Sealing material composition

Abstract

The present invention relates to an encapsulant composition and an organic electronic device including the same, which can effectively block moisture or oxygen from entering an organic electronic device from the outside, thereby ensuring the life of the organic electronic device, and can realize a top-emitting organic electronic device and can be applied in an inkjet method to provide a thin display.

Description

[Technical field]

[0001] Cross-reference to related applications This application claims the benefit of priority based on Korean Patent Application No. 10-2018-0067307, filed on June 12, 2018, the entire contents of which are incorporated herein by reference.

[0002] Technical Field The present invention relates to an encapsulant composition, an organic electronic device including the same, and a method for making the organic electronic device. [Background technology]

[0003] Organic electronic device (OED) refers to a device containing layers of organic materials that generate an alternating current of charge using holes and electrons, and examples of OED include photovoltaic devices, rectifiers, transmitters, and organic light emitting diodes (OLEDs).

[0004] Among the organic electronic devices, organic light emitting diodes (OLEDs) consume less power and have a faster response speed than conventional light sources, which is advantageous for making displays or lighting thinner. In addition, OLEDs have excellent space utilization and are expected to be applied in various fields such as various portable devices, monitors, notebook computers, and TVs.

[0005] The most important problem in commercializing and expanding the use of OLEDs is their durability. Organic materials and metal electrodes contained in OLEDs are very easily oxidized by external factors such as moisture. Therefore, products containing OLEDs are very sensitive to environmental factors. As a result, various methods have been proposed to effectively block the penetration of external oxygen or moisture into organic electronic devices such as OLEDs. Summary of the Invention [Problem to be solved by the invention]

[0006] The present invention provides an encapsulant composition that can effectively block moisture or oxygen from entering an organic electronic device from the outside to ensure the life of the organic electronic device, can realize a top-emitting organic electronic device, can be applied in an inkjet method, and can provide a thin display, and an organic electronic device including the encapsulant composition. [Means for solving the problem]

[0007] The present invention relates to an encapsulant composition. The encapsulant composition may be an encapsulant applied to encapsulate or seal an organic electronic device such as an OLED. In one embodiment, the encapsulant composition of the present invention may be applied to encapsulate or seal the entire surface of an organic electronic device. Thus, after the encapsulant composition is applied for encapsulation, it may exist in the form of an organic layer that seals the entire surface of the organic electronic device. In addition, the organic layer may be laminated on the organic electronic device together with a protective film and / or an inorganic layer, which will be described later, to form an encapsulating structure.

[0008] In an embodiment of the present invention, the present invention relates to an encapsulant composition for encapsulating an organic electronic device that is applicable to an inkjet process, and the composition can be designed to have appropriate physical properties when discharged onto a substrate using inkjet printing that is capable of patterning in a non-contact manner.

[0009] As used herein, the term "organic electronic device" refers to an article or device having a structure including an organic material layer that generates an alternating current of charge using holes and electrons between a pair of opposing electrodes, examples of which include, but are not limited to, photovoltaic cells, rectifiers, transmitters, and organic light-emitting diodes (OLEDs), etc. In one embodiment of the present invention, the organic electronic device may be an OLED.

[0010] An exemplary encapsulant composition may include an epoxy compound, a compound having an oxetane group, and a moisture adsorbent. The epoxy compound may be a photocurable or thermosetting compound. The compound having an oxetane group may be included in a range of 45 to 145 parts by weight, 48 to 144 parts by weight, 63 to 143 parts by weight, or 68 to 142 parts by weight, based on 100 parts by weight of the epoxy compound. In the present specification, the term "parts by weight" may mean the weight ratio between each component. The present invention can form an organic layer in an organic electronic device by an inkjet method by controlling the content ratio of the composition, and the applied encapsulant composition can provide an organic layer having excellent diffusibility within a short time and excellent curing strength after curing.

[0011] The sealant composition of the present invention may include a moisture adsorbent. The term "moisture adsorbent" may be used as a general term for a component capable of adsorbing or removing moisture or humidity introduced from the outside through a physical or chemical reaction, etc. That is, it means a chemically reactive adsorbent or a physical adsorbent, and a mixture thereof may also be used.

[0012] The specific type of moisture adsorbent used in the present invention is not particularly limited, and examples of the chemically reactive adsorbent include one or a mixture of two or more of metal oxides, metal salts, and phosphorus pentoxide (PO), and examples of the physical adsorbent include zeolite, zirconia, and montmorillonite.

[0013] The sealant composition of the present invention may contain the moisture adsorbent in an amount of 5 to 150 parts by weight, 5 to 110 parts by weight, 5 to 90 parts by weight, 10 to 50 parts by weight, 12 to 38 parts by weight, or 14 to 23 parts by weight, based on 100 parts by weight of the epoxy compound. The sealant composition of the present invention preferably controls the content of the moisture adsorbent to 5 parts by weight or more, so that the sealant composition or its cured product can exhibit excellent moisture and moisture barrier properties. In addition, the present invention controls the content of the moisture adsorbent to 150 parts by weight or less, so that it can be blended with the above-mentioned composition to provide a thin-film sealing structure while having physical properties that allow inkjet printing.

