KR102223910B1 - Encapsulation composition for organic electronic element - Google Patents

Abstract

The present application relates to a composition for sealing an organic electronic device and an organic electronic device including the same, and it is possible to form a structure that can effectively block moisture or oxygen flowing into the organic electronic device from the outside, thereby securing the life of the organic electronic device. It is possible to implement a top emission type organic electronic device, and provide a sealing composition capable of preventing defects such as dark spots that may occur in the organic electronic device, and an organic electronic device including the same.

Description

Composition for sealing organic electronic devices {ENCAPSULATION COMPOSITION FOR ORGANIC ELECTRONIC ELEMENT}

The present application relates to a composition for encapsulating an organic electronic device, an organic electronic device including the same, and a method of manufacturing the organic electronic device.

An organic electronic device (OED) refers to a device including an organic material layer that generates an exchange of charges using holes and electrons, and examples thereof include a photovoltaic device, a rectifier, and And a transmitter and an organic light emitting diode (OLED).

Among the organic electronic devices, an organic light emitting diode (OLED) consumes less power than a conventional light source, has a faster response speed, and is advantageous in reducing the thickness of a display device or lighting. In addition, OLED has excellent space utilization and is expected to be applied in various fields ranging from various portable devices, monitors, notebooks, and TVs.

In the commercialization and expansion of OLED use, the most important problem is the durability problem. Organic materials and metal electrodes included in OLEDs are very easily oxidized by external factors such as moisture. Therefore, products containing OLED are highly sensitive to environmental factors. Accordingly, various methods have been proposed to effectively block the penetration of oxygen or moisture from the outside into an organic electronic device such as OLED.

This application enables the formation of a structure that can effectively block moisture or oxygen flowing into the organic electronic device from the outside, thereby securing the life of the organic electronic device, and the realization of a top emission type organic electronic device. It provides an encapsulation composition capable of preventing defects such as dark spots that may occur in a device, and an organic electronic device including the same.

The present application relates to a composition for sealing an organic electronic device. The composition may be an adhesive composition or an adhesive composition. The encapsulation composition may be, for example, an encapsulant applied to encapsulating or encapsulating an organic electronic device such as an OLED. In one example, the encapsulation composition of the present application may be applied to encapsulating or encapsulating the entire surface of an organic electronic device. Therefore, after the encapsulation composition is applied to encapsulation, it may exist in a form that seals the entire surface of the organic electronic device.

In the present specification, the term "organic electronic device" refers to an article or device having a structure including an organic material layer that generates an exchange of charges using holes and electrons between a pair of electrodes facing each other, for example Examples include, but are not limited to, a photovoltaic device, a rectifier, a transmitter, and an organic light-emitting diode (OLED). In one example of the present application, the organic electronic device may be an OLED.

An exemplary composition for sealing an organic electronic device includes a curable compound. In addition, the sealing composition has a viscosity measured at a temperature of 25° C. and ^{a shear rate of 0.1 sec -1} of 1 million cps or more, 1.15 million cps or more, 1.28 million cps or more, or 1.36 million cps or more, and a temperature of 25° C. and The ^{viscosity measured at a shear rate of 5.0sec -1} may be 150,000 cps or less, 140,000 cps or less, 130,000 cps or less, or 120,000 cps or less. The present application is to control the viscosity of the encapsulation composition according to the shear rate, thereby improving the application characteristics on the organic electronic device during application, and at the same time implementing a high viscosity after application so that the composition penetrates into cracks that may be generated on the device. prevent.

Specifically, the encapsulation composition of the present application is applied to the entire surface of the organic electronic device to form a front encapsulation layer, and the liquid composition may damage the device during the application process. For example, in the organic electronic device, a protective film to be described later may be formed on the electrode, and a crack may be generated in the protective film by foreign substances such as dust on the device. These cracks may cause dark spots, and there may be a problem in which the liquid composition penetrates between these cracks. However, in the present application, after the encapsulation composition is applied to the entire surface of the device to form a front encapsulation layer, the composition maintains a high viscosity to prevent crack growth due to penetration of the composition between the cracks.

In addition, the composition for sealing may have a curing shrinkage (φ) of 5% or less or 4% or less represented by the following General Formula 1.

[General Formula 1]

φ = (1/ρ _l -1/ρ _s ) × ρ _l × 100

In General Formula 1, ρ _l is a liquid density measured according to ASTM D1475 before curing of the composition, and ρ _s is a solid density measured according to KS M3010 after curing of the composition. The present application prevents physical and chemical damage to the device due to the characteristics applied to the organic electronic device by controlling the curing shrinkage rate.

In one example, the curable compound may include at least one curable functional group. The curable functional group may be, for example, one or more selected from a glycidyl group, an isocyanate group, a hydroxy group, a carboxyl group, an amide group, an epoxide group, a cyclic ether group, a sulfide group, an acetal group, and a lactone group. In addition, the curable compound may be at least one functional or more or bifunctional or more, and may be a combination of a monofunctional compound and a bifunctional or more compound. That is, one or two or more curable functional groups may be present in the compound. The curable compound implements an appropriate degree of crosslinking in the encapsulant to realize excellent heat resistance and durability at high temperature and high humidity.

