Flexible high-temperature ultrabarrier

The present invention relates to barrier films and electronic devices.

Organic light emitting devices (OLEDs) can suffer power loss or premature failure when exposed to water vapor or oxygen. Metals and glasses are used for encapsulation and extended life of OLED devices, but metals typically lack transparency and glass lacks flexibility. Intensive efforts are underway to find other encapsulation materials for OLEDs and other electronic devices. Flexible polymer barrier films, which exhibit low permeability to water vapor and oxygen, are particularly useful, but so far only limited success has been achieved despite hard industrial efforts. References related to flexible barrier films include US Pat. No. 5,440,446 (Shaw et al.), US Pat. No. 5,530,581 (Cogan), US Pat. No. 5,681,666 ( Treger et al., US Pat. No. 5,686,360 (Harvey, III et al.), US Pat. No. 5,736,207 (Walther et al.), US Pat. No. 6,004,660 (Topolsky (Topolsky)). Topolski et al.), US Pat. No. 6,083,628 (Yializis), US Pat. No. 6,146,225 (Sheats et al.), US Pat. No. 6,214,422 (Yializis), US Patent. 6,268,695 (Affinito), US Pat. No. 6,358,570 (Affinito), US Pat. No. 6,413,645 (Graff et al.), US Pat. No. 6,492,026 (Graph). (Graff) et al.), And US Pat. No. 6,497,598 (Affnito).inito)), US Patent Application No. 2001/0015620 A1 (Affinito), US Patent Application No. 2002/0125822 A1 (Graff et al.), US Patent Application No. 2002/0150745 A1 Specification (Martin et al.), US Patent Application No. 2002/0176993 A1 (Graff et al.), European Patent Application No. 0 777 280 A2 (Motorola, Inc.). )) And PCT Publication Application International Publication No. 97/16053 Pamphlet (Robert Bosch GmbH). Walther et al.'S patent has a minimum oxygen permeability of 0.375 cc / m.²Describes barrier assemblies for plastic containers that are reported as / day / bar.

<p> The present invention, in one embodiment, is overcoated with a first polymer layer having a Tg above the glass transition temperature (Tg) of heat-stabilized polyethylene terephthalate (HSPET), and a Tg greater than or equal to the Tg of HSPET. A flexible visible light transmissive substrate with a Tg greater than or equal to Tg of HSPET, further overcoated with at least two visible light transmissive inorganic barrier layers separated by at least one second polymer layer having. Containing barrier assembly (sometimes referred to as "barrier film"), 0.005 cc / m at 23 ° C and 90% RH.²Provide a barrier assembly with an oxygen permeability of less than / day.</p><p> In another aspect, the invention a) A step of providing a flexible light-transmitting support having a Tg greater than or equal to Tg of HSPET, and b) The step of forming a first polymer layer having a Tg of HSPET Tg or more on the support, and c) A step of forming a first visible light-transmitting inorganic barrier layer on the first polymer layer, and d) A step of forming a second polymer layer having a Tg of HSPET Tg or more on the first inorganic barrier layer, and e) A step of forming a visible light-transparent second inorganic barrier layer on the second polymer layer, and A method of manufacturing a barrier assembly comprising 0.005 cc / m at 23 ° C and 90% RH.²Provided is a method for manufacturing a barrier assembly having an oxygen permeability of less than / day.</p><p> In a further embodiment, the invention is overcoated with a first polymer layer having a Tg greater than or equal to Tg of HSPET and separated by at least two second polymer layers having a Tg greater than or equal to Tg of HSPET. Feeling, at least partially covered by a barrier assembly comprising a flexible visible light permeable substrate with a Tg greater than or equal to the HSPET Tg, which is further overcoated with a visible light permeable inorganic barrier layer. Provided is a display or lighting device comprising a moisture or oxygen sensitive light source or light valve.</p><p> These and other aspects of the invention will become apparent from the detailed description below. However, in no case shall the above summary be construed as a limitation in the claims. Claims are defined only by the scope of claims, which may be modified during review.</p><p> Similar symbols in various drawings indicate similar elements. The elements of the drawing are not life-size.</p>

With respect to the location of the various layers in the barrier assembly or device of the present invention, by using orientation terms such as "top", "top", "top", etc., one or more layers with respect to the horizontal support layer. Refers to a relative position. It is not intended that the barrier assemblies or devices should have any particular orientation during or after their manufacture.

By using the term "overcoated" to describe the location of a layer with respect to the substrate or other element of the barrier assembly of the invention, that the layer is on top of the substrate or other element. As indicated, the layer does not necessarily have to be in contact with the substrate or other elements. By using the term "separated" to describe the location of the polymer layers with respect to the two inorganic barrier layers, it refers to the polymer layers being between the inorganic barrier layers, but the layers are not necessarily either. It does not have to be in contact with the inorganic barrier layer.

By using the term "polymer", it refers to homopolymers and copolymers, as well as homopolymers or copolymers that can be formed in miscible blends, for example by coextrusion or by reactions involving, for example, transesterification reactions. The term "copolymer" includes both random and block copolymers. The term "cured polymer" includes both crosslinked and uncrosslinked polymers. The term "crosslinked" polymer refers to a polymer in which polymer chains are bonded together by covalent chemical bonds, usually through a crosslinked molecule or group to form a reticulated polymer. Crosslinked polymers are generally characterized by being sparingly soluble, but can swell in the presence of suitable solvents.

By using the term "Tg", it refers to the glass transition temperature of a cured polymer when evaluated in bulk rather than in thin film form. In examples where the polymer can only be investigated in thin film form, it is usually possible to estimate Tg in bulk form with reasonable accuracy. The Tg value in bulk form is usually determined by assessing the rate of heat flow vs. temperature using differential scanning calorimetry (DSC), the initiation of segmental mobility of the polymer, and the state of the polymer in glass. Determine the anti-curvature point (usually the secondary transition) that can be said to have changed from to rubber state. The Tg value in bulk form can also be estimated using electromechanical thermal analysis (DMTA) techniques, which measure changes in polymer modulus as a function of temperature and frequency.

