | 琳得科株式会社 | Gas barrier laminate, method for producing same, member for electronic devices, and electronic device |
| CN104203560B (en) * | 2012-03-29 | 2015-12-30 | 琳得科株式会社 | Gas barrier property lamilated body, its manufacture method, use for electronic equipment component and electronic installation |
| TWI660841B (en) * | 2012-03-29 | 2019-06-01 | 琳得科股份有限公司 | Gas-barrier laminate, method for manufacturing the same, element for electronic device, and electronic device |
Also Published As
| Publication number | Publication date |
|---|---|
| KR101502167B1 (en) | 2015-03-12 |
| KR20090028450A (en) | 2009-03-18 |
| JP2009083465A (en) | 2009-04-23 |
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Application publication date: 20090318 |