In the specific example of the present application, the curable compound has a weight average molecular weight of more than 300 g/mol, and may include a compound having a cyclic structure in the molecular structure. The compound may have a weight average molecular weight in the range of 300 g/mol to 10,000 g/mol, 340 g/mol to 5,000 g/mol, 360 g/mol to 1,000 g/mol, or 390 g/mol to 800 g/mol have. The compound having the cyclic structure may be a hydrogenated compound. In the specification, the term hydrogenated compound may mean a compound obtained by adding hydrogen to an unsaturated bond in an organic compound, for example, a carbon-carbon double bond or a triple bond, or a multiple bond such as a carbonyl group. The hydrogenated compound in the above may mean a compound in which all of the unsaturated bonds are hydrogenated. By including the curable compound, the present application may prevent shrinkage and expansion of the encapsulant after curing and implement excellent optical properties.

In one example, the weight average molecular weight is greater than 300 g/mol, and the compound having a cyclic structure may be, for example, an aromatic (eg, phenyl group) compound. For example, the curable compound of the present application may include a hydrogenated aromatic epoxy compound. Specific examples of compounds having a cyclic structure that can be used in the present application include biphenyl-type epoxy resins, dicyclopentadiene-type epoxy resins, naphthalene-type epoxy resins, dicyclopentadiene-modified phenol-type epoxy resins, cresol-based epoxy resins, It may be a bisphenol-based epoxy resin, a xylog-based epoxy resin, a polyfunctional epoxy resin, a phenol novolac epoxy resin, a triphenolmethane-type epoxy resin, and an alkyl-modified triphenolmethane epoxy resin, but is not limited thereto.

In one example, the curable compound may further include a compound having a weight average molecular weight of 300 g/mol or less. The compound may have a weight average molecular weight in the range of 50 g/mol to 295 g/mol, 100 g/mol to 288 g/mol, or 120 g/mol to 275 g/mol. In the present specification, a compound having a weight average molecular weight of 300 g/mol or less may be referred to as a low molecular weight curable compound. The weight average molecular weight of the compound having a weight average molecular weight of 300 g/mol or less is 20 parts by weight to 80 parts by weight, 23 to 75 parts by weight, 25 to 73 parts by weight, 28 to 68 parts by weight or 32 based on 100 parts by weight of the compound having the aforementioned cyclic structure. It may be included in to 67 parts by weight. The present application includes the low molecular weight curable compound, so that the application characteristics of the encapsulation composition applied in a liquid form are excellently implemented, the desired viscosity is realized after being applied, and the curing shrinkage rate before and after curing can be minimized. .

In the present specification, the weight average molecular weight refers to a value converted to standard polystyrene measured by GPC (Gel Permeation Chromatograph).

The low molecular weight curable compound may include a linear, branched or cyclic curable compound.

Linear or branched curable compounds are, for example, aliphatic glycidyl ether, 1,4-butanediol diglycidyl ether, ethylene glycol diglycidyl ether, 1,6-hexanediol di Glycidyl ether, propylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether or neopentyl glycol diglycidyl ether It may include, but is not limited thereto.

In one example, the low molecular weight curable compound may include a compound containing an oxetane group, and the structure is not limited as long as the compound has the oxetane functional group. The compound having an oxetane functional group may be, for example, OXT-221, CHOX, OX-SC, OXT101, OXT121, OXT221 or OXT212 from TOAGOSEI, or EHO, OXBP, OXTP or OXMA from ETERNACOLL.

In addition, in one example, the compound having a cyclic structure in the molecular structure is 3,4-epoxycyclohexylmethyl 3',4'-epoxycyclohexanecarboxylate (EEC) and derivatives, dicyclopentadiene dioxide and derivatives, vinyl Cyclohexene dioxide and derivatives, 1,4-cyclohexanedimethanol bis (3,4-epoxycyclohexanecarboxylate) and derivatives may be exemplified, but are not limited thereto. As the compound, a commercially available product may be exemplified by Daicel's Celloxide 2021, Celloxide 2080 or Celloxide 3000.

In one example, the encapsulation composition of the present application may include a thermal initiator and/or a photoinitiator. The thermal initiator or photo initiator may be a cationic initiator. As the cationic initiator, a cationic photopolymerization initiator or a cationic thermal initiator can be used.

In one example, as the cationic thermal initiator, materials known in the art may be used. For example, the cationic thermal initiators include amine groups and a cation portion AsF centered ^may include a compound having, or tetrakis (penta-fluorophenyl) borate anion portion ^-, SbF ₆ ^-, PF _6.

In addition, it is possible to use a known material in the art for cationic photo-polymerization initiator, for example, aromatic sulfonium, aromatic iodonium, aromatic diazonium and aromatic ammonium cation portion and AsF _6, including ^-, SbF ₆ ^-, It may include a compound having, or tetrakis (penta-fluorophenyl) borate anion portion containing ^- PF _6. In addition, as the cationic photopolymerization initiator, an onium salt or an organometallic salt-based ionized cationic initiator or an organosilane or latent sulfonic acid-based or non-ionized cationic photopolymerization initiator may be used. Examples of the onium salt-based initiator include a diaryliodonium salt, a triarylsulfonium salt, or an aryldiazonium salt. Initiation of an organometallic salt series As the zero, iron arene, etc. may be exemplified, and examples of the organosilane-based initiator include o-nitrobenzyl triaryl silyl ether, triaryl silyl peroxide. Alternatively, acyl silane may be exemplified, and the latent sulfuric acid-based initiator may include α-sulfonyloxy ketone or α-hydroxymethylbenzoin sulfonate, but is not limited thereto. .