By using the term "visible light transmissive" support, layer, assembly or device, the support, layer, assembly or device is on the visible portion of a spectrum of at least about 20% measured along the vertical axis. Average transmittance T_visMeans to have.

With reference to Figure 1, 110 shows the barrier assembly in general. Assembly 110 includes a support 112 made of visible light transmissive, flexible plastic film with a Tg greater than or equal to Tg of HSPET (Tg = about 78 ° C). The support 112 is overcoated with a polymer layer 114 having a Tg greater than or equal to the Tg of HSPET, and two or more visible light transmissions such as layers 116, 120 and 124 separated by polymer layers such as layers 118 and 122. It is further overcoated with a sex-inorganic barrier layer. The assembly 110 also preferably comprises a protective polymer overlayer 126 on top of the visible light transmissive inorganic barrier layer 124.

FIG. 2 shows a laminated barrier assembly 130 that can be manufactured by laminating two pieces of assembly 110 together in a face-to-face relationship using a layer 132 of visible light transmissive adhesive.

The preferred flexible light-transmitting support 112 has a visible light transmittance of at least about 70% at 550 nm. Preferably, the support is heat-fixed, annealed under tension, or heat-stabilized using other techniques that prevent shrinkage to at least the heat-stabilized temperature when the support is not constrained. If the support is not thermally stabilized, it preferably has a Tg higher than the Tg of polymethylmethacrylate (PMMA, Tg = 105 ° C). More preferably, the support has a Tg of at least about 110 ° C, even more preferably at least about 120 ° C, and most preferably at least about 128 ° C. In addition to HSPET, particularly preferred supports include other heat-stabilized high Tg polyesters, PMMA, styrene / acrylonitrile (SAN, Tg = 110 ° C), styrene / maleic anhydride (SMA, Tg =). 115 ° C), polyethylene naphthalate (PEN, Tg = approx. 120 ° C), polyoxymethylene (POM, Tg = approx. 125 ° C), polyvinyl naphthalene (PVN, Tg = approx. 135 ° C) ), Polyetheretherketone ("PEEK", Tg = approx. 145 ° C), Polyaryletherketone ("PAEK", Tg = 145 ° C), High Tg fluoropolymer (eg, DYNEON®) HTE, hexafluoropropylene, tetrafluoroethylene and ethylene tarpolymer, Tg = about 149 ° C), polycarbonate (PC, Tg = about 150 ° C), polyα-methylstyrene (Tg = about 175 ° C) , Polyallylate ("PAR", Tg = 190 ° C), Polysulfone ("PSul", Tg = approx. 195 ° C), Polyphenylene oxide ("PPO", Tg = approx. 200 ° C), Polyetherimide ("" PEI , Tg = approx. 218 ° C), Polyarylsulfone (PAS, Tg = 220 ° C), Polyethersulfone (PES, Tg = approx. 225 ° C), Polyetherimide (PAI, Tg = Approximately 275 ° C), Polyetherimide (Tg = Approximately 300 ° C) And polyphthalamide (heat deflection temperature of 120 ° C). Supports made of HSPET and PEN are particularly preferred for applications where material cost is important. Supports made of more expensive materials may be used for applications where barrier performance is paramount. Preferably, the support has a thickness of about 0.01 mm to about 1 mm, more preferably about 0.05 mm to about 0.25 mm.

The first polymer layer with a Tg greater than or equal to the HSPET Tg is located on the support. Various polymer materials can be used. Volatile monomers that form suitable high Tg polymers are particularly preferred. Preferably, the first polymer layer has a Tg higher than the Tg of PMMA, more preferably at least about 110 ° C, even more preferably at least about 150 ° C, and most preferably at least about 200 ° C. Has. Particularly preferred monomers that can be used to form the first layer are urethane acrylates (eg, CN-968, Tg = about 84 ° C and CN-983, Tg = about 90 ° C, both sertmers. Commercially available from the company (Sartomer Co.), Isobornyl acrylate (eg SR-506, commercially available from the Sartomer Co., Tg = approx. 88 ° C), Dipentaerythritol Pentaacrylate (eg SR-399, Sartomer) Available as a commercial product from Co.), Tg = approx. 90 ° C), Epoxy acrylate blended with styrene (eg CN-120S80, commercially available from Sartomer Co.), Tg = approx. 95 ° C), Di-trimethylolpropane tetraacrylate (eg SR-355, commercially available from Sartomer Co., Tg = approx. 98 ° C), diethylene glycol diacrylate (eg SR-230, Available as a commercial product from Sartomer Co., Tg = approx. 100 ° C), 1,3-butylene glycol diacrylate (eg SR-212, commercially available from Sartomer Co.) , Tg = approx. 101 ° C), pentaacrylate ester (eg SR-9041, commercially available from Sartomer Co., Tg = approx. 102 ° C), pentaerythritol tetraacrylate (eg SR-9041) 295, Sartomer Company Available as a commercial product from Co.), Tg = approx. 103 ° C), Pentaerythritol triacrylate (eg SR-444, commercially available from Sartomer Co., Tg = approx. 103 ° C) , Esterylated (3) Trimethylolpropane triacrylate (eg SR-454, commercially available from Sartomer Co., Tg = approx. 103 ° C), Esterylated (3) Trimethylolpropane triacrylate (For example, SR-454HP, commercially available from Sartomer Co., Tg = approx. 103 ° C), Alkoxylated trifunctional acrylate ester (eg SR-9008, Sartomer Co.) Available as a commercial product from, Tg = approx. 103 ° C), Dipropylene glycol diacrylate (eg SR-508, available as a commercial product from Sartomer Co., Tg = approx. 104 ° C), Neo Pentyl glycol diacrylate (eg SR-247, sertomer) Available as a commercial product from the company (Sartomer Co.), Tg = approx. 107 ° C), ethoxylated (4) bisphenoldimethacrylate (eg, CD-450, available as a commercial product from the Sartomer Co.), Tg = approx. 108 ° C), cyclohexanedimethanol diacrylate ester (eg, CD-406, commercially available from Sartomer Co., Tg = approx. 110 ° C), isobornyl methacrylate (eg, eg) SR-423, commercially available from Sartomer Co., Tg = approx. 110 ° C), cyclic diacrylate (eg, IRR-214, commercially available from UCB Chemicals, Tg = Approximately 208 ° C), as well as tris (2-hydroxyethyl) isocyanurate triacrylate (eg SR-368, Sartomer) Available as a commercial product from Co.), Tg = about 272 ° C), the acrylate of the methacrylate and the methacrylate of the acrylate.

