KR102171283B1 - Encapsulating composition - Google Patents

Abstract

The present application relates to a sealing material composition, an organic electronic device including the same, and a method of manufacturing the organic electronic device, and can secure the life of the organic electronic device by effectively blocking moisture or oxygen flowing into the organic electronic device from the outside, Provides a sealing material composition excellent in storage stability during distribution and storage.

Description

Sealing material composition {ENCAPSULATING COMPOSITION}

The present application relates to a sealing material composition, 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, has a faster response speed, and is advantageous in reducing the thickness of a display device or lighting compared to a conventional light source. 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 durability. 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.

The present application provides a sealing material composition capable of securing the life of the organic electronic device by effectively blocking moisture or oxygen flowing into the organic electronic device from the outside, and having excellent storage stability during distribution and storage.

The present application relates to a sealing material composition. The sealing material composition may be, for example, a sealing material applied to sealing or encapsulating an organic electronic device such as an OLED. In one example, the sealing material composition of the present application may be applied to encapsulating or encapsulating the entire surface of an organic electronic device. Accordingly, after the sealing material composition is applied to encapsulation, it may exist in the form of an organic layer sealing the entire surface of the organic electronic device. In addition, the organic layers may be alternately stacked on the organic electronic device together with an inorganic protective film and/or an inorganic layer to be described later to form an encapsulation structure.

In a specific example of the present application, the present application relates to a sealing material composition for encapsulating an organic electronic device applicable to an inkjet process and a method for manufacturing the same, wherein the composition is applied to a substrate using inkjet printing capable of non-contact patterning, with appropriate physical properties It can be designed to have.

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 electric charges using holes and electrons between a pair of electrodes facing each other. 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 sealing material composition is a solvent-free type photocurable sealing material composition, and may include a curable compound, a photoinitiator, a photosensitizer, and a heat stabilizer. The curable compound, photoinitiator, photosensitizer, and heat stabilizer may be included in the composition in a weight ratio of 90 to 98 parts by weight, 1 to 5 parts by weight, 0.01 to 3 parts by weight, and 0.06 to 3 parts by weight, respectively, another example As, 91 to 97 parts by weight, 1.5 to 4.5 parts by weight, 0.1 to 2 parts by weight and 0.1 to 2 parts by weight; 92 to 96 parts by weight, 2 to 4 parts by weight, 0.2 to 1.4 parts by weight, and 0.2 to 1.4 parts by weight; 93 to 96 parts by weight, 2.5 to 3.5 parts by weight, 0.3 to 0.9 parts by weight, and 0.3 to 0.9 parts by weight may be included in the composition. The present application is a composition capable of ink jetting by controlling the specific composition to a limited content range, suppressing side reactions in the distribution and storage stages before the sealing material composition is applied to the organic electronic device, and maintaining the viscosity desired in the present application. Storage stability can be maintained.

In a specific example of the present application, the curable compound may include at least one or more curable functional groups. The curable functional group, for example, may be one or more selected from oxetane group, glycidyl group, isocyanate group, hydroxy group, carboxyl group, amide group, epoxide group, sulfide group, acetal group and lactone group. The curable functional group may be at least one functional or two or more functional. In the present application, by using the curable compound, excellent durability reliability, adhesion properties, and moisture barrier properties can be implemented.

Exemplary curable compounds may include an epoxy compound and a compound having an oxetane group. In a specific example of the present application, the compound having an oxetane group may be included in the range of 45 parts by weight to 145 parts by weight based on 100 parts by weight of the epoxy compound. The compound having an oxetane group may be included in the range of 45 parts by weight to 145 parts by weight, 48 parts by weight to 144 parts by weight, 63 parts by weight to 143 parts by weight, or 68 parts by weight to 142 parts by weight based on 100 parts by weight of the epoxy compound. have. The term "part by weight" in the present specification may mean a weight ratio between each component. In this application, by controlling the above specific composition and its content range, an organic layer can be formed on an organic electronic device by an inkjet method, and the applied sealing material composition has excellent spreadability within a short time, and excellent curing strength after curing. It is possible to provide an organic layer having. In addition, the specific content of the curable compound can implement excellent storage stability, particularly together with the above-described photoinitiator, photosensitizer, and heat stabilizer.