[0014] The moisture adsorbent may have an average particle size controlled to 10-15000 nm, 30 nm-10000 nm, 50 nm-8000 nm, 80 nm-5 μm, 90 nm-3 μm, 95 nm-980 nm, or 98 nm-495 nm. In this specification, the particle size may be measured by a known method using a D50 particle size analyzer. The moisture adsorbent having a size in the above range can effectively block moisture penetrating from the outside by appropriately controlling the reaction rate with moisture, and can also realize excellent processability by preventing aggregation of the adsorbent during inkjetting.

[0015] The sealant composition of the present invention may be an ink composition applied to an inkjet process as described above. However, controlling the viscosity of the ink composition in the inkjet process and thereby realizing a composition having physical properties that allow inkjetting is a very delicate task. However, since the moisture adsorbent is included in the composition in the form of particles, for example, the adsorbent aggregates in the composition or its dispersibility decreases, which may cause problems such as nozzle clogging or uniform inkjetting during the inkjet process. However, the present invention provides a sealant composition having the above-mentioned specific composition, so that the inkjet process can be smoothly performed even when the moisture adsorbent is included.

[0016] In one example, the sealant composition of the present invention may have a contact angle with respect to glass of 15° or less, 12° or less, 10° or less, or 8° or less. The lower limit is not particularly limited, and may be 1° or 3° or more. By adjusting the contact angle to 15° or less, the present invention can ensure diffusion within a short time in inkjet coating, thereby forming a thin organic layer. In the present invention, the contact angle may be measured by applying one drop of the sealant composition on glass using a Sessile Drop measurement method, or may be measured by applying five times and then measuring the average value.

[0017] In one example, the epoxy compound may be at least monofunctional or bifunctional or more, that is, the compound may have one or more epoxy functional groups, and the upper limit is not particularly limited, but may be 10 or less. The epoxy compound realizes an appropriate degree of crosslinking in the ink composition, thereby realizing excellent heat resistance and durability under high temperature and humidity.

[0018] In a specific example of the present invention, the epoxy compound may include a compound having a ring structure in its molecular structure and / or a linear or branched aliphatic compound. That is, the sealant composition of the present invention may include at least one of a compound having a ring structure in its molecular structure and a linear or branched aliphatic compound as the epoxy compound, or may include them together. In one example, the compound having a ring structure in its molecular structure may have ring-constituting atoms in the range of 3 to 10, 4 to 8, or 5 to 7 in its molecular structure, and the compound may have 1 or more, 2 or more, and 10 or less ring structures. When the compound having a cyclic structure and the linear or branched aliphatic compound are used together, the linear or branched aliphatic compound may be included in the sealant composition in an amount of 20 parts by weight or more, less than 205 parts by weight, 23 parts by weight to 204 parts by weight, 30 parts by weight to 203 parts by weight, 34 parts by weight to 202 parts by weight, 40 parts by weight to 201 parts by weight, 60 parts by weight to 200 parts by weight, or 100 parts by weight to 173 parts by weight, based on 100 parts by weight of the compound having a cyclic structure. By controlling the amount in the above range, the sealant composition according to the present invention can prevent damage to an organic electronic device when sealing the entire surface of the device, have suitable physical properties for inkjet printing, have excellent curing strength after curing, and can also realize excellent moisture blocking properties.

[0019] In one example, the epoxy compound may have an epoxy equivalent ranging from 50 to 350 g / eq, 73 to 332 g / eq, 94 to 318 g / eq, or 123 to 298 g / eq. In addition, the compound having an oxetane group and / or the epoxy compound may have a weight average molecular weight ranging from 150 to 1,000 g / mol, 173 to 980 g / mol, 188 to 860 g / mol, 210 to 823 g / mol, or 330 to 780 g / mol. The present invention improves the degree of curing completion after curing of the sealant and prevents the composition from becoming too viscous, which makes the inkjet process impossible, by controlling the epoxy equivalent of the epoxy compound to be low or adjusting the weight average molecular weight of the compound to be low, and at the same time, provides moisture barrier properties and excellent curing sensitivity. In the present specification, the weight average molecular weight means a value converted to standard polystyrene measured by GPC (Gel Permeation Chromatograph). In one example, a metal tube column having a length of 250-300 mm and an inner diameter of 4.5-7.5 mm is filled with 3-20 mm polystyrene beads. When a diluted solution of the substance to be measured dissolved in THF solvent is passed through the column, the weight average molecular weight can be indirectly measured based on the time it takes to flow out. The amount of separated substances by size from the column can be detected by plotting it against time. In addition, the epoxy equivalent in this specification is the number of grams of resin containing 1 gram equivalent of epoxy groups (g / eq), and can be measured by the method specified in JIS K 7236.

[0020] The compound having an oxetane group may have a boiling point within the range of 90 to 300°C, 98 to 270°C, 110 to 258°C, or 138 to 237°C. By controlling the boiling point of the compound within the above range, the present invention makes it possible to provide a sealant that realizes excellent printability even at high temperatures in an inkjet process, has excellent moisture barrier properties from the outside, and prevents damage to elements by suppressing outgassing. In this specification, the boiling point may be measured at 1 atmosphere, unless otherwise specified.