A layer of monomer or oligomer is applied to the substrate, and the layers are cross-linked to form a polymer at that location, for example by flash evaporation and deposition of radiation cross-linking monomers, followed by, for example, an electron beam device. The first polymer layer can be formed by cross-linking with a UV light source, discharge device or other suitable device. Coating efficiency can be improved by cooling the support. Monomers or oligomers are applied to the substrate using conventional coating methods such as roll coating (eg gravure roll coating) or spray coating (eg electrostatic spray coating) and then as revealed above. Can also be bridged to. The first polymer layer can also be formed by applying a layer containing an oligomer or polymer in the solvent and drying the applied layer to remove the solvent. Plasma polymerization may be utilized to provide a polymer layer having a glassy state at a high temperature and having a glass transition temperature equal to or higher than the glass transition temperature of HSPET. Most preferably, the first polymer layer is formed by flash evaporation and vapor deposition, followed by cross-linking at that location. For example, US Pat. No. 4,696,719 (Bischoff), US Pat. No. 4,722,515 (Ham), US Pat. No. 4,842,893 (Yializis et al.), US Pat. No. 4,954,371. Specification (Yializis), US Pat. No. 5,018,048 (Shaw et al.), US Pat. No. 5,032,461 (Shaw et al.), US Pat. No. 5,097,800 (Shaw et al.) ) Et al., US Pat. No. 5,125,138 (Shaw et al.), US Pat. No. 5,440,446 (Shaw et al.), US Pat. No. 5,547,

The smoothness and continuity of each polymer layer, as well as its adhesion to the underlying layer, is preferably enhanced by appropriate pretreatment. Preferred pretreatment measures are discharges in the presence of a suitable reactive or non-reactive atmosphere (eg, plasma, glow discharge, corona discharge, dielectric barrier discharge or atmospheric pressure discharge); chemical pretreatment or flame pretreatment. Use. These pretreatments help the underlying surface to be more receptive to the formation of subsequent polymer layers. Plasma pretreatment is particularly preferred. Another adhesion-promoting layer, which may have a different composition than the high Tg polymer layer, may also be utilized on top of the lower layer to improve the adhesiveness of the intermediate layer. The adhesion promoting layer can be, for example, another polymer layer or a metal-containing layer, for example, a layer of metal, metal oxide, metal nitride or metal oxynitride. The adhesion promoting layer may have a thickness of several nm (eg, 1 nm or 2 nm) to about 50 nm, and may be thicker if desired.

The desired chemical composition and thickness of the first polymer layer depends in part on the nature of the support and surface topography. The thickness is preferably sufficient to provide a smooth, defect-free surface to which the first inorganic barrier layer can subsequently be applied. For example, the first polymer layer may have a thickness of a few nm (eg, 2 nm or 3 nm) to about 50 micrometers, and may be thicker if desired.

At least two visible light transmissive inorganic barrier layers separated by a polymer layer having a Tg greater than or equal to Tg of HSPET are placed on top of the first polymer layer. These layers can be referred to as a "first inorganic barrier layer", a "second inorganic barrier layer" and a "second polymer layer", respectively. If desired, additional inorganic barrier layers and polymer layers may be present, including polymer layers that do not have a Tg greater than or equal to the Tg of HSPET. However, preferably, each adjacent pair of inorganic barrier layers is separated only by a polymer layer having a Tg greater than or equal to Tg of HSPET, and more preferably only by a polymer layer having a Tg greater than Tg of PMMA.

The inorganic barrier layers do not have to be the same. Various inorganic barrier materials can be used. Preferred inorganic barrier materials include metal oxides, metal nitrides, metal carbides, metal oxynitrides, metal borides and combinations thereof, such as silicon oxide such as silica, aluminum oxide such as alumina, titania. Such as titanium oxide, indium oxide, tin oxide, indium tin oxide (ITO), tantalum oxide, zirconium oxide, niobide oxide, boron carbide, tungsten carbide, silicon carbide, aluminum nitride, silicon nitride, boron nitride, oxynitride. Examples include aluminum, silicon oxynitride, boron oxynitride, zirconium oxyboride, titanium borohydride and combinations thereof. Indium tin oxide, silicon oxide, aluminum oxide and combinations thereof are particularly preferred inorganic barrier materials. ITO is an example of a special kind of ceramic material that can be made conductive by proper selection of the relative proportions of each constituent element. The inorganic barrier layer preferably employs techniques utilized in the field of film metallizing such as sputtering (eg, cathode or planar magnetron sputtering), evaporation (eg, resistance or electron beam evaporation), chemical vapor deposition, plating, etc. Formed using. Most preferably, the inorganic barrier layer is formed using sputtering, for example reactive sputtering. Enhanced barrier properties are observed when the inorganic layer is formed by a high energy deposition technique such as sputtering as compared to a low energy technique such as conventional chemical vapor deposition. Without being bound by theory, the enhanced properties are thought to be due to the concentration of species arriving at the substrate with greater kinetic energy, which results in a lower void ratio distribution as a result of compression. Guide. The smoothness and continuity of each inorganic barrier layer, as well as its adhesion to the underlying layer, can be enhanced by pretreatment (eg, plasma pretreatment) such as those described above for the first polymer layer.