In one example, the sealing material composition of the present application may have a contact angle with respect to glass of 30° or less, 25° or less, 20° or less, or 12° or less. The lower limit is not particularly limited, but may be 1° or 3° or more. According to the present application, by adjusting the contact angle to be 30° or less, spreadability can be secured within a short time in inkjet coating, and thus a thin organic layer can be formed. In the present application, the contact angle may be measured by applying a drop of the sealing material composition on the glass using the Sessile Drop measurement method, and may be measured by measuring an average value after 5 times application.

In one example, the curable compound including the epoxy compound and the compound having an oxetane group may be included in 70 wt% or more, 75 wt% or more, 80 wt% or more, 85 wt% or more, or 89 wt% or more in the entire component of the sealing material composition. The upper limit is not particularly limited, and may be 99 wt% or less, 95 wt% or less, or 93 wt% or less.

In one example, the epoxy compound may be at least one functional or more. That is, one or more or two or more of the epoxy functional groups may be present in the compound, and the upper limit is not particularly limited, but may be 10 or less. The epoxy compound implements an appropriate degree of crosslinking in the adhesive to realize excellent heat resistance and durability at high temperature and high humidity.

In the embodiments of the present application, the epoxy compound may include a compound having a cyclic structure and/or a linear or branched aliphatic compound in the molecular structure. That is, the sealing material composition of the present application may include, as an epoxy compound, at least one of a compound having a cyclic structure in a molecular structure and a linear or branched aliphatic compound, and may be included together. In one example, the compound having a cyclic structure in the molecular structure may have a cyclic atom in the molecular structure in the range of 3 to 10, 4 to 8, or 5 to 7, and the cyclic structure in the compound is 1 or more or 2 or more, 10 It may exist below. When the compound having the cyclic structure and the linear or branched aliphatic compound are included together, the linear or branched aliphatic compound is 20 parts by weight or more, less than 205 parts by weight, 23 parts by weight based on 100 parts by weight of the compound having a cyclic structure. Sealing material composition in the range of 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 Can be included in By controlling the content range, the present application allows the sealing material composition to have suitable physical properties for sealing an organic electronic device, have excellent curing strength after curing, and also realize excellent moisture barrier properties.

In one example, the epoxy compound may have an epoxy equivalent in the range of 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 may have a weight average molecular weight of 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. In this application, by controlling the epoxy equivalent of the epoxy compound to be low, or by adjusting the weight average molecular weight of the compound having an oxetane group to be low, the viscosity of the composition becomes excessively high while improving the curing completion degree after curing of the sealing material, making the inkjet process impossible. It can be prevented, and at the same time, it is possible to provide moisture barrier properties and excellent curing sensitivity. In the present specification, the weight average molecular weight refers to a value in terms of standard polystyrene measured by GPC (Gel Permeation Chromatograph). In one example, a column consisting of a metal tube having a length of 250 to 300 mm and an inner diameter of 4.5 to 7.5 mm is filled with 3 to 20 mm of polystyrene bead. When the diluted solution in which the substance to be measured is dissolved in a THF solvent is passed through a column, the weight average molecular weight can be indirectly measured according to the time outflow. The amount separated by size from the column can be detected by plotting by time. In addition, in the present specification, the epoxy equivalent is the number of grams (g/eq) of a resin containing 1 gram equivalent of an epoxy group, and can be measured according to the method specified in JIS K 7236.