In the embodiment of the present application, the thermal initiator and/or the photoinitiator may be included in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the curable compound. The content may be a range of content when the thermal initiator is used alone, when a photoinitiator is used alone, or when used together. In a specific example of the present application, the thermal initiator is 0.01 to 0.45 parts by weight, 0.01 to 0.4 parts by weight, 0.01 to 0.35 parts by weight, 0.01 to 0.3 parts by weight, 0.01 to 0.25 parts by weight, or 0.01 to 0.45 parts by weight based on 100 parts by weight of the curable compound. It may be included in 0.2 parts by weight. In addition, the photoinitiator may be included in an amount of 0.01 to 0.45 parts by weight, 0.01 to 0.4 parts by weight, 0.01 to 0.35 parts by weight, or 0.01 to 0.3 parts by weight based on 100 parts by weight of the curable compound. The encapsulation composition of the present application may contain a photo initiator and a thermal initiator in a small amount compared to the prior art, and since the desired viscosity or hardness can be realized during UV temporary curing in the weight ratio range, it will be effective in preventing damage to the aforementioned device. I can. In addition, it is possible to provide an encapsulant having sufficient moisture barrier properties and durability reliability in encapsulating the entire device.

In the embodiment of the present application, the encapsulation composition may further include a curing retardant. The curing retardant may be included in an amount of 0.01 to 10 parts by weight, 0.05 to 5 parts by weight, or 0.05 to 3 parts by weight based on 100 parts by weight of the curable compound. The present application can improve the storage stability of the encapsulation composition and perform photo-curing and thermal curing more efficiently within the above content range. The curing retardant is, for example, benzyl amine, cyclic polyether, boric acid, phenylboric acid, salicylic acid, hydrochloric acid, sulfuric acid, oxamic acid, tetraphthalic acid, isophthalic acid, phosphoric acid, acetic acid, and lactic acid. It is preferable that one or more types are selected from the group.

In one example, the encapsulation composition may have excellent light transmittance with respect to the visible light region after curing. In one example, the encapsulation composition of the present application may exhibit a light transmittance of 90% or more according to JIS K7105 standard after curing. For example, the encapsulant may have a light transmittance of 92% or more or 95% or more with respect to the visible light region. In addition, the encapsulant of the present application may exhibit excellent light transmittance and low haze. In one example, the encapsulation composition may have a haze of 5% or less, 4% or less, 3% or less, or 1% or less after curing according to the standard of JIS K7105. The optical properties may be measured at 550 nm using a UV-Vis Spectrometer.

In one example, the encapsulation composition may further include a thixotropic agent. The thixotropic imparting agent may be an inorganic filler. The inorganic filler may be included to control thixotropy of the encapsulation composition. The specific type of the filler that can be used in the present application is not particularly limited, and for example, one type of silica, calcium carbonate, alumina, or talc, or a mixture of two or more types may be used. Meanwhile, in the present specification, "thixotropic" may mean a property that the composition has no fluidity when it is stationary, but has fluidity when it vibrates. The method of measuring the thixotropic index is not particularly limited, and can be measured using a rheological property measuring instrument known in the art. For example, DV-II+Pro or ARES-G2 (TA company) is used as a Brookfield viscometer. I can.

In addition, the BET surface area of the inorganic filler may be in the range of 35 to 500m ² /g, 40 to 400m ² /g, 50 to 300m ² /g, or 60 to 200m ² /g. The specific surface area was measured using the BET method, and specifically, by adding a sample of 1 g of the inorganic filler to a tube, it can be measured using ASAP2020 (Micromeritics, USA) without pretreatment at -195°C. The average value can be obtained by measuring three times for the same sample. The present application may provide an encapsulant capable of easily implementing the encapsulation structure shape desired in the present application by adjusting the specific surface area of the inorganic filler within the above range.

In the present application, a product surface-treated with an organic material may be used as the filler, or a coupling agent may be additionally added to increase the bonding efficiency between the filler and the organic binder.

The encapsulation composition of the present application may include a moisture adsorbent, if necessary. The term “moisture adsorbent” may be used as a generic term for a component capable of adsorbing or removing moisture or moisture introduced from the outside through a physical or chemical reaction. That is, it means a moisture-reactive adsorbent or a physical adsorbent, and a mixture thereof may also be used.

The moisture-reactive adsorbent absorbs moisture or moisture by chemically reacting with moisture, moisture, or oxygen introduced into the encapsulation composition or the cured product thereof. The physical adsorbent can inhibit the penetration by lengthening the movement path of moisture or moisture penetrating into the resin composition or its cured product, and moisture and moisture through interaction with the matrix structure of the resin composition or its cured product and a moisture-reactive adsorbent, etc. The barrier to moisture can be maximized.

The specific type of moisture adsorbent that can be used in the present application is not particularly limited, and for example, in the case of a moisture-reactive adsorbent, one or more mixtures of _{metal oxides, metal salts, or phosphorus pentoxide (P 2} O _{5) may be mentioned.} And, in the case of a physical adsorbent, zeolite, zirconia, montmorillonite, etc. are mentioned.