The inorganic barrier layers do not have to have the same thickness. The desired chemical composition and thickness of each inorganic barrier layer depends in part on the nature and surface topography of the underlying layer and on the desired optical properties of the barrier assembly. The inorganic barrier layer is preferably thick enough to be continuous, and to ensure that the barrier assembly and the article containing the assembly have the desired degree of visible light transmission and flexibility. Thin enough. Preferably, the physical thickness (as opposed to the optical thickness) of each inorganic barrier layer is from about 3 nm to about 150 nm, more preferably from about 4 nm to about 75 nm.

In addition to its barrier function, all or part of one or more visible light transmissive inorganic barrier layers can be used for purposes such as electrodes (if properly conductive) or contact sensitive surfaces. .. It can be manufactured by leaving a portion of the exposed layer or by connecting the layer to lead, circuit traces or other electronic elements.

The second polymer layer that separates the first, second and any additional inorganic barrier layers may not be the same and may not all have the same thickness. Various second polymer layer materials are available. Preferred second polymer layer materials include those described above with respect to the first polymer layer. Preferably, the second polymer layer is applied by flash evaporation and vapor deposition as described above for the first polymer layer, followed by cross-linking at that location. Pretreatments such as those described above (eg, plasma pretreatments) are also preferably utilized prior to the formation of the second polymer layer. The desired chemical composition and thickness of the second polymer layer depends in part on the nature and surface topography of the underlying layer. The thickness of the second polymer layer is preferably sufficient to provide a smooth, defect-free surface to which the inorganic barrier layer can subsequently be applied. Typically, the second polymer layer may have a thickness less than that of the first polymer layer. For example, each second polymer layer may have a thickness of about 5 nm to about 10 micrometers, and may be thicker if desired.

Preferably, the barrier assembly may have a protective polymer topcoat. This topcoat can be called the "third polymer layer". Volatile (meth) acrylate monomers are preferred for use in the third polymer layer, and volatile acrylate monomers having a Tg greater than or equal to Tg of HSPET are particularly preferred (eg, as described above for the first and second polymer layers). , And volatile acrylate monomers with a higher Tg than PMMA are most preferred. If desired, a third polymer layer can be applied using conventional coating methods such as roll coating (eg gravure roll coating) or spray coating (eg electrostatic spray coating), and then , For example, can be crosslinked using UV radiation. Most preferably, the third polymer layer is formed by flash evaporation, vapor deposition, and cross-linking of the monomers, as described above for the first and second polymer layers. Pretreatments such as those described above (eg, plasma pretreatments) are also preferably utilized prior to the formation of the third polymer layer. The desired chemical composition and thickness of the third polymer layer depends in part on the nature and surface topography of the underlying layer, the risk of exposure of the barrier assembly, and applicable device requirements. The thickness of the third polymer layer is preferably sufficient to provide a smooth, defect-free surface that protects the underlying layer from the usual hazards. Typically, the third polymer layer may have a thickness less than that of the first polymer layer and greater than the thickness of the second polymer layer. For example, the third polymer layer may have a thickness of about 5 nm to about 10 micrometers, and may be thicker if desired.

The barrier assembly is visible light transmissive and approximately 0.005 g / m at 38 ° C and 100% relative humidity.²Less than / day, more preferably about 0.005 g / m at 50 ° C and 100% relative humidity²Less than / day, and most preferably about 0.005 g / m at 85 ° C and 100% relative humidity²The preferred barrier assembly has a sufficient number of inorganic barrier layers and substrates so that it has a water vapor permeability (WVTR) of less than / day, and the first and second polymer layers are preferably sufficiently high Tg. Has. A transparency value of at least about 20%, more preferably at least about 60% (Tvis, determined by averaging percent transmittance T between 400 nm and 700 nm) is preferred.

FIG. 3 shows a preferred device 180 that can be used for roll-to-roll manufacturing of the barrier assembly of the present invention. The powered rolls 181a and 181b move the support web 182 back and forth through device 180. Temperature-controlled rotating drums 183a and 183b, as well as idler rolls 184a, 184b, 184c, 184d and 184e, carry web 182 through a metal sputtering applicator 185, a plasma pretreatment machine 186, a monomer evaporator 187 and an electron beam cross-linking device 188. .. Liquid monomer 189 is supplied from reservoir 190 to evaporator 187. A continuous layer or layer pair can be applied to the web 182 using multiple passages through device 180. For example, additional applicators, pretreatment machines, evaporators, and cross-linking devices can be added to device 180 along the perimeter of drums 183a and 183b to allow continuous deposition of several pairs of layers. .. Equipment 180 is housed in a suitable chamber (not shown in Figure 3) to prevent oxygen, water vapor, dust and other atmospheric pollutants that interfere with various pretreatment, monomer coating, cross-linking and sputtering processes. It can be maintained under vacuum or can provide a suitable inert atmosphere.

Various functional layers and coatings can be added to the barrier assembly of the present invention to alter or improve their physical or chemical properties, especially on the surface of the barrier film. Such layers or coatings include, for example, visible light transmissive conductive layers or electrodes (eg, those of indium tin oxide); antistatic coatings or films; flame retardants; UV stabilizers; abrasion resistant or hard coat materials; optics. Coating; Anti-fog material; Magnetic or magnetic optical coating or film; Photoemulsion; Prism film; Holographic film or image; Adhesives such as pressure sensitive or hot melt adhesives; To facilitate adhesion to adjacent layers Primers; as well as low adhesive backsize materials for use when the barrier assembly is used in the form of adhesive rolls. These functional ingredients can be incorporated into one or more outermost layers of the barrier assembly or applied as separate films or coatings.