In addition, the compound having an oxetane group may have a boiling point in the range of 90 to 300°C, 98 to 270°C, 110 to 258°C, or 138 to 237°C. The present application is a sealing material capable of preventing damage to the device by controlling the boiling point of the compound within the above range, implementing excellent printability even at high temperatures in the inkjet process, excellent moisture barrier properties from the outside, and suppressing outgassing It is possible to provide. In the present specification, the boiling point may be measured at 1 atmosphere unless otherwise specified.

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, vinylcyclohexene Dioxide and derivatives, 1,4-cyclohexanedimethanol bis (3,4-epoxycyclohexanecarboxylate) and derivatives may be exemplified, but are not limited thereto.

In one example, the structure of the compound containing the oxetane group is not limited as long as it has the functional group, and for example, TOAGOSEI's OXT-221, CHOX, OX-SC, OXT101, OXT121, OXT221 or OXT212, or ETERNACOLL's EHO, OXBP, OXTP or OXMA may be exemplified. In addition, the linear or branched aliphatic epoxy compound is aliphatic glycidyl ether, 1,4-butanediol diglycidyl ether, ethylene glycol diglycidyl ether, 1,6-hexanediol digly Cidyl ether, propylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether or neopentyl glycol diglycidyl ether Can, but is not limited thereto.

In the embodiment of the present application, the sealing material composition may further include a photoinitiator. The photoinitiator may be a cationic photopolymerization initiator.

Can be used a known material in the art for cationic photo-polymerization initiator, for example, aromatic sulfonium, aromatic iodonium, aromatic dia cation portion containing jonyum or aromatic ammonium and _{^{AsF 6 -, SbF 6 -,}} PF 6 ^- , or a compound having an anion moiety including tetrakis (pentafluorophenyl) borate. In addition, as the cationic photopolymerization initiator, an onium salt or an organometallic salt based ionized cationic initiator or an organic silane 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 Examples of zero may be iron arene, and the like, 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 one example, the present application is particularly applied to the use of sealing organic electronic devices in an ink-jet method, and considering that it is included together with the above-described curable compound, photosensitizer, and heat stabilizer, sulfonium salt as a photoinitiator It may include. The present application can implement excellent storage stability by controlling the content ratio between each composition in the above specific composition formulation.

The photoinitiator including the sulfonium salt may have at least one or more cyclic structures in the molecular structure. The cyclic structure is a cyclic structure in which cyclic atoms are in the range of 3 to 10, 4 to 8, or 5 to 7 in the molecular structure, and may be an aliphatic ring structure or an aromatic ring structure. In a specific example of the present application, the sulfonium salt may include at least one aryl group, and may include, for example, a phenyl group. The aryl group may be optionally substituted with one or more substituents, and as the substituent, a halogen atom, a hydroxy group, a carboxyl group, a thiol group, an alkyl group, an alkoxy group, an alkenyl group, an epoxy group, a cyano group, a carboxyl group, an acryloyl group, A mercapto group substituted with an aromatic such as a methacryloyl group, an acryloyloxy group, a methacryloyloxy group, an aryl group or a thiolphenol group may be exemplified, but is not limited thereto. In one example, the sulfonium salt may have at least one aryl group in which a mercapto group substituted with an aromatic group exists as a substituent. The photoinitiator may be included in an amount of 0.1 to 15 parts by weight, 0.5 to 10 parts by weight, or 1 to 4 parts by weight based on 100 parts by weight of the total curable compound in the composition. By including the specific photoinitiator, the present application can maintain long-term reliability of the composition together with a photosensitizer and a heat stabilizer.

In a specific example of the present application, the sealing material composition may include a photosensitizer to supplement curability in a long wavelength active energy ray of 300 nm or more. The photosensitizer may be a compound that absorbs a wavelength in the range of 200 nm to 400 nm, 250 nm to 400 nm, 300 nm to 400 nm, 350 nm to 398 nm, or 375 nm to 397 nm.

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 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 it may be one or more selected from the group consisting of 3-methyl-b-naphthothiazoline.