[0021] As an example, compounds having a ring structure in their molecular structure include, but are not limited to, 3,4-epoxycyclohexylmethyl 3',4'-epoxycyclohexanecarboxylate (EEC) and derivatives, dicyclopentadiene dioxide and derivatives, vinylcyclohexene dioxide and derivatives, and 1,4-cyclohexanedimethanol bis(3,4-epoxycyclohexanecarboxylate) and derivatives.

[0022] As an example, the structure of the compound containing the oxetane group is not limited as long as it has the functional group, and examples thereof include OXT-221, CHOX, OX-SC, OXT101, OXT121, and OXT212 from TOAGOSEI Co., Ltd., and EHO, OXBP, OXTP, and OXMA from ETERNACOLL Co., Ltd. In addition, the linear or branched aliphatic epoxy compound may include, but is not limited to, aliphatic glycidyl ether, 1,4-butanediol diglycidyl ether, ethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, propylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, and neopentyl glycol diglycidyl ether.

[0023] In an embodiment of the present invention, the sealant composition may further include a photoinitiator. The photoinitiator may be an ionic photoinitiator. The photoinitiator may also be a compound that absorbs wavelengths in the range of 200 nm to 400 nm. By using the photoinitiator, the present invention can realize excellent curing properties in a specific composition of the present invention.

[0024] In one embodiment, the photoinitiator may be a cationic photoinitiator. For the cationic photoinitiator, a material known in the art may be used, such as a cationic moiety including aromatic sulfonium, aromatic iodonium, aromatic diazonium, or aromatic ammonium, and AsF6 - , SbF6 - , PF6 -Or, a compound having an anion moiety including tetrakis(pentafluorophenyl)borate may be included. In addition, examples of the cationic photopolymerization initiator include an ionized cationic initiator of an onium salt or an organometallic salt series, an organic silane or a latent sulfonic acid series, or a non-ionized cationic photopolymerization initiator. Examples of the onium salt initiator include diaryliodonium salt, triarylsulfonium salt, and aryldiazonium salt. Examples of the organometallic salt initiator include iron arene. Examples of the organosilane initiator include o-nitrobenzyl triaryl silyl ether, triaryl silyl peroxide, and acyl silane. Examples of the latent sulfonic acid initiator include α-sulfonyloxyketone and α-hydroxymethylbenzoin sulfonate, but are not limited thereto.

[0025] In one embodiment, the encapsulant composition of the present invention may include a photoinitiator containing a sulfonium salt as a photoinitiator in the above-mentioned specific composition so as to be suitable for use in sealing an organic electronic device using an inkjet method. The encapsulant composition according to the above composition generates a small amount of outgas even when directly sealed on an organic electronic device, so that chemical damage to the device can be prevented. In addition, the photoinitiator containing a sulfonium salt has excellent solubility and can be applied to be suitable for an inkjet process.

[0026] In a specific example of the present invention, the photoinitiator may be included in an amount of 1 to 15 parts by weight, 3 to 14 parts by weight, or 7 to 13.5 parts by weight based on 100 parts by weight of the epoxy compound. By adjusting the content range of the photoinitiator, the present invention can minimize physical and chemical damage to an organic electronic device due to the characteristics of the encapsulant composition of the present invention that is directly applied onto the device.

[0027] In an embodiment of the present invention, the encapsulant composition may further include a surfactant. In one embodiment, the surfactant may include a polar functional group, and the polar functional group may be present at the end of the compound structure of the surfactant. The polar functional group may include, for example, a carboxyl group, a hydroxyl group, a phosphate, an ammonium salt, a carboxylate group, a sulfate, or a sulfonate. In addition, in an embodiment of the present invention, the surfactant may be a non-silicon-based surfactant or a fluorine-based surfactant. The non-silicon-based surfactant or the fluorine-based surfactant is applied together with the above-mentioned epoxy compound and the compound having an oxetane group to provide excellent coating properties on the organic electronic device. Meanwhile, in the case of a surfactant containing a polar reactive group, it is possible to realize an excellent effect in terms of adhesion since it has a high affinity with other components of the above-mentioned encapsulant composition. In an embodiment of the present application, a hydrophilic fluorine-based surfactant or a non-silicon-based surfactant may be used to improve inkjet coating properties on a substrate.

[0028] Specifically, the surfactant may be a polymer or oligomer type fluorosurfactant. The surfactant may be a commercially available product, such as Glide 100, Glide 110, Glide 130, Glide 460, Glide 440, Glide 450, or RAD2500 from TEGO, Megaface F-251, F-281, F-552, F-554, F-560, F-561, F-562, F-563, F-565, F-568, F-570, and F-571 from DIC (DaiNippon Ink & Chemicals), Surflon S-111, S-112, S-113, S-121, S-131, S-132, S-141, and S-145 from Asahi Glass Co., Ltd., or Fluorad from Sumitomo 3M Co., Ltd. It is possible to use those selected from the group consisting of FC-93, FC-95, FC-98, FC-129, FC-135, FC-170C, FC-430 and FC-4430, or Zonyl FS-300, FSN, FSN-100 and FSO from DuPont, and BYK-350, BYK-354, BYK-355, BYK-356, BYK-358N, BYK-359, BYK-361N, BYK-381, BYK-388, BYK-392, BYK-394, BYK-399, BYK-3440, BYK-3441, BYKETOL-AQ, BYK-DYNWET 800, etc.