For some applications, for example, by laminating a dyed film layer on a barrier assembly, by applying a colored coating to the surface of the barrier assembly, or by making a barrier assembly. It is desirable to alter the appearance or performance of the barrier assembly by including dyes or pigments in one or more of the materials to be made. The dye or pigment is absorbable in one or more selected regions of the spectrum, including parts of the infrared, ultraviolet or visible spectrum. Dyes or pigments can be used to complete the properties of the barrier assembly, especially if the barrier assembly transmits some frequencies while reflecting others.

The barrier assembly can be processed with ink or other printed markings, such as those used to display product identification, placement information, advertisements, warnings, decorations or other information. Various techniques can be used to print on the barrier assembly, such as screen printing, inkjet printing, thermal transfer printing, letterpress printing, offset printing, flexo ink printing, stippling printing, laser printing, etc. , And various types of inks can be used, including one- and two-component inks, oxidative-dried and UV-dried inks, dissolved inks, dispersed inks and 100% ink systems.

In various applications, the barrier assembly of the present invention can be used to prevent the permeation of water vapor, oxygen or other gases. The barrier assembly of the present invention is particularly useful for encapsulation of OLEDs, light valves such as liquid crystal displays (LCDs) and other electronic devices. A representative encapsulated OLED device 200 of the present invention is shown in FIG. In FIG. 4, the front or light emitting side of the device 200 faces downward. The device 200 includes the visible light transmissive barrier assembly 210 of the present invention having an outer ITO layer (not shown in FIG. 4, but oriented downwards) that acts as an anode. The luminescent structure 220 is formed on the barrier assembly 210 in contact with the outer ITO layer. The structure 220 contains a plurality of layers (not individually shown in FIG. 4) that cooperate in downward emission through the barrier assembly 210 when properly energized. The device 200 also includes a conductive cathode 230 and a metal foil enclosure 250. The foil siege 250 is glued to the rear, side and front of the device 220 by an adhesive 240. The opening 260 formed in the adhesive 240 deforms a portion 270 of the foil 250 to allow contact with the cathode 230. Another opening in the foil 250 (not shown in FIG. 4) allows contact to be made by the anode formed by the outer ITO layer of the barrier assembly 210. The metal foil 250 and the barrier assembly 210 primarily prevent water vapor and oxygen from reaching the luminescent structure 220.

The present invention is described by reference to the following non-limiting examples. Here, all parts and percentages are by weight unless otherwise noted.

Example 1 Polyethylene naphthalate ("PEN") supported by a laminate of acrylate and indium tin oxide ("ITO") layers arranged in seven layers in an alternating arrangement of acrylate / ITO / acrylate / ITO / acrylate / ITO / acrylate. Covered the film. The individual layers were formed as follows.

(Layer 1) 91 m long, 0.127 mm thick x 508 mm wide roll, available commercially from KALADEX® 1020 PEN film (Dupont-Teijin Films) , Tg = 120 ° C) was loaded into a roll-to-roll vacuum processing chamber. Chamber pressure 8x10^-6Pumped down to Thor. Using a web speed of 9.1 m / min, and keeping the back of the film in contact with the coating drum cooled to 0 ° C, the film was operated by a nitrogen plasma operated at 600 W using a titanium cathode. Processed. Immediately after plasma treatment and with the film still in contact with the drum, the plasma treated film surface is commercially available from 97% IRR-214 cyclic diacrylate (UCB Chemicals, Tg = 208 °. It was coated with an acrylate mixture prepared by combining C) with 3% EBECRYL® 170 Acrylic Acid Adhesion Accelerator (available commercially from UCB Chemicals). This acrylate mixture was evacuated prior to coating and operated at a frequency of 60 kHz to an ultrasonic atomizer (Sonotec Corporation). It was pumped into a heated evaporation chamber maintained at 275 ° C through (commercially available from Corp.) at a flow rate of 3.0 ml / min. The resulting monomer vapor stream was concentrated on the plasma treated film surface and electron beam crosslinked using a single filament operated with an 8 kV and 2.5 mm amplifier to form a 426 nm thick acrylate layer. ..

(Layer 2) Inside the chamber, reverse the web orientation, and 90% In₂O₃/ 10% SnO₂A target (available commercially from Umicore Indium Products) was used to sputter-deposit an ITO inorganic oxide layer onto a 20 meter long acrylate-coated web surface. The ITO was sputtered using a gas mixture containing 134 sccm argon and 3.0 sccm oxygen at a power of 1500 watts, a pressure of 3 mitol, and a web rate of 0.55 m / min and deposited on the acrylate of layer 1. An ITO layer with a thickness of 48 nm was provided.

(Layer 3) Again, the web direction was reversed. The second acrylate layer was coated and crosslinked on the same 20 meter web length using the same general conditions as for layer 1, with the exception of these. Plasma treatment was performed at 3000 W using a titanium cathode and a layer 2 argon / oxygen gas mixture, and the monomer flow rate was 1.1 ml / min. As a result, an acrylate layer having a thickness of 104 nm was provided on the layer 2.

(Layer 4) Again, the web direction was reversed. A 48 nm thick ITO layer was deposited on layer 3 using the same conditions as for layer 2.

(Layer 5) Again, the web direction was reversed. An acrylate layer with a thickness of 104 nm was coated on layer 4 using the same conditions as for layer 3.

(Layer 6) Again, the web direction was reversed. A 48 nm thick ITO layer was deposited on layer 5 using the same conditions as for layer 2.

(Layer 7) Again, the web direction was reversed. An acrylate layer with a thickness of 104 nm was coated on layer 6 using the same conditions as for layer 3.