Specific examples of the metal oxide in the above include lithium oxide (Li ₂ O), sodium oxide (Na ₂ O), barium oxide (BaO), calcium oxide (CaO), or magnesium oxide (MgO). Examples include lithium sulfate (Li ₂ SO ₄ ), sodium sulfate (Na ₂ SO ₄ ), calcium sulfate (CaSO ₄ ), magnesium sulfate (MgSO ₄ ), cobalt sulfate (CoSO ₄ ), gallium sulfate (Ga ₂ (SO ₄ ) ₃ ), titanium sulfate (Ti(SO ₄ ) ₂ ) or nickel sulfate (NiSO ₄ ) sulfate, calcium chloride (CaCl ₂ ), magnesium chloride (MgCl ₂ ), strontium chloride (SrCl ₂ ), yttrium salt (YCl ₃ ) , Copper chloride (CuCl ₂ ), cesium fluoride (CsF), tantalum fluoride (TaF ₅ ), niobium fluoride _{(NbF 5} ), lithium bromide (LiBr), calcium bromide (CaBr ₂ ), cesium bromide (CeBr ₃ ), selenium bromide Metal halides such as (SeBr ₄ ), vanadium bromide (VBr ₃ ), magnesium bromide (MgBr ₂ ), barium iodide (BaI ₂ ), or magnesium iodide (MgI _{2 );} Alternatively, a metal chlorate such as barium perchlorate (Ba(ClO ₄ ) ₂ ) or magnesium perchlorate (Mg(ClO ₄ ) ₂ ) may be mentioned, but is not limited thereto.

In the present application, a moisture adsorbent such as the metal oxide may be blended into the composition in an appropriately processed state. For example, a pulverization process of the moisture adsorbent may be required, and a process such as a three roll mill, a bead mill, or a ball mill may be used for pulverization of the moisture adsorbent.

The encapsulation composition of the present application may contain a moisture adsorbent in an amount of 5 parts by weight to 100 parts by weight, 5 to 80 parts by weight, 5 parts by weight to 70 parts by weight, or 10 to 30 parts by weight based on 100 parts by weight of the curable compound. have. The encapsulation composition of the present application may preferably control the content of the moisture adsorbent to 5 parts by weight or more so that the encapsulation composition or the cured product thereof exhibits excellent moisture and moisture barrier properties. In addition, when the content of the moisture adsorbent is controlled to 100 parts by weight or less, when forming the encapsulation structure of the thin film, it is possible to exhibit excellent moisture barrier properties.

In one example, the composition for encapsulation of the present application may further include a photosensitizer. The photosensitizers include anthracene compounds such as anthracene, 9,10-dibutoxyanthracene, 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, and 2-ethyl-9,10-dimethoxyanthracene; Benzophenone, 4,4-bis(dimethylamino)benzophenone, 4,4-bis(diethylamino)benzophenone, 2,4,6-trimethylaminobenzophenone, methyl-o-benzoylbenzoate, 3,3 -Benzophenone compounds such as dimethyl-4-methoxybenzophenone and 3,3,4,4-tetra(t-butylperoxycarbonyl)benzophenone; Acetophenone; Ketone compounds such as dimethoxyacetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and propanone; Perylene; Fluorenone compounds, such as 9-fluorenone, 2-chloro-9-prorenone, and 2-methyl-9-fluorenone; Thioxanthone, 2,4-diethyl thioxanthone, 2-chloro thioxanthone, 1-chloro-4-propyloxy thioxanthone, isopropyl thioxanthone (ITX), diisopropyl thioxanthone, etc. Thioxanthone compounds; Xanthone compounds such as xanthone and 2-methylxanthone; Anthraquinone compounds such as anthraquinone, 2-methyl anthraquinone, 2-ethyl anthraquinone, t-butyl anthraquinone, and 2,6-dichloro-9,10-anthraquinone; 9-phenylacridine, 1,7-bis(9-acridinyl)heptane, 1,5-bis(9-acridinylpentane), 1,3-bis(9-acridinyl)propane, etc. Acridine-based compounds; Dicarbonyl compounds such as benzyl, 1,7,7-trimethyl-bicyclo[2,2,1]heptane-2,3-dione, and 9,10-phenanthrenequinone; Phosphine oxide compounds such as 2,4,6-trimethylbenzoyl diphenylphosphine oxide and bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentyl phosphine oxide; Benzoate compounds such as methyl-4-(dimethylamino)benzoate, ethyl-4-(dimethylamino)benzoate, and 2-n-butoxyethyl-4-(dimethylamino)benzoate; 2,5-bis(4-diethylaminobenzal)cyclopentanone, 2,6-bis(4-diethylaminobenzal)cyclohexanone, 2,6-bis(4-diethylaminobenzal)-4- Amino synergists such as methyl-cyclopentanone; 3,3-carbonylvinyl-7-(diethylamino)coumarin, 3-(2-benzothiazolyl)-7-(diethylamino)coumarin, 3-benzoyl-7-(diethylamino)coumarin, 3 -Benzoyl-7-methoxy-coumarin, 10,10-carbonylbis[1,1,7,7-tetramethyl-2,3,6,7-tetrahydro-1H,5H,11H-C1]-benzo Coumarin compounds such as pyrano[6,7,8-ij]-quinolizin-11-one; Chalcone compounds such as 4-diethylamino chalcone and 4-azidebenzalacetophenone; 2-benzoylmethylene; And 3-methyl-b-naphthothiazoline.

The photosensitizer may be included in the range of 0.01 to 10 parts by weight based on 100 parts by weight of the curable compound. In the present application, by adjusting the content of the photosensitizer, while implementing the effect of increasing the curing sensitivity at a desired wavelength, it is possible to prevent the photosensitizer from deteriorating the adhesion due to not being dissolved.