[0029] The surfactant may be included in an amount of 0.01 to 10 parts by weight, 0.05 to 10 parts by weight, 0.1 to 10 parts by weight, 0.5 to 8 parts by weight, or 1 to 4 parts by weight, based on 100 parts by weight of the epoxy compound. Within the above content range, the present invention allows the sealant composition to be applied to an inkjet method to form a thin organic layer.

[0030] In an embodiment of the present invention, the sealant composition may further include a photosensitizer to complement the curability with active energy rays having a long wavelength of 300 nm or more. The photosensitizer may be a compound that absorbs light having a wavelength in the range of 200 nm to 400 nm, 250 nm to 400 nm, 300 nm to 400 nm, or 350 nm to 395 nm.

[0031] The photosensitizer may be an anthracene-based compound such as anthracene, 9,10-dibutoxyanthracene, 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, or 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-dimethyl-4-methoxybenzophenone, or 3,3,4,4-tetra(t-butylperoxy)benzophenone; benzophenone compounds such as dicarbonyl)benzophenone; acetophenone; ketone compounds such as dimethoxyacetophenone, diethoxyarthrophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and propanone; perylene; fluorenone compounds such as 9-fluorenone, 2-chloro-9-fluorenone, and 2-methyl-9-fluorenone; thioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 1-chloro-4-propyloxythioxanthone, and isopropylthioxanthone ( Thioxanthone compounds such as ITX, diisopropyl thioxanthone; xanthone compounds such as xanthone, 2-methyl xanthone; anthraquinone compounds such as anthraquinone, 2-methyl anthraquinone, 2-ethyl anthraquinone, t-butyl anthraquinone, 2,6-dichloro-9,10-anthraquinone; acridine compounds such as 9-phenyl acridine, 1,7-bis(9-acridinyl)heptane, 1,5-bis(9-acridinylpentane, 1,3-bis(9-acridinyl)propane; benzyl, 1, Dicarbonyl compounds such as 7,7-trimethyl-bicyclo[2,2,1]heptane-2,3-dione and 9,10-phenanthrenequinone; phosphine oxide compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide; benzoate compounds such as methyl-4-(dimethylamino)benzoate, ethyl-4-(dimethylamino)benzoate, and 2-n-butoxyethyl-4-(dimethylamino)benzoate;Amino synergists such as 2,5-bis(4-diethylaminobenzal)cyclopentanone, 2,6-bis(4-diethylaminobenzal)cyclohexanone, and 2,6-bis(4-diethylaminobenzal)-4-methyl-cyclopentanone; 3,3-carbonylvinyl-7-(diethylamino)coumarin, 3-(2-benzothiazoyl)-7-(diethylamino)coumarin, 3-benzoyl-7-(diethylamino)coumarin, and 3-benzoyl-7-methyl The compound may be one or more selected from the group consisting of coumarin compounds such as 10,10-carbonylbis[1,1,7,7-tetramethyl-2,3,6,7-tetrahydro-1H,5H,11H-C1]-benzopyrano[6,7,8-ij]-quinolridin-11-one; chalcone compounds such as 4-diethylaminochalcone and 4-azidobenzalacetophenone; 2-benzoylmethylene; and 3-methyl-b-naphthothiazoline.

[0032] The photosensitizer may be included in an amount of 28 to 40 parts by weight, 31 to 38 parts by weight, or 32 to 36 parts by weight, based on 100 parts by weight of the photoinitiator. By adjusting the content of the photosensitizer, the present invention can realize an increase in curing sensitivity at a desired wavelength, while preventing the photosensitizer from being insoluble in inkjet coating and reducing adhesive strength.

[0033] The sealant composition of the present invention may further include a coupling agent. The present invention may improve the adhesion of the cured product of the sealant composition to an adherend and the moisture permeability of the cured product. The coupling agent may include, for example, a titanium-based coupling agent, an aluminum-based coupling agent, or a silane coupling agent.

[0034] In a specific example of the present application, the silane coupling agent may be, for example, an epoxy-based silane coupling agent such as 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropyl(dimethoxy)methylsilane, or 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane; a mercapto-based silane coupling agent such as 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, or 11-mercaptoundecyltrimethoxysilane; a 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldimethoxymethylsilane, N-phenyl-3-aminopropyltrimethoxysilane, N-methylaminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, or N-(2-aminoethyl)-3-aminopropyltrimethoxysilane; ureido-based silane coupling agents such as 3-ureidopropyltriethoxysilane, vinyl-based silane coupling agents such as vinyltrimethoxysilane, vinyltriethoxysilane, and vinylmethyldiethoxysilane; styryl-based silane coupling agents such as p-styryltrimethoxysilane; acrylate-based silane coupling agents such as 3-acryloxypropyltrimethoxysilane and 3-methacryloxypropyltrimethoxysilane; isocyanate-based silane coupling agents such as 3-isocyanatepropyltrimethoxysilane, sulfide-based silane coupling agents such as bis(triethoxysilylpropyl)disulfide and bis(triethoxysilylpropyl)tetrasulfide; phenyltrimethoxysilane, methacryloxypropyltrimethoxysilane, imidazole silane, and triazine silane.