The resulting 7-layer laminate (not counting substrates) was obtained by averaging the average spectral transmittance Tvis = 50% (percentage T between 400 nm and 700 nm) measured at an incident angle of 30 °. 0.005 g / m of (determined), and MOCON PERMATRAN-W® 3/31 WVTR testing system (commercially available from MOCON Inc)²Water vapor permeability (determined at 85 ° C and 100% RH according to ASTM F-129) was below the lower detection limit of / day. The film is also commercially available from MOCON OXTRAN® 2/20 Oxygen Permeability Testing System (MOCON Inc) when evaluated at 38 ° C and 90% RH. ) 0.005cc / m²Shows oxygen permeability that was below the lower detection limit of / day (determined according to ASTM D-3985 and evaluated on both sides of the film facing the test gas), and evaluated at 50 ° C and 90% RH. If so, 0.030cc / m²It showed less than the average value of / day.

The barrier assembly of Example 1 was impregnated with liquid nitrogen, folded in half, and cross-section tested using a scanning electron microscope. FIG. 5 shows the obtained micrograph. In FIG. 5, the support 312, the first polymer layer 314, the visible light transmissive inorganic barrier layers 316, 320 and 324, the second polymer layers 318 and 322, and the third polymer layer 326 are clearly visible.

Example 2 A 7-layer laminate was prepared in the same manner as in Example 1 with SR-368D mixed acrylate mixture (SR-351 trimethylolpropane triacrylate and SR-368 tris (2-hydroxyethyl) isocyanurate triacrylate. A 50:50 mixture (available commercially from Artomer Co.) was used, and no plasma treatment was used in the formation of layers 3, 5 and 7. Based on the arithmetic mean of SR-351's 62 ° C Tg and SR-368's 272 ° C Tg, the estimated Tg for SR-368D is 167 ° C.

The resulting 7-layer laminate had an average spectral transmittance of Tvis = 68% measured at an incident angle of 30 °, and 0.005 g / m of the WVTR testing system.²WVTR (determined at 50 ° C and 100% RH) was below the lower detection limit of / day.

Example 3 A 7-layer laminate was prepared in the same manner as in Example 1, but commercially available from MELINEX® 617 polyethylene terephthalate (PET) film substrate (DuPont-Teijin Films). Available as an article, Tg = 70 ° C) and various acrylates were used. As the acrylate of layer 1, tripropylene glycol diacrylate (TRPGDA, commercially available from UCB Chemicals, Tg = 62 ° C) was used. Layers 3, 5 and 7 were formed using a mixture containing 97% TRPGDA and 3% EBECRY L170 acrylic acid adhesion accelerator and having an estimated Tg = 62 ° C.

The resulting 7-layer laminate had an average spectral transmittance of Tvis = 71% and 0.036 g / m measured at an incident angle of 30 °.²/ Day WVTR (determined at 50 ° C and 100% RH) was shown.

Example 4 Heat-stabilized PET substrate A 7-layer laminate was prepared in the same manner as in Example 1, but obtained as a commercial product from MELINEX® ST725 heat-stabilized PET film substrate (DuPont-Teijin Films). Possible, Tg = 78 ° C), 100% IRR-214 acrylate without the use of EBECRYL170 acrylic acid adhesion accelerator for layers 1, 3, 5 and 7, and silicon when depositing layers 3, 5 and 7. Plasma treatment performed at 2000 W with a cathode and layer 2 argon / oxygen gas mixture was used.

The resulting 7-layer laminate had an average spectral transmittance of Tvis = 77% and 0.006 g / m measured at an incident angle of 30 °.²/ Day WVTR (determined at 60 ° C and 100% RH) was shown.

Example 5 Effect of base material Tg on WVTR SiAlO Inorganic Oxide Arranged in Inorganic Oxide / Barrier Polymer / Inorganic Oxide Arrangement and Commercially Available Barrier Polymer (SARAN® F-278, Commercially Available from Dow Chemical Company) A three-layer laminate (available as) covering several substrates with varying glass transition temperatures. As a preparatory step, parts of polymethylpentene, polypropylene, PET and polyether sulfone film substrates were spliced end-to-end together to produce a single roll. Individual inorganic oxide and barrier polymer layers were formed on these substrates as follows.

(Layer 1) Roll-to-roll Splice rolls were loaded into a sputter coater. The pressure in the film formation chamber is 2 x 10^-6Pumped down to Thor. Using a gas mixture containing 51 sccm argon and 30 sccm oxygen at a pressure of 2 kW and 600 V, 1 mitol, and a web rate of 0.43 m / min, the Si-Al (95/5) target (Academy Precision Materials (Academy Precision Materials) A 60 nm thick SiAlO inorganic oxide layer was deposited on the substrate film by reactive sputtering (available as a commercial product from Academy Precision Materials).

(Layer 2) Oxide-coated webs were removed from the vacuum coater. Tetrahydrofuran and toluene using a model CAG-150 microgravure coater (commercially available from Yasui-Seiki Co.) with a 150R knurled roll operated at a web speed of 6.1 m / min. A 10% solution of Saran F278 polymer in a 65 / 35v / v mixture with was continuously coated on layer 1. The solution was evaporated in the dry portion of the coater at a temperature of 80 ° C.

(Layer 3) A polymer-coated web was loaded into a vacuum coater. A second SiAlO inorganic oxide layer was deposited on layer 2 using the same conditions as for layer 1.

The WVTR of each part of the coated barrier assembly was then determined at 38 ° C and 100% RH. The results are summarized in Table 1 below.

<tables num="1"><img file="JP5117717B2_D0001.tif" /></tables>

As shown in Table 1 by PET and PES substrates, increasing substrate Tg tended to decrease WVTR values. Since PMP and PP substrates had Tg values below the WVTR test temperature, therefore, their WVTR values can be somewhat affected, unlike higher Tg substrates.