In addition to the above-described configuration, various additives may be included in the encapsulation composition according to the present application within a range that does not affect the effects of the above-described invention. For example, the encapsulation composition may contain an antifoaming agent, a coupling agent, a tackifier, an ultraviolet stabilizer, or an antioxidant in an appropriate range depending on the desired physical properties. In one example, the encapsulation composition may further include an antifoam. In the present application, by including the antifoaming agent, in the application process of the above-described encapsulation composition, degassing characteristics may be implemented, thereby providing a reliable encapsulation structure. In addition, the type of the antifoaming agent is not particularly limited as long as the properties of the encapsulation composition required in the present application are satisfied.

In one example, the encapsulation composition may be liquid at room temperature, for example, about 25°C. In the embodiment of the present application, the encapsulation composition may be a solvent-free type liquid. The encapsulation composition may be applied to encapsulating the organic electronic device, and specifically, may be applied to encapsulating the entire surface of the organic electronic device. In the present application, since the encapsulation composition has a liquid form at room temperature, the device may be encapsulated by applying the composition to the side of the organic electronic device.

The present application also relates to an organic electronic device. An exemplary organic electronic device includes a substrate 21 as shown in FIG. 1; An organic electronic device 23 formed on the substrate 21; And a front encapsulation layer 11 including the above-described encapsulation composition and sealing the entire surface of the organic electronic device 23. In addition, the exemplary organic electronic device may further include a side encapsulation layer 10 formed on the substrate 21 to surround the side surfaces of the organic electronic device 23.

The front encapsulation layer and the side encapsulation layer may exist on the same plane. In the above, "the same" may mean substantially the same. For example, substantially the same on the same plane means that an error of ±5 μm or ±1 μm can be obtained in the thickness direction. The front encapsulation layer may encapsulate the upper surface of the device, and may encapsulate not only the upper surface but also the side surface. The side encapsulation layer may be formed on the side of the device, but may not directly contact the side of the organic electronic device. For example, the front encapsulation layer may be encapsulated so as to directly contact the upper and side surfaces of the device. That is, the side encapsulation layer may be located at the periphery of the substrate in a plan view of the organic electronic device without contacting the device.

In this specification, the term "peripheral part" means a peripheral edge part. That is, in the above, the periphery of the substrate may mean an edge of the periphery of the substrate.

The organic electronic device of the present application may further include a cover substrate 22 present on the front encapsulation layer. The material of the substrate or the cover substrate is not particularly limited, and a material known in the art may be used. For example, the substrate or the cover substrate may be a glass or a polymer film. Polymer films are, for example, polyethylene terephthalate film, polytetrafluoroethylene film, polyethylene film, polypropylene film, polybutene film, polybutadiene film, vinyl chloride copolymer film, polyurethane film, ethylene-vinyl acetate film, ethylene -A propylene copolymer film, an ethylene-ethyl acrylate copolymer film, an ethylene-methyl acrylate copolymer film, or a polyimide film may be used.

The material constituting the side encapsulation layer is not particularly limited, but may include the aforementioned encapsulation composition.

On the other hand, the side encapsulation layer may include an encapsulation resin, and the encapsulation resin is an acrylic resin, an epoxy resin, a silicone resin, a fluorine resin, a styrene resin, a polyolefin resin, a thermoplastic elastomer, a polyoxyalkylene resin, a polyester resin, a poly A vinyl chloride resin, a polycarbonate resin, a polyphenylene sulfide resin, a polyamide resin, or a mixture thereof may be exemplified. Components constituting the side encapsulation layer may be the same as or different from the aforementioned encapsulation composition.

In one example, the organic electronic device may include a reflective electrode layer formed on a substrate, an organic layer formed on the reflective electrode layer and including at least a light emitting layer, and a transparent electrode layer formed on the organic layer.

In the present application, the organic electronic device 23 may be an organic light emitting diode.

In one example, the organic electronic device according to the present application may be a top emission type, but is not limited thereto, and may be applied to a bottom emission type.

The organic electronic device may further include a protective layer protecting an electrode and a light emitting layer of the device. The protective layer may be a protective layer by chemical vapor deposition (CVD), and the material may be a known inorganic material, and, for example, silicon nitride (SiNx) may be used. In one example, silicon nitride (SiNx) used as the protective layer may be deposited to a thickness of 0.01 μm to 5 μm.

In addition, the present application relates to a method of manufacturing an organic electronic device.

In one example, the manufacturing method includes the steps of applying the above-described encapsulation composition on a substrate 21 on which the organic electronic device 23 is formed to seal the entire surface of the organic electronic device 23; And curing the composition. The step of applying the encapsulation composition may be a step of forming the front encapsulation layer 11 described above.

In the above, the substrate 21 on which the organic electronic device 23 is formed, for example, a reflective electrode or a transparent electrode is formed on a substrate 21 such as glass or film by a method such as vacuum deposition or sputtering, and the It can be manufactured by forming an organic material layer on the reflective electrode. The organic material layer may include a hole injection layer, a hole transport layer, an emission layer, an electron injection layer, and/or an electron transport layer. Subsequently, a second electrode is further formed on the organic material layer. The second electrode may be a transparent electrode or a reflective electrode. Thereafter, the above-described front encapsulation layer 11 is applied on the substrate 21 to cover the organic electronic device 23. In this case, a method of forming the front encapsulation layer 11 is not particularly limited, and a process such as screen printing or dispenser application may be used to apply the aforementioned encapsulation composition to the entire surface of the substrate 21. In addition, a side encapsulation layer 10 may be applied to encapsulate the side surface of the organic electronic device 23. As a method of forming the front encapsulation layer 11 or the side encapsulation layer 10, a method known in the art may be applied. For example, a liquid crystal drop filling process may be used.