In the specific example of the present application, the content ratio of the photosensitizer to the content of the photoinitiator may be in the range of 0.1 to 0.8, 0.12 to 0.75, 0.13 to 0.72, 0.14 to 0.68, 0.15 to 0.63, or 0.16 to 0.58. The present application implements a synergistic effect of curing sensitivity at a desired wavelength by adjusting the content of the photosensitizer to the photoinitiator, while reducing the reliability of the composition due to problems such as phase separation in relation to the photoinitiator including the sulfonium salt described above. Can be prevented.

As described above, the sealing material composition of the present application may include a heat stabilizer. The thermal stabilizer may be exemplified by a cresol compound, and specifically, 2,6-di-tert-Butyl-p-cresol, and the like. As another example, the heat stabilizer may include a thiazine compound, a quinone compound, an amino alcohol, and the like, and specific examples thereof may include Phenothiazine (PTZ), Methylenequinones, 2-dimethyl amino methanol or Mono methyl ether hydroquinone. . In a specific example of the present application, the content ratio of the thermal stabilizer to the content of the photoinitiator may be in the range of 0.12 to 0.78, 0.13 to 0.72, 0.15 to 0.68, or 0.16 to 0.53. In the present application, by controlling the content of the thermal stabilizer in the photoinitiator, it is possible to prevent viscosity increase, gelation, or curing reaction due to unnecessary thermal energy in the above-described composition, while maintaining inkjettable properties even for long-term distribution or storage.

In the embodiment of the present application, the sealing material composition may further include a surfactant. The sealing material composition may be provided as a liquid ink with improved spreadability by including a surfactant. In one example, 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 hydroxy group, a phosphate or a sulfonate. In addition, in the embodiment of the present application, the surfactant may be a non-silicone surfactant or a fluorine surfactant. The non-silicone-based surfactant or fluorine-based surfactant is applied together with the above-described curable compound to provide excellent coating properties on an organic electronic device. On the other hand, in the case of a surfactant including a polar reactive group, an excellent effect can be realized in terms of adhesion because the affinity with other components of the sealing material composition is high. In the specific example of the present application, a hydrophilic fluorine-based surfactant or a non-silicone-based surfactant may be used to improve coating properties on the substrate.

Specifically, the surfactant may be a polymeric or oligomeric fluorine-based surfactant. The surfactant may be a commercial product, for example, TEGO's Glide 100, Glide110, Glide 130, Glide 460, Glide 440, Glide450 or RAD2500, DIC (DaiNippon Ink & Chemicals) Megaface F-251, F-281, F-552, F554, F-560, F-561, F-562, F-563, F-565, F-568, F-570 and F-571 or Surflon S-111, S-112 from Asahi Glass , S-113, S-121, S-131, S-132, S-141 and S-145 or Sumitomo SriM's Fluorad 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 from BYK, 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. Can be used.

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 curable compound. Within the above content range, the present application allows the sealing material composition to be applied to an inkjet method to form a thin organic layer.

The sealing material composition of the present application may further include a coupling agent. The present application may improve the adhesion of the sealing material composition to the adherend of the cured product or the moisture permeability of the cured product. The coupling agent may include, for example, a titanium-based coupling agent, an aluminum-based coupling agent, and a silane coupling agent.

In a specific example of the present application, as the silane coupling agent, specifically, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropyl (dime Epoxy-based silane coupling agents such as oxy)methylsilane and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane; Mercapto-based silane coupling agents such as 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, and 11-mercaptoundecyltrimethoxysilane; 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldimethoxymethylsilane, N-phenyl-3-aminopropyltrimethoxysilane, N-methylaminopropyltrimethoxysilane, Amino-based silane coupling agents such as N-(2-aminoethyl)-3-aminopropyltrimethoxysilane and N-(2-aminoethyl)-3-aminopropyldimethoxymethylsilane; Ureide-based silane coupling agents such as 3-ureidepropyltriethoxysilane, vinyl-based silane coupling agents such as vinyl trimethoxysilane, vinyl triethoxysilane, 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-isocyanate propyltrimethoxysilane, bis(triethoxysilylpropyl) disulfide, and sulfide-based silane coupling agents such as bis(triethoxysilylpropyl)tetrasulfide; Phenyl trimethoxysilane, methacryloxypropyl trimethoxysilane, imidazole silane, triazine silane, etc. are mentioned.