Example 6 Effect of polymer layer Tg on WVTR A continuous 4-layer polymer / inorganic oxide / polymer / inorganic oxide laminate utilizing polymer layers with various glass transition temperatures, available commercially from HSPE100 0.1 mm PET film (Teijin Films), Tg = 70 ° C) was covered. The inorganic oxide was ITO and formed a polymer from the components presented in Table 2. Here, the amount of each component is shown as parts by weight in the formulation.

<tables num="2"><img file="JP5117717B2_D0002.tif" /></tables>

(Layer 1) Using a model CAG-150 microgravure coater and 150R knurl at a line speed of 6.1 m / min, the continuous portion of the PET film substrate was coated with the five formulations shown in Table 2. The coating was cured using a 100% powered 6kW Fusion H bulb (commercially available from Fusion UV Systems).

(Layer 2) The coated film substrate is loaded into a sputter coater and 2x10^-6Pumped down to Thor's base pressure. 300W and 420V and 90/10 tin oxide / indium oxide targets (commercially available from Arconium Specialty Alloys), a gaseous mixture containing 30 sccm argon and 8 sccm oxygen at a pressure of 4 millitorols, and 0.127 A 40 nm thick ITO inorganic oxide layer was deposited on top of the Layer 1 formulation using a web rate of metric / min.

(Layer 3 and Layer 4) A second polymer layer is coated over layer 2 to form layer 3 using the same conditions as for layer 1 and layer 2, respectively, and a second ITO Layers were deposited on top of layer 3 to form layer 4.

The WVTR of each part of the coated barrier assembly was then determined at 50 ° C and 100% RH. The results are summarized in Table 3 below.

<tables num="3"><img file="JP5117717B2_D0003.tif" /></tables>

As shown by formulations 1, 2 and 5 in Table 3, increasing polymer Tg tended to decrease WVTR values. The polymers of Formulations 1, 2 and 5 were made from substantial amounts of polyfunctional monomers or oligomers. For formulations 3 and 4, some different behavior was observed. Formulation 3 contains 75% monofunctional monomers and is therefore not crosslinked in the same manner as Formulations 1, 2 and 5. Formulation 4 is based on a liquid crystal polymer obtained by UV curing a liquid crystal diacrylate monomer and therefore does not act in the same manner as Formulations 1, 2 and 5.

Example 7 Laminated barrier structure A laminated barrier assembly was assembled to bond two barrier assemblies with a six-layer laminate on a PET substrate together in a face-to-face manner using an optical adhesive. The completed laminated barrier assembly had a PET / Polymer 1 / SiAlO / Polymer 2 / SiAlO / Polymer 2 / SiAlO / Optical Adhesive / SiAlO / Polymer 2 / SiAlO / Polymer 2 / SiAlO / Polymer 1 / PET arrangement. .. Barrier assemblies were formed and laminated together as follows.

(Layer 1) Formulation using model CAG-150 microgravure coater and 110R knurling at 6.1 m / min<u style="single">1</u>(In Table 4<u style="single">Show</u>) Was coated with HSPE50 0.05mm PET film (commercially available from Teijin, Tg = 70 ° C). The coating was cured using a 100% power operated Fusion F600 H bulb to provide a layer identified as "Polymer 1". Polymer 1 had a Tg of 122.8 ° C, as determined using optical differential scanning calorimetry (optical DSC).

(Layer 2) A 60 nm thick SiAlO inorganic oxide layer was deposited on layer 1 using the conditions described for the SiAlO inorganic oxide layer of Example 5.

(Layer 3) Use the conditions described for Layer 1, but use a coating rate of 4.6 m / min, formulation.<u style="single">2</u>(In Table 4<u style="single">Show</u>) To coat and cure layer 2 to provide a layer identified as "Polymer 2". Polymer 2 had a Tg of 90 ° C.

(Layer 4, Layer 5 and Layer 6) Using the same conditions for Layer 2 and Layer 3, respectively, a second SiAlO layer was deposited on Layer 3 to form Layer 4 and a second. A layer of polymer 2 of the polymer 2 is coated over layer 4 to form layer 5, and a third SiAlO layer is deposited on layer 5 to form layer 6, thereby PET / polymer 1 / SiAlO /. Barrier assemblies with Polymer 2 / SiAlO / Polymer 2 / SiAlO configurations were provided.

<tables num="4"><img file="JP5117717B2_D0004.tif" /></tables>

The resulting coated barrier assembly roll was split into two rolls and 3M® 8141 optically transparent laminated adhesive (available commercially from 3M Company (3M Co.)). And using a roll-to-roll laminator, they were laminated together in a face-to-face fashion. WVTR values were determined for non-laminated barrier assemblies at 38 ° C and 100% RH, and for laminated barrier assemblies at 38 ° C / 100% RH and 50 ° C / 100% RH. The results are shown in Table 5 below.

<tables num="5"><img file="JP5117717B2_D0005.tif" /></tables>

As shown by the results in Table 5, the area-to-area stratification step results in a reduction in WVTR. WVTR is 0.005 g / m of MOCON PERMATRAN-W3 / 31 WVTR testing system at both 38 ° C and 50 ° C measurement temperatures.²It remained below the lower detection limit of / day.

Example 8 OLED device Samples from the barrier assembly of Example 1 were again loaded into a roll-to-roll vacuum chamber for deposition of the top surface ITO conductive layer formed as follows.

(Layer 8) The ITO was sputter-deposited using the same conditions as for Layer 6, but using a web rate of 0.19 m / min, an ITO deposited on the acrylate of Layer 7 with a thickness of 138 nm. Provided a layer.