[0035] In the present invention, the coupling agent may be included in an amount of 0.1 to 10 parts by weight or 0.5 to 5 parts by weight based on 100 parts by weight of the epoxy compound. The present invention can realize the effect of improving adhesion by adding the coupling agent within the above range.

[0036] In one example, the sealant composition may further include an inorganic filler, if necessary. The specific type of filler used in the present invention is not particularly limited, and may be, for example, one or a mixture of two or more of clay, talc, alumina, calcium carbonate, silica, etc.

[0037] The sealant composition of the present invention may contain 0 to 50 parts by weight, 1 to 40 parts by weight, 1 to 20 parts by weight, or 1 to 10 parts by weight of an inorganic filler relative to 100 parts by weight of an epoxy compound. The present invention can provide a sealing structure having excellent moisture or humidity barrier properties and mechanical properties by controlling the content of the inorganic filler to preferably 1 part by weight or more. In addition, the present invention can provide a cured product that exhibits excellent moisture barrier properties even when formed as a thin film by controlling the content of the inorganic filler to 50 parts by weight or less.

[0038] In addition to the above-mentioned components, the sealant composition according to the present invention may contain various additives within a range that does not affect the above-mentioned effects of the invention. For example, the sealant composition may contain an antifoaming agent, a tackifier, an ultraviolet stabilizer, an antioxidant, etc. in an appropriate range of content depending on the desired physical properties.

[0039] In one example, the encapsulant composition may be liquid at room temperature, for example, 25° C. In an embodiment of the present invention, the encapsulant composition may be liquid in a solvent-free form. The encapsulant composition may be applied to encapsulate an organic electronic device, and more specifically, may be applied to encapsulate the entire surface of an organic electronic device. The encapsulant composition of the present invention may have a specific composition and physical properties that allow it to be inkjetted.

[0040] The sealant composition of the present invention may also be an ink composition. The sealant composition of the present invention may also be an ink composition capable of being inkjetted. The sealant composition of the present application may have a specific composition and physical properties to be inkjettable.

[0041] In addition, in an embodiment of the present invention, the encapsulant composition may have a viscosity of 50 cPs or less, 1 to 46 cPs, or 5 to 44 cPs, as measured by Brookfield DV-3 at a temperature of 25° C., a torque of 90%, and a shear rate of 100 rpm. By controlling the viscosity of the composition within the above range, the present invention can realize physical properties that allow inkjetting when applied to an organic electronic device, and can provide a thin-film encapsulant with good coating properties.

[0042] In one example, the sealant composition may have a surface energy of a cured product after curing in the range of 5 mN / m to 45 mN / m, 10 mN / m to 40 mN / m, 15 mN / m to 35 mN / m, or 20 mN / m to 30 mN / m. The surface energy may be measured by a method known in the art, for example, the Ring Method. The present invention can realize excellent coating properties within the above surface energy range.

[0043] In an embodiment of the present invention, the surface energy (γ surface , mN / m) is γ surface =γ dispersion +γ polar In one example, the surface energy can be measured using a drop shape analyzer (DSA100 product of KRUSS). For example, the surface energy can be calculated by applying the sealant composition to be measured to a SiNx substrate with a thickness of about 50 μm and a thickness of 4 cm. 2 After forming a sealing film by applying the coating to a coating area (width: 2 cm, length: 2 cm) (spin coater), it was dried at room temperature in a nitrogen atmosphere for about 10 minutes, and then irradiated with 1000 mW / cm 2 with an intensity of 4000mJ / cm 2After curing, deionized water, which has a known surface tension, is dropped onto the film, and the contact angle is measured five times to obtain an average value of the five contact angles. Similarly, diiodomethane, which has a known surface tension, is dropped onto the film, and the contact angle is measured five times to obtain an average value of the five contact angles. The average values ​​of the contact angles for deionized water and diiodomethane are then used to obtain the average value of the surface tension of the solvent (Strom value) according to the Owens-Wendt-Rabel-Kaelble method to obtain the surface energy.

[0044] In one example, the sealant composition of the present invention may have an amount of volatile organic compounds measured after curing of less than 50 ppm. In this specification, the volatile organic compounds may be expressed as outgassing. The volatile organic compounds may be measured after curing the sealant composition and maintaining a cured product sample at 110° C. for 30 minutes using Purge & Trap-Gas Chromatography / Mass Spectrometry. The measurement may be performed using a Purge & Trap sampler (JAI JTD-505III)-GC / MS (Agilent 7890b / 5977a) instrument.

[0045] The present invention also relates to an organic electronic device. As shown in FIG. 1, an exemplary organic electronic device 3 may include a substrate 31, an organic electronic element 32 formed on the substrate 31, and an organic layer 33 that seals the entire surface of the organic electronic element 32 and includes the above-mentioned sealant composition.

[0046] In an embodiment of the present invention, the organic electronic device may include a first electrode layer, an organic layer formed on the first electrode layer and including at least an emission layer, and a second electrode layer formed on the organic layer. The first electrode layer may be a transparent electrode layer or a reflective electrode layer, and the second electrode layer may also be a transparent electrode layer or a reflective electrode layer. More specifically, 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 an emission layer, and a transparent electrode layer formed on the organic layer.

[0047] In the present invention, the organic electronic device 32 may be an organic light emitting diode.