In the present application, 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 curable compound. The present application may implement an effect of improving adhesion by adding a coupling agent within the above range.

The sealing material 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 specific types of moisture adsorbents that can be used in the present application are 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.

The sealing material 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. In the sealing material composition of the present application, by controlling the content of the moisture adsorbent to be preferably 5 parts by weight or more, the sealing material composition or the cured product thereof may exhibit excellent moisture and moisture barrier properties. In addition, the present application may provide a thin film encapsulation structure by controlling the content of the moisture adsorbent to 100 parts by weight or less.

In one example, the sealing material composition may further include an inorganic filler, if necessary. The specific type of the filler that can be used in the present application is not particularly limited, and for example, one type of clay, talc, alumina, calcium carbonate, or silica, or a mixture of two or more types may be used.

The sealing material composition of the present application may include 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 based on 100 parts by weight of the curable compound. have. The present application may provide a sealing structure having excellent moisture or moisture barrier properties and mechanical properties by controlling the inorganic filler to preferably 1 part by weight or more. In addition, the present invention can provide a cured product exhibiting excellent moisture barrier properties even when formed as a thin film by controlling the inorganic filler content to 50 parts by weight or less.

In addition to the above-described configuration, various additives may be included in the sealing material composition according to the present application within a range that does not affect the effects of the above-described invention. For example, the sealing material composition may contain a defoaming agent, a tackifier, an ultraviolet stabilizer, or an antioxidant in an appropriate range depending on the desired physical properties.

In one example, the sealing material composition may be liquid at room temperature, for example, about 25°C. In a specific example of the present application, the sealing material composition may be a liquid in a solvent-free form. The sealing material 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 sealing material composition has a liquid form at room temperature, the device may be sealed by applying the composition to the side of the organic electronic device. In addition, since the present application has a solvent-free form, it is possible to adjust the volatile organic compound and/or the moisture content.

In addition, the sealing material composition of the present application may be an ink composition. The sealing material composition of the present application may be an ink composition capable of an ink jetting process. The sealing material composition of the present application may have a specific composition and properties to enable ink jetting.

In addition, in a specific example of the present application, the sealing material composition has a viscosity measured by Brookfield's DV-3 at a temperature of 25° C., a torque of 90% and a shear rate of 100 rpm, 50 cPs or less, 1 to 46 cPs, or 5 to It may be in the range of 44 cPs. In the present application, by controlling the viscosity of the composition within the above range, it is possible to implement inkjettable properties when applied to an organic electronic device, and to provide a thin film encapsulant by improving coating properties.

In one example, the sealing material composition has a surface energy 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 after curing. It may be within the range of mN/m. It can be measured by a method known in the art for the measurement of the surface energy, for example, it can be measured by the Ring Method method. The present application may implement excellent coating properties within the surface energy range.

In the specific example of the present application, the surface energy (γ ^surface , mN/m) may be calculated as γ ^surface = γ ^dispersion + γ ^polar . In one example, the surface energy may be measured using a drop shape analyzer (DSA100 manufactured by KRUSS). For example, the surface energy is obtained by applying a sealing material composition to be measured on a SiNx substrate with a thickness of about 50 µm and a coating area of 4 cm ² (width: 2 cm, length: 2 cm) to form a sealing film (spin coater), and nitrogen after drying in an atmosphere at room temperature for about 10 minutes then UV cured with the light quantity of 4000mJ / cm ² at an intensity of 1000mW / cm ^2. After curing, deionized water having a known surface tension was dropped on the film and the process of obtaining the contact angle was repeated five times to obtain the average value of the obtained five contact angle values, and in the same way, the surface tension was known. Diiodomethane (diiodomethane) is dropped and the process of obtaining the contact angle is repeated five times, and the average value of the five contact angle values obtained is obtained. Thereafter, the surface energy can be calculated by substituting a value (Strom value) about the surface tension of the solvent by the Owens-Wendt-Rabel-Kaelble method using the obtained average value of the contact angle for deionized water and diiodomethane.