In addition, in the present invention, a curing process may be performed on the front or side encapsulation layer that encapsulates the organic electronic device, and such a curing process (main curing) may be performed in, for example, a heating chamber or a UV chamber. It can be done in all. The conditions at the time of main curing may be appropriately selected in consideration of the stability of the organic electronic device and the like.

In one example, after the above-described encapsulation composition is applied to form the front encapsulation layer, the composition may be irradiated with light to induce crosslinking. ^{Irradiating the light is 0.3 to 20 J/cm 2 of} light having a wavelength range in the UV-A region, It may include irradiation with a light amount of 0.3 to 6 J/cm ² or 0.5 to 5 J/cm ^{2 of light.} As described above, it is possible to implement the shape of the encapsulation structure that can be the basis by main curing or temporary curing through irradiation of light.

In one example, the manufacturing method may further perform thermal curing after irradiation with light. The light-irradiated encapsulation composition is 40°C to 200°C, 50°C to 180°C, 60°C to 170°C, 70°C to 160°C, 80°C to 150°C or 90°C to 130°C for 1 hour to 24 hours It may further include thermal curing for 1 hour to 20 hours, 1 hour to 10 hours, or 1 hour to 5 hours. Through the step of applying the heat, the encapsulation composition may undergo main curing.

This application enables the formation of a structure that can effectively block moisture or oxygen flowing into the organic electronic device from the outside, thereby securing the life of the organic electronic device, and the realization of a top emission type organic electronic device. It provides a sealing composition capable of preventing defects such as dark spots that may occur in a device, and an organic electronic device including the same.

1 is a cross-sectional view showing an organic electronic device according to an example of the present invention.

Hereinafter, the present invention will be described in more detail through examples according to the present invention and comparative examples not according to the present invention, but the scope of the present invention is not limited by the examples presented below.

Example One

BPA epoxy resin (YX-8034, Mw 400g/mol, MITSUBISHI) and alicyclic epoxy compound (DAICEL's Celloxide2021P, Mw 270g/mol, viscosity 300cps) as curable compounds at room temperature were 65:35 (YX-8034:Celloxide2021P). It was put into the mixing container at a weight ratio. With respect to 100 parts by weight of the curable compound, 0.5 parts by weight of a photocationic initiator (BASF, Irgacure 290) and a thixotropic imparting agent (Fumed silica, R805, BET 150 m ² /g, Aerosil, Evonik) 10 parts by weight in the container Was put in.

A homogeneous composition solution was prepared using the mixing vessel using a Planetary mixer (Kurabo, KK-250s).

Example 2

BPA epoxy resin (YX-8010, Mw 550g/mol, MITSUBISHI) and oxetane compound (TOAGOSEI's OXT-221, Mw 210g/mol, viscosity 12cps) as curable compounds at room temperature were 75:25 (YX-8010:OXT- 221) was added to the mixing container. With respect to 100 parts by weight of the curable compound, 0.7 parts by weight of a photocationic initiator (BASF, Irgacure 290), 0.5 parts by weight of a thermal cationic initiator (CXC-1612 from KING) and a thixotropic imparting agent (Fumed silica, R805, BET 150m ²⁾ /g, Aerosil, Evonik) 9 parts by weight were added to the container.

A homogeneous composition solution was prepared using the mixing vessel using a Planetary mixer (Kurabo, KK-250s).

Example 3

BPA epoxy resin (YX-8010, Mw 550 g/mol, MITSUBISHI) as a curable compound at room temperature and Neopentyl Glycol Diglycidyl Ether (NGDE, Mw 270 g/mol) as an aliphatic epoxy compound 60:40 (YX-8010:NGDE) It was put into the mixing container at a weight ratio. Based on 100 parts by weight of the curable compound, 1.0 parts by weight of a photocationic initiator (BASF, Irgacure 290), 0.5 parts by weight of a curing retardant 18-crown-6-ether (SIGMA-ALDRICH) and a thixotropic imparting agent (Fumed silica , R805, BET 150m ² /g, Aerosil, Evonik) 12 parts by weight were added to the container.

A homogeneous composition solution was prepared using the mixing vessel using a Planetary mixer (Kurabo, KK-250s).

Example 4

As a curable compound at room temperature, BPA epoxy resin (YX-8034, Mw 400g/mol, MITSUBISHIS), oxetane compound (TOAGOSEI's OXT-221, Mw 210g/mol, viscosity 12cps) and alicyclic epoxy compound (DAICEL's Celloxide2021P, Mw 270g/mol, viscosity 300cps) was added to the mixing container at a weight ratio of 60:10:30 (YX-8034:OXT-221: Celloxide2021P). Based on 100 parts by weight of the curable compound, 1.0 parts by weight of a photocationic initiator (BASF, Irgacure 290), 0.5 parts by weight of a curing retardant 18-crown-6-ether (SIGMA-ALDRICH) and a thixotropic imparting agent (Fumed silica , R805, BET 150m ² /g, Aerosil, Evonik) 15 parts by weight was added to the container.

A homogeneous composition solution was prepared using the mixing vessel using a Planetary mixer (Kurabo, KK-250s).

Comparative example One

BPA epoxy resin (YX-8034, Mw 400g/mol, MITSUBISHIS), and BPA epoxy resin (YX-8010, Mw 550g/mol, MITSUBISHI) as a curable compound at room temperature were 60:40 (YX-8034:YX-8010) It was put into the mixing container at a weight ratio of. With respect to 100 parts by weight of the curable compound, 0.5 parts by weight of a thermal cationic initiator (CXC-1612 from KING) was added to the container.