[0048] In one embodiment, the organic electronic device according to the present invention may be a top emission type, but is not limited thereto, and may also be a bottom emission type.

[0049] The organic electronic device may further include a protective film 35 for protecting the electrodes and the light-emitting layer of the element. The protective film 35 may be an inorganic protective film. The protective film may be a protective layer formed by chemical vapor deposition (CVD), and the material may be the same as or different from the inorganic layer described below, and known inorganic materials may be used. For example, the protective film may be silicon nitride (SiNx). In one example, silicon nitride (SiNx) used in the protective film may be deposited to a thickness of 0.01 μm to 50 μm.

[0050] In an embodiment of the present invention, the organic electronic device 3 may further include an inorganic layer 34 formed on the organic layer 33. The material of the inorganic layer 34 is not limited, and may be the same as or different from the protective film described above. The inorganic layer 34 may be formed in the same manner as the protective film 35. In one embodiment, the inorganic layer may be one or more metal oxides or nitrides selected from the group consisting of Al, Zr, Ti, Hf, Ta, In, Sn, Zn, and Si. The thickness of the inorganic layer may be 0.01 μm to 50 μm, 0.1 μm to 20 μm, or 1 μm to 10 μm. In one embodiment, the inorganic layer of the present invention may be an inorganic material that does not contain a dopant, or an inorganic material that contains a dopant. The dopant that can be doped may be one or more elements selected from the group consisting of Ga, Si, Ge, Al, Sn, B, In, Tl, Sc, V, Cr, Mn, Fe, Co, and Ni, or oxides of the elements, but is not limited thereto.

[0051] In one embodiment, the thickness of the organic layer may be in the range of 2 μm to 20 μm, 2.5 μm to 15 μm, or 2.8 μm to 9 μm. The present invention provides a thin organic layer to provide a thin-film organic electronic device.

[0052] The organic electronic device 3 of the present invention may include a sealing structure including the above-mentioned organic layer 33 and inorganic layer 34, and the sealing structure may include at least one or more organic layers and at least one or more inorganic layers, and the organic layers and the inorganic layers may be repeatedly laminated. For example, the organic electronic device may have a structure of substrate / organic electronic element / protective film / (organic layer / inorganic layer)n, where n may be a number within a range of 1 to 100. FIG. 1 is a cross-sectional view illustrating an example where n is 1.

[0053] In one embodiment, the organic electronic device 3 of the present invention may further include a cover substrate on the organic layer 33. The material of the substrate and / or cover substrate is not particularly limited, and any material known in the art may be used. For example, the substrate or cover substrate may be glass, a metal substrate, or a polymer film. The polymer film may be, for example, a polyethylene terephthalate film, a polytetrafluoroethylene film, a polyethylene film, a polypropylene film, a polybutene film, a polybutadiene film, a vinyl chloride copolymer film, a polyurethane film, an ethylene-vinyl acetate film, an ethylene-propylene copolymer film, an ethylene-ethyl acrylate copolymer film, an ethylene-methyl acrylate copolymer film, or a polyimide film.

[0054] 2, the organic electronic device 3 of the present invention may further include a sealing film 37 disposed between the cover substrate 38 and the substrate 31 on which the organic electronic element 32 is formed. The sealing film 37 may be used to attach the substrate 31 on which the organic electronic element 32 is formed to the cover substrate 38, and may be, for example, but is not limited to, an adhesive film or a bonding film. The sealing film 37 may seal the entire surface of the sealing structure 36 of the organic layer and inorganic layer laminated on the organic electronic element 32.

[0055] The present invention also relates to a method for manufacturing an organic electronic device.

[0056] In one example, the manufacturing method may include a step of forming an organic layer 33 on a substrate 31 having an organic electronic element 32 formed thereon, so that the above-mentioned sealant composition seals the entire surface of the organic electronic element 32.

[0057] The organic electronic device 32 may be manufactured by forming a reflective electrode or a transparent electrode on a substrate 31 such as glass or a polymer film by a method such as vacuum deposition or sputtering, and then forming an organic material layer on the reflective electrode. The organic material layer may include a hole injection layer, a hole transport layer, a light emitting layer, an electron injection layer, and / or an electron transport layer. Then, a second electrode is further formed on the organic material layer. The second electrode may be a transparent electrode or a reflective electrode.

[0058] The manufacturing method of the present invention may further include a step of forming a protective film 35 on the first electrode, the organic material layer, and the second electrode formed on the substrate 31. Then, the above-mentioned organic layer 33 is applied to the substrate 31 so as to cover the entire surface of the organic electronic device 32. At this time, the step of forming the organic layer 33 is not particularly limited, and the above-mentioned sealant composition may be applied to the entire surface of the substrate 31 by a process such as inkjet printing, gravure coating, spin coating, screen printing, or reverse offset coating.

[0059] In addition, the method may further include a step of irradiating the organic layer with light. In the present invention, a curing process may be performed on the organic layer that encapsulates the organic electronic device, and the curing process may be performed, for example, in a heating chamber or a UV chamber, and preferably in a UV chamber.