In addition, in the specific example of the present application, the sealing material composition may have a light transmittance of 90% or more, 92% or more, or 95% or more in a visible light region after curing. Within the above range, the present application provides an organic electronic device with high resolution, low power consumption and long life by applying a sealing material composition to a top emission type organic electronic device. In addition, the sealing material composition of the present application may have a haze of 3% or less, 2% or less, or 1% or less according to the JIS K7105 standard test after curing, and the lower limit is not particularly limited, but may be 0%. Within the haze range, the sealing material composition may have excellent optical properties after curing. In the present specification, the aforementioned light transmittance or haze may be measured while the sealing material composition is cured with an organic layer, and may be an optical characteristic measured when the thickness of the organic layer is any one of 2 μm to 50 μm. . In the specific example of the present application, in order to implement the optical properties, the aforementioned moisture adsorbent or inorganic filler may not be included.

The present application also relates to an organic electronic device. An exemplary organic electronic device 3 includes a substrate 31 as shown in FIG. 1; An organic electronic device 32 formed on the substrate 31; And an organic layer 33 that seals the entire surface of the organic electronic device 32 and includes the above-described sealing material composition.

In a specific example of the present application, 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 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 35 for protecting an electrode and a light emitting layer of the device. The protective layer 35 may be an inorganic protective layer. 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 50 μm.

In the specific example of the present application, 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 above-described protective layer. In one example, 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, or 0.1 μm to 20 μm, or 1 μm to 10 μm. In one example, the inorganic layer of the present application may be an inorganic material without a dopant or an inorganic material including a dopant. The dopant that can be doped is one or more elements selected from the group consisting of Ga, Si, Ge, Al, Sn, Ge, B, In, Tl, Sc, V, Cr, Mn, Fe, Co, and Ni, or the element It may be an oxide of, but is not limited thereto.

In one example, the thickness of the organic layer may be in the range of 2㎛ to 20㎛, 2.5㎛ to 15㎛, 2.8㎛ to 9㎛. The present application may provide a thin organic electronic device by providing a thin organic layer.

The organic electronic device 3 of the present application may include an encapsulation structure including the organic layer 33 and the inorganic layer 34 described above, and the encapsulation structure includes at least one organic layer and at least one inorganic material layer, , The organic layer and the inorganic layer may be repeatedly stacked. For example, the organic electronic device may have a structure of a substrate/organic electronic device/protective layer/(organic layer/inorganic layer) n, and n may be a number within the range of 1 to 100. 1 is a cross-sectional view illustrating an example when n is 1.

In one example, the organic electronic device 3 of the present application may further include a cover substrate present on the organic layer 33. The material of the substrate and/or the cover substrate is not particularly limited, and a material known in the art may be used. For example, the substrate or cover substrate may be a glass, a metal substrate, 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 can be used.

In addition, the organic electronic device 3 of the present application, as shown in FIG. 2, is an encapsulation film 37 present between the cover substrate 38 and the substrate 31 on which the organic electronic device 32 is formed. It may further include. The encapsulation film 37 may be applied to attach the substrate 31 on which the organic electronic device 32 is formed and the cover substrate 38, and may be, for example, an adhesive film or an adhesive film, but is limited thereto. It is not. The encapsulation film 37 may seal the entire surface of the encapsulation structure 36 of the organic and inorganic layers stacked on the organic electronic device 32.