A homogeneous composition solution was prepared using the mixing vessel using a Planetary mixer (Kurabo, KK-250s).

Comparative example 2

BPA epoxy resin as a curable compound at room temperature (YX-8010, Mw 550g/mol, MITSUBISHI) alicyclic epoxy compound (DAICE's Celloxide8000, Mw 160g/mol, viscosity 60cps) and oxetane compound (TOAGOSEI's OXT-221, Mw 210g /mol, viscosity 12cps) was added to the mixing container at a weight ratio of 35:40:25 (YX-8010:Celloxide8000:OXT-221). Based on 100 parts by weight of the curable compound, 1.0 parts by weight of a photocationic initiator (BASF, Irgacure 290), 0.5 parts by weight of a curing retardant 18-crown-6-ether (SIGMA-ALDRICH) and a thixotropic imparting agent (Fumed silica , R805, BET 150m ² /g, Aerosil, Evonik) 15 parts by weight was added to the container.

A homogeneous composition solution was prepared using the mixing vessel using a Planetary mixer (Kurabo, KK-250s).

Comparative example 3

BPA epoxy resin (YX-8034, Mw 400g/mol, MITSUBISHI) and alicyclic epoxy compound (DAICEL's Celloxide2021P, Mw 270g/mol, viscosity 300cps) as curable compounds at room temperature were 85:15 (YX-8034:Celloxide2021P). It was put into the mixing container at a weight ratio. Based on 100 parts by weight of the curable compound, 4 parts by weight of a photocationic initiator (BASF, Irgacure 290), 0.5 parts by weight of a thermal cationic initiator (CXC-1612 from KING) and a thixotropic imparting agent (Fumed silica, R805, BET 150m ²⁾ /g, Aerosil, Evonik) 15 parts by weight were added to the container.

A homogeneous composition solution was prepared using the mixing vessel using a Planetary mixer (Kurabo, KK-250s).

Comparative example 4

BPA epoxy resin (YD-128H, Mw 400g/mol, 1500cps, KUKDO) and alicyclic epoxy compound (DAICEL's Celloxide2021P, Mw 270g/mol, viscosity 300cps) as curable compounds at room temperature at 70:30 (YD-128H:Celloxide2021P) ) Was added to the mixing container at a weight ratio of. With respect to 100 parts by weight of the curable compound, 0.5 parts by weight of a photocationic initiator (BASF, Irgacure 290), and a thixotropic imparting agent (Fumed silica, R805, BET 150 m ² /g, Aerosil, Evonik) 10 parts by weight of the container Was put into.

A homogeneous composition solution was prepared using the mixing vessel using a Planetary mixer (Kurabo, KK-250s).

Comparative example 5

The weight ratio of alicyclic epoxy compound (DAICEL's Celloxide2021P, Mw 270g/mol, viscosity 300cps) and acrylic compound (SR348L, Mw 410g/mol, 1800cps, SARTOMER) 40:60 (Celloxide2021P:SR348L) as curable compounds at room temperature The furnace was put into the mixing container. Based on 100 parts by weight of the curable compound, 1.0 part by weight of a radical initiator (BASF, Irgacure 651), and ^{15 parts by weight of a thixotropic imparting agent (Fumed silica, R805, BET 150m 2} /g, Aerosil, Evonik) in the container Was put in.

A homogeneous composition solution was prepared using the mixing vessel using a Planetary mixer (Kurabo, KK-250s).

Physical properties in Examples and Comparative Examples were evaluated in the following manner.

1. Viscosity measurement

The viscosity of the encapsulation compositions prepared in Examples and Comparative Examples was measured in a cone and plate mode using TA's ARES (Advanced Rheometric Expansion System)-G2. Specifically, the shear rate in the range of 0.01 to 100sec ^-1 was measured, the angle of the cone was 0.1002rad, and the gap was 0.1mm.

The viscosity was measured at a temperature of 25°C and a shear rate of ^{0.1sec -1} , and the viscosity was measured at a temperature of 25°C and a shear rate of ^{5.0sec -1.}

2. Cementing properties

After applying the side encapsulant sealant to the lower soda lime glass (0.7T), dotting a certain amount of the solution mixed in Examples and Comparative Examples, and then the upper soda lime glass (0.7T) was bonded under vacuum (bonding condition 10 ^-2 torr, 1bar, 2min). After bonding, photo-curing (metal halide 3J/cm ² ), curing at 100° C. for 1 hour, and magnified observation (OLYMPUS STM6-LM). When bubbles occurred, they were classified as X and when bubbles did not occur, they were classified as O.

3. crack Penetration or not

The encapsulation compositions prepared in Examples and Comparative Examples were applied on the organic electronic device on which the inorganic vapor deposition film (chemical vapor deposition film) film was formed. After that, it was photo-cured after bonding with the bonding method of 2. When thermal curing is required (Example 2, Comparative Examples 2 and 3), curing was performed at 100° C. for 1 hour.

After curing, the penetration of cracks was observed (FESEM (HITACHI S-4800).

If the mixed solution did not penetrate, it was classified as O, and if it penetrated, it was classified as X.

4. Shrinkage measurement

The cure shrinkage ratio (φ) represented by the following general formula 1 was measured.