[0060] In one embodiment, after forming the front organic layer by applying the above-mentioned sealant composition, the composition may be irradiated with light to induce crosslinking. The light irradiation may be performed by applying light having a wavelength range of 250 nm to 450 nm or 300 nm to 450 nm at an intensity of 0.3 to 6 J / cm. 2 or 0.5~5J / cm 2 The method can include irradiating the substrate with an amount of light of

[0061] In addition, the manufacturing method of the present invention may further include a step of forming an inorganic layer 34 on the organic layer 33. The step of forming the inorganic layer may be performed using a method known in the art, and may be the same as or different from the method of forming the protective film described above. Effect of the Invention

[0062] The present invention provides an encapsulant composition that can effectively block moisture or oxygen from entering an organic electronic device from the outside to ensure the life of the organic electronic device, can realize a top-emitting organic electronic device, can be applied in an inkjet method, and can provide a thin encapsulant, and an organic electronic device including the same. [Brief description of the drawings]

[0063] 1 and 2 are cross-sectional views illustrating an organic electronic device according to one embodiment of the present application. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0064] The present invention will be described in more detail below 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 to the following examples.

[0065] <Example 1> At room temperature, an alicyclic epoxy compound (Celloxide 2021P from Daicel) and an aliphatic epoxy compound (DE203 from HAJIN CHEM TECH) as epoxy compounds, an oxetane group-containing compound (OXT-221 from TOAGOSEI), a photoinitiator (Irgacure PAG 290 from BASF, hereinafter referred to as I290), and a fluorine-based surfactant (F552 from DIC) were added to a mixing vessel in a weight ratio of 22.2:18.8:49.0:5.0:1.0 (Celloxide2021P:DE203:OXT-221:I290:F552). CaO (Aldrich, average particle size about 150 nm) was added to the epoxy compound so that the moisture adsorbent was 15 parts by weight per 100 parts by weight.

[0066] The mixing vessel was mixed with a planetary mixer (Kurabo, KK-250s) to prepare a uniform sealant composition.

[0067] <Example 2> A sealant composition was prepared in the same manner as in Example 1, except that an alicyclic epoxy compound (Celloxide 2021P from Daicel), an oxetane group-containing compound (OXT-221 from Toagio), a photoinitiator containing a sulfonium salt (I290), and a fluorosurfactant (F552 from DIC) were added to a mixing vessel at room temperature in a weight ratio of 37.5:52.5:5.0:1.0 (Celloxide 2021P:OXT-221:I290:F552), respectively.

[0068] <Example 3> A sealant composition was prepared in the same manner as in Example 1, except that an alicyclic epoxy compound (Celloxide 2021P from Daicel), an aliphatic epoxy compound (DE203 from HAJIN CHEM TECH), an oxetane group-containing compound (OXT-221 from TOAGOSEI), a photoinitiator (I290), and a fluorine-based surfactant (F552 from DIC) were added to a mixing vessel at room temperature in a weight ratio of 37.5:7.0:45.5:5.0:1.0 (Celloxide2021P:DE203:OXT-221:I290:F552), respectively.

[0069] <Example 4> A sealant composition was prepared in the same manner as in Example 1, except that BASF's iodonium photoinitiator Irgacure 250 (active contents 75 wt%, solvent (propylene carbonate) 25 wt%) was used instead of I290 as the photoinitiator.

[0070] <Example 5> At room temperature, an alicyclic epoxy compound (Celloxide 2021P from Daicel) and an aliphatic epoxy compound (DE203 from HAJIN CHEM TECH), an oxetane group-containing compound (OXT-221 from TOAGOSEI), a photoinitiator (Irgacure PAG 290 from BASF, hereinafter referred to as I290), a fluorine-based surfactant (F552 from DIC) and diethylene glycol monobutyl ether acetate were added to a mixing vessel at a weight ratio of 17.2:18.8:44.0:5.0:1.0:10.0 (Celloxide2021P:DE203:OXT-221:I290:F552:diethylene glycol monobutyl ether acetate), respectively. The sealant composition was prepared in the same manner as in Example 1.

[0071] <Example 6> At room temperature, an alicyclic epoxy compound (Celloxide 2021P from Daicel) and an aliphatic epoxy compound (DE203 from HAJIN CHEM TECH), an oxetane group-containing compound (OXT-221 from TOAGOSEI), a photoinitiator (Irgacure PAG 290 from BASF, hereinafter referred to as I290), and a fluorine-based surfactant (F552 from DIC) were added to a mixing vessel in a weight ratio of 5:26:48:5:1 (Celloxide2021P:DE203:OXT-221:I290:F552), respectively. The sealant composition was prepared in the same manner as in Example 1.

[0072] <Comparative Example 1> A sealant composition was prepared in the same manner as in Example 1, except that an alicyclic epoxy compound (Celloxide 2021P from Daicel) and an aliphatic epoxy compound (DE203 from HAJIN CHEM TECH), an oxetane group-containing compound (OXT-221 from TOAGOSEI), a photoinitiator (I290) and a fluorine-based surfactant (F552 from DIC) were added to a mixing vessel at room temperature in a weight ratio of 2.3:23.4:64.3:5.0:1.0 (Celloxide2021P:DE203:OXT-221:I290:F552).