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

In one example, the manufacturing method includes forming an organic layer 33 so that the above-described sealing material composition seals the entire surface of the organic electronic device 32 on the substrate 31 on which the organic electronic device 32 is formed. It may include.

In the above, the organic electronic device 32 is a substrate 31, for example, a reflective electrode or a transparent electrode is formed on a substrate 31 such as glass or a polymer film by 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.

The manufacturing method of the present application may further include forming an inorganic protective layer 35 on the first electrode, the organic material layer, and the second electrode formed on the substrate 31. Then, the above-described organic layer 33 is applied on the substrate 31 to cover the organic electronic device 32 entirely. At this time, the step of forming the organic layer 33 is not particularly limited, and inkjet printing, gravure coating, spin coating, screen printing, or reverse offset using the above-described sealing material composition on the entire surface of the substrate 31 A process such as coating (Reverse Offset) may be used.

The manufacturing method is also; It may further include the step of irradiating light to the organic layer. In the present invention, a curing process may be performed on the organic layer encapsulating the organic electronic device, such a curing process) may be performed in, for example, a heating chamber or a UV chamber, and preferably may be performed in a UV chamber.

In one example, after the above-described sealing material composition is applied to form the front organic layer, the composition may be irradiated with light to induce crosslinking. Irradiating the light may include irradiating light having a wavelength range of 250 nm to 450 nm or 300 nm to 450 nm at a light amount of 0.3 to 6 J/cm ² or 0.5 to 5 J/cm ² .

In addition, the manufacturing method of the present application may further include forming the inorganic layer 34 on the organic layer 33. In the forming of the inorganic layer, a method known in the art may be used, and may be the same as or different from the above-described method for forming a protective layer.

The present application provides a sealing material composition that can secure the life of an organic electronic device by effectively blocking moisture or oxygen flowing into the organic electronic device from the outside, and has excellent storage stability during distribution and storage, and an organic electronic device including the same. .

1 and 2 are cross-sectional views 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

As curable compounds at room temperature, alicyclic epoxy compounds (Daicel's Celloxide 2021P), aliphatic epoxy compounds 1,4-butanediol diglycidyl ether (DE200, HAJIN CHEM TECH's), and oxetane group-containing curable compounds (TOAGOSEI's OXT- 212), a photoinitiator having a triphenylsulfonium salt (UV693 from TETRA CHEM), a fluorine-based surfactant (F447 from DIC), a photosensitizer (9,10-Dibutoxyanthracene), and a heat stabilizer 2,6-di-tert-Butyl-p -cresol (BHT from SIGMA aldrich) 20:20:54:3:1:0.5:0.5 (Celloxide2021P:DE200:OXT-212:UV693:F447:9,10-Dibutoxyanthracene:2,6-di-tert-Butyl -p-cresol) was added to the mixing container in a weight ratio.

The mixing container was prepared with a uniform sealing material composition ink using a Planetary mixer (Kurabo, KK-250s).

Example 2

A sealing material composition was prepared in the same manner as in Example 1, except that the content of the photoinitiator was changed to 1 part by weight and the content of the oxetane group-containing curable compound was changed to 56 parts by weight.

Comparative example One

A sealing material composition was prepared in the same manner as in Example 1, except that a photoinitiator (TTA UV-694) having a diphenyliodonium salt was used as the photoinitiator.

Comparative example 2

A sealing material composition was prepared in the same manner as in Example 1, except that the content of the heat stabilizer was changed to 5 parts by weight and the content of the curable compound containing an oxetane group was changed to 49.5 parts by weight.

Comparative example 3

A sealing material composition was prepared in the same manner as in Example 1, except that the content of the photosensitizer was changed to 5 parts by weight and the content of the oxetane group-containing curable compound was changed to 49.5 parts by weight.

Comparative example 4

A sealing material composition was prepared in the same manner as in Example 1, except that the content of the heat stabilizer was changed to 0.001 parts by weight.