[General Formula 1]

φ = (1/ρ _l -1/ρ _s ) × ρ _l × 100

ρ _l was measured according to ASTM D1475 before curing of the composition, and ρ _s was measured according to KS M3010 after curing of the composition.

5. Haze Measure

After curing the encapsulation compositions prepared in Examples and Comparative Examples, measurements were made according to JIS K7105 standard using an NDH-5000 measuring instrument manufactured by Nippon Denshoku.

6. Measurement of b* and Yellow Index

The encapsulation compositions prepared in Examples and Comparative Examples were applied between soda lime glass (0.7T), and then cured to form an encapsulation layer.

The YI (yellow index) value was measured according to ASTM D 1003 standard using a Nippon Denshoku's COH400 transmittance meter.

Viscosity
(0.1s ^-1 ) Viscosity
(5.0s ^-1 ) Cementation properties Crack penetration Shrinkage rate
(%) Example 1 1.5 million cps 110,000 cps O O 3.5 Example 2 1.6 million cps 130,000 cps O O 3.7 Example 3 1.7 million cps 90,000 cps O O 3.3 Example 4 1.5 million cps 80,000 cps O O 3.6 Comparative Example 1 7000cps 6000cps O X 3.1 Comparative Example 2 610,000 cps 10,000 cps O X 4.2 Comparative Example 3 1.8 million cps 330,000 cps X O 3.2 Comparative Example 4 230,000 cps 30,000 cps O X 3.5 Comparative Example 5 1.1 million cps 100,000 cps O X 7.5

Haze (%) b* YI Example 1 0.56 0.55 0.86 Example 2 0.43 0.30 0.70 Example 3 0.62 0.42 0.84 Example 4 0.58 0.35 0.80 Comparative Example 1 0.32 0.31 0.75 Comparative Example 2 0.70 0.58 0.89 Comparative Example 3 0.53 3.2 4.8 Comparative Example 4 10.2 0.62 0.90 Comparative Example 5 9.8 0.55 0.87

1: Encapsulant
10: side encapsulation layer
11: Front encapsulation layer
21: substrate
22: cover substrate
23: organic electronic device

Claims (21)

Including a curable compound including a compound having a weight average molecular weight of more than 300 g/mol and 10,000 g/mol or less, a cyclic structure in the molecular structure, and a compound having a weight average molecular weight of 300 g/mol or less,
The weight average molecular weight of the compound having a weight average molecular weight of 300 g/mol or less is contained in an amount of 20 parts by weight to 80 parts by weight based on 100 parts by weight of the compound having a cyclic structure in the molecular structure, and the weight average molecular weight exceeds 300 g/mol and is 10,000 g/mol or less ,
The viscosity measured at a temperature of 25℃ and ^{a shear rate of 0.1sec -1} is more than 1 million cps, and the viscosity measured at a temperature of 25℃ and ^{a shear rate of 5.0sec -1} is less than 150,000 cps,
A composition for encapsulating an organic electronic device having a curing shrinkage (φ) of 5% or less represented by the following general formula 1 and in a liquid state at 25°C:
[General Formula 1]
φ = (1/ρ _l -1/ρ _s ) × ρ _l × 100
In General Formula 1, ρ _l is a liquid density measured according to ASTM D1475 before curing of the composition, and ρ _s is a solid density measured according to KS M3010 after curing of the composition. The composition of claim 1, wherein the curable compound includes at least one curable functional group. The method of claim 2, wherein the curable functional group is at least one selected from glycidyl group, isocyanate group, hydroxy group, carboxyl group, amide group, epoxide group, cyclic ether group, sulfide group, acetal group, and lactone group. Composition. The composition for sealing an organic electronic device according to claim 2, wherein the curable compound is monofunctional or more. delete The composition for sealing an organic electronic device according to claim 1, wherein the compound having a cyclic structure is a hydrogenated compound. The composition for sealing an organic electronic device according to claim 1, wherein the compound having a cyclic structure is an aromatic compound. delete delete The composition for sealing an organic electronic device according to claim 1, wherein the compound having a weight average molecular weight of 300 g/mol or less is a linear, branched or cyclic curable compound. The composition for sealing an organic electronic device according to claim 1, comprising a thermal initiator and/or a photo initiator. The composition for sealing an organic electronic device according to claim 11, wherein the thermal initiator or photoinitiator is a cationic initiator. The composition for sealing an organic electronic device according to claim 1, wherein the thermal initiator and/or the photoinitiator is contained in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the curable compound. The composition for sealing an organic electronic device according to claim 1, further comprising a curing retardant. The composition for sealing an organic electronic device according to claim 14, wherein the curing retardant is contained in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the curable compound. The composition for sealing an organic electronic device according to claim 1, further comprising a thixotropic agent. The composition for encapsulating an organic electronic device according to claim 16, wherein the thixotropic imparting agent comprises an inorganic filler. The composition for sealing an organic electronic device according to claim 1, wherein after curing, the haze measured according to the standard of JIS K7105 is 5% or less. Board; An organic electronic device formed on the substrate; And a front encapsulation layer comprising the composition for encapsulating an organic electronic device according to claim 1 and sealing the entire surface of the organic electronic device. The organic electronic device of claim 19, further comprising a side encapsulation layer formed on the substrate to surround a side surface of the organic electronic device, wherein the side encapsulation layer and the front encapsulation layer are on the same plane. Applying the composition for encapsulating an organic electronic device of claim 1 to seal the entire surface of the organic electronic device on a substrate having an organic electronic device formed thereon; And curing the composition.

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