The resulting top surface conductive barrier was cut into 22 mm x 22 mm squares using an X-ACTO® knife (commercially available from Hunt Corporation). After rinsing with acetone and air drying, use the MICRO-RIE® Series 80 Plasma System (commercially available from Technics, Inc.) to make this square. It was cleaned with oxygen plasma and exposed at 50 watt power and 200 mitol oxygen pressure for 4 minutes. On a cleaned square, BAYTRON® P4083 Polythiophene (Bayer Corporation) A 1% solid aqueous solution (available as a commercial product from Corporation) was spin-coated at 2500 rpm for 30 seconds. First, a 22 x 22 x 1 mm glass slide is placed on a vacuum chuck, a vacuum is applied to hold the glass slide in place, a drop of methanol is added to the top of the glass slide and cleaned. The squares were placed on top of the methanol and the edges of the squares were aligned with the edges of the glass slides to hold the squares in place on the spin coater vacuum chuck. Methanol fills the space between the glass slide and the square and holds the square in place during the spin coating operation. The coated squares were dried on a hot plate at 70 ° C under a nitrogen atmosphere.

Transfer the coated squares to a bell jar type evaporation chamber, and about 10^-6Exhausted to Thor. Subsequent layers were sequentially thermally deposited onto the coated square through a shadow mask containing a 19.5 mm square opening.

(Layer 1) Dope with 7% tetrafluorotetracyanoquinodimethane ("FTCNQ", commercially available from Tokyo Kasei Kogyo Co., Tokyo, Japan), Tokyo, Japan. 4,4', 4 -Tris (N- (3-Methylphenyl) -N-Phenylamino) Triphenylamine (MTDATA, commercially available from HW Sands Corp.) Thickness 2245 Å layer.

(Layer 2) N, N'-di (naphthalene-1-yl) -N, N'-diphenylbenzidine ("Alpha-NPB", commercially available from HW Sands Corp. as OPD7534) A layer with a thickness of 300 Å.

(Layer 3) 1% (10- (2-benzothiazolyl) -2,3,6,7-tetrahydro-1,1,7,7, -tetramethyl l-1H, 5H, 11H- [1] benzopyrano [6] , 7,8-ij] Quinolizidine-11-one (C545T dye, commercially available from Eastman Kodak Co.) doped with Tris (8-hydroxyquinolinolato) aluminum ("AlQ₃A 300 Å thick layer (available commercially from HW Sands Corp.).

(Layer 4) AlQ₃200Å thick layer.

Due to the thermal deposition of the cathode, the deposited squares were transferred to a glove box containing a thin film evaporation chamber (Edwards 500, commercially available from BOC Edwards). 1 cm arranged so that the cathode is deposited approximately in the center of the square²Through a metal shadow mask with a circular opening of about 10^-7In Thor, a 1000 Å thick calcium layer (using a target commercially available from Alfa-Aesar Co.) and a 2000 Å thick silver layer (Alfa-Aesar Co.) (Using a commercially available target from Co.) was deposited continuously on a square. By contacting the ITO anode with the alligator clip and the Ca / Ag cathode with the pure gold wire, a green light was emitted when approximately 4-9 volt DC passed through the finished OLED device.

The device was encapsulated with copper foil as described in US Patent Application No. 10 / 324,585, pending a December 19, 2002 application. Approximately 50mm x 100mm piece of 3M® Thermo-Bond Film 845 EG heat laminated film (adhesive thickness 0.06mm) into a 25mm square with 2x8 grid on its release liner side I pressed it. A 6 mm circular hole was cut at the center of each 25 mm square using a handheld paper punch. Approximately 125 x 75 mm piece thickness 0.05 mm Cu foil (McMaster-Carr Supply Co.) that contacts the perforated fused deposition film with the foil on the adhesive side is available as a commercial product. 76 x 229 x 0.64 mm aluminum plate placed on top and then in contact with the aluminum plate on the release liner side (Q-panel Company (Q-panel) (Available as a commercial product from Company)) placed on. The resulting assembly was operated three times in a row at approximately 102 ° C. TDE Systems Model HL-406 2-Roll Thermal Laminator (Kmart Corporation) Supplied through (commercially available from Corp.)), the adhesive film was laminated on Cu foil, and the foil was transformed into 6 mm holes in the adhesive. Laminated Cu foil was removed from the aluminum carrier plate, cut into 25 mm squares with scissors, and placed in a glove box containing a green radiant OLED device. The 25 mm square of the laminated Cu foil was scissored into approximately 20 mm squares so that the 6 mm holes in the adhesive layer remained approximately in the center of the square. The release liner is then removed and the exposed adhesive layer is placed relative to one cathode side of the 22 mm square OLED device, with a 6 mm hole through the adhesive layer approximately in the center of the cathode of the OLED device. Positioned, and the laminated Cu foil square was rotated up to 45 ° with respect to the OLED substrate, the corners of the laminated Cu foil square were snug and extended approximately beyond the edge of the OLED substrate. Using tweezers, the resulting assembly was held together and placed on a hot plate at 100 ° C for about 20 seconds, causing adhesion of the laminated Cu foil to the OLED substrate. The resulting assembly was then placed in the inert nitrogen atmosphere of the glove box from the BESTECH® model 2962 2 roll thermal laminator (Rose Art Industries) operated at approximately 100 ° C. The corners of the Cu foil were folded over the front of the OLED device and laminated there by passing it through (available as a commercial product). Upon cooling, an anode connection to the encapsulated OLED was made by contacting the exposed ITO portion at the corner of the device, and a cathode connection was made by contacting the Cu foil. A green light was emitted from the device when the current was applied.

Various modifications and modifications of the present invention will be apparent to those skilled in the art without departing from the present invention. The present invention should not be limited to those specified herein for purposes of illustration only.

<figref num="1">Schematic cross-sectional view of the disclosed barrier assembly.</figref><figref num="2">Schematic cross-sectional view of the disclosed laminated barrier assembly.</figref><figref num="3">Schematic of a device for performing the disclosed method.</figref><figref num="4">Schematic cross-sectional view of the disclosed OLED device.</figref><figref num="5">A photomicrograph of the disclosed barrier assembly.</figref>