[0073] <Comparative Example 2> At room temperature, an alicyclic epoxy compound (Celloxide 2021P from Daicel) and an aliphatic epoxy compound (DE203 from HAJIN CHEM TECH), an oxetane group-containing compound (OXT-221 from TOAGOSEI), a photoinitiator (Irgacure PAG 290 from BASF, hereinafter referred to as I290), and a fluorine-based surfactant (F552 from DIC) were added to a mixing vessel in a weight ratio of 10:10:59:5:1 (Celloxide2021P:DE203:OXT-221:I290:F552), respectively. The sealant composition was prepared in the same manner as in Example 1.

[0074] <Comparative Example 3> At room temperature, an alicyclic epoxy compound (Celloxide 2021P from Daicel), an oxetane group-containing compound (3-allyloxy oxetane from TCI), tri(ethylene glycol) divinyl ether (TEGDVE), a photoinitiator (Irgacure PAG 290 from BASF, hereinafter referred to as I290), and a fluorine-based surfactant (F552 from DIC) were added to a mixing vessel in a weight ratio of 20:50:30:5:1 (Celloxide2021P:3-allyloxy oxetane:TEGDVE:I290:F552), respectively. The sealant composition was prepared in the same manner as in Example 1.

[0075] The physical properties in the examples and comparative examples were evaluated by the following methods.

[0076] 1. SiNx deposition film experiment The sealant compositions prepared in the Examples and Comparative Examples were inkjet coated on the glass substrate on which the SiNx deposition film was formed to form an organic layer having a thickness of 5 μm.

[0077] The samples were then subjected to constant temperature and humidity conditions of 85° C. and 85% RH to observe the lifting phenomenon of the deposition film. After 1000 hours of observation, samples were classified into those in which lifting occurred on 50% or more of the total area: X, those in which lifting occurred on less than 50% of the total area: △, and those in which lifting did not occur at all: O.

[0078] 2. Judging the presence or absence of ejection and suitability for inkjetting The sealant compositions prepared in the examples and comparative examples were inkjetted using Unijet UJ-200 (Inkjet head - Dimatix 10P1 256). A discharge test was performed every 5 minutes, and the dischargeable duration was classified as O for 3 hours or more, △ for 1 hour or more but less than 3 hours, and X for less than 1 hour.

[0079] [Table 1] [Explanation of symbols]

[0080] 3:Organic electronic devices 31: Substrate 32: Organic electronic devices 33:Organic layer 34: Inorganic layer 35:Protective film 36: Sealing structure 37: Sealing film 38: Cover board

Claims

1. an ink composition in a solvent-free form, comprising an epoxy compound, a compound having an oxetane group in a range of 45 parts by weight to 145 parts by weight based on 100 parts by weight of the epoxy compound, and a moisture adsorbent in a range of 5 to 110 parts by weight based on 100 parts by weight of the epoxy compound; The epoxy compound includes a compound having an alicyclic structure in its molecular structure and a linear or branched aliphatic compound, the linear or branched aliphatic compound is contained in an amount within a range of 20 parts by weight or more and less than 205 parts by weight based on 100 parts by weight of the compound having an alicyclic structure, The moisture adsorbent has an average particle size of 98 nm to 495 nm.

2. The sealant composition according to claim 1, wherein the epoxy compound is at least difunctional.

3. 2. The sealant composition according to claim 1, wherein the compound having an alicyclic structure in its molecular structure has a ring-constituting atom number in the range of 3 to 10 in the molecular structure.

4. The sealing material composition according to any one of claims 1 to 3, wherein the compound having an oxetane group has a boiling point within a range of 90 to 300°C.

5. 5. The sealing material composition according to claim 1, wherein the compound having an oxetane group has a weight average molecular weight in the range of 150 to 1,000 g / mol.

6. The sealant composition according to any one of claims 1 to 5, further comprising an ionic photoinitiator.

7. The sealant composition of claim 6, wherein the photoinitiator is a photoinitiator containing a sulfonium salt.

8. The sealant composition according to claim 6 or 7, wherein the photoinitiator is included in an amount of 1 to 15 parts by weight based on 100 parts by weight of the epoxy compound.

9. The sealant composition according to claim 1 , further comprising a surfactant.

10. 10. The sealant composition of claim 9, wherein the surfactant comprises a polar functional group.

11. The sealant composition according to claim 9 or 10, wherein the surfactant includes a fluorine-based compound.

12. The sealant composition according to any one of claims 9 to 11, wherein the surfactant is included in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the epoxy compound.

13. 13. The sealant composition according to any one of claims 1 to 12, characterized in that the viscosity measured with a Brookfield DV-3 at a temperature of 25°C, 90% torque and a shear rate of 100 rpm is 50 cPs or less.

14. 14. The sealant composition of claim 1, wherein the moisture adsorbent is a chemically reactive adsorbent.

15. 15. An organic electronic device comprising: a substrate; an organic electronic element formed on the substrate; and an organic layer sealing the entire surface of the organic electronic element, the organic electronic element comprising the sealant composition according to claim 1.

16. A method for manufacturing an organic electronic device, comprising the step of forming an organic layer on a substrate having an organic electronic element formed thereon, the organic layer being formed with the encapsulant composition according to claim 1 so as to encapsulate the entire surface of the organic electronic element.

17. 20. The method of claim 16, wherein the step of forming an organic layer comprises inkjet printing.

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