Comparative example 5

A sealing material composition was prepared in the same manner as in Example 1, except that the content of the photosensitizer was changed to 3.2 parts by weight.

Comparative example 6

A sealing material composition was prepared in the same manner as in Example 1, except that the content of the heat stabilizer was changed to 3.5 parts by weight.

Comparative example 7

A sealing material composition was prepared in the same manner as in Example 1, except that the content of the photoinitiator was changed to 3.3 parts by weight and the content of the thermal stabilizer was changed to 0.05 parts by weight.

Experimental example 1-storage stability evaluation

The sealing material compositions prepared in Examples and Comparative Examples were stored under the following conditions.

1) Under N ₂ atmosphere, the temperature of 25℃ to 35℃, moisture and oxygen are less than 1000ppm, and stored for 15 days in a light-blocked container

2) Stored for 15 days in a container protected from light and at a temperature of 45℃ under atmospheric atmosphere

3) Stored for 15 days in a container exposed to a temperature of 25℃ to 35℃ and yellow

4) Although exposed to white fluorescent lamps, UV cut films (green and yellow) are attached, and stored for 15 days in a container with a temperature of 25℃ to 35℃, moisture and oxygen below 1000ppm

Measure the change in viscosity under the above four conditions (Brookfield Co., Ltd., using a con&plate, measured at a temperature of 25°C, a torque of 90%, and a shear rate of 100 rpm), and the viscosity immediately before storage and the viscosity after storage for 15 days. If the change is within ±10%, it is marked as O, and if the viscosity is changed by exceeding ±10%, it is marked as X.

1) conditions 2) conditions 3) conditions 4) conditions Example 1 O O O O Example 2 O O O O Comparative Example 1 X X X X Comparative Example 2 X X X X Comparative Example 3 X X X X Comparative Example 4 X X X X Comparative Example 5 X X X X Comparative Example 6 X X X X Comparative Example 7 X X X X

3: organic electronics
31: substrate
32: organic electronic device
33: organic layer
34: inorganic layer
35: shield
36: bag structure
37: bag film
38: cover substrate

Claims (16)

It is a solvent-free type photocurable sealing material composition,
Including a curable compound, a photoinitiator including a sulfonium salt, a photosensitizer and a heat stabilizer,
The curable compound, photoinitiator, photosensitizer, and thermal stabilizer are included in a weight ratio of 90 to 98 parts by weight, 1 to 5 parts by weight, 0.01 to 3 parts by weight, and 0.06 to 3 parts by weight, respectively,
A sealing material composition for sealing an organic electronic device in which the content ratio of the photosensitizer to the content of the photoinitiator is in the range of 0.1 to 0.8. The sealing material composition for sealing an organic electronic device according to claim 1, wherein the curable compound includes at least one curable functional group. The sealing material for sealing an organic electronic device according to claim 2, wherein the curable functional group is at least one selected from glycidyl group, oxetane group, isocyanate group, hydroxy group, carboxyl group, amide group, epoxide group, sulfide group, acetal group and lactone group Composition. The sealing material composition according to claim 2, wherein the curable compound is at least bifunctional or higher. The method of claim 1, wherein the curable compound is an epoxy compound; And a sealing material composition for sealing an organic electronic device comprising a compound having an oxetane group. The sealing material composition for sealing an organic electronic device according to claim 5, wherein the epoxy compound comprises a compound having a cyclic structure in a molecular structure and/or a linear or branched aliphatic compound. The sealing material composition of claim 5, wherein the compound having an oxetane group is contained in an amount of 45 parts by weight to 145 parts by weight based on 100 parts by weight of the epoxy compound. The sealing material composition for sealing an organic electronic device according to claim 6, wherein the linear or branched aliphatic compound is contained in an amount of 20 parts by weight or more and less than 205 parts by weight based on 100 parts by weight of the compound having a cyclic structure. The sealing material composition for sealing an organic electronic device according to claim 1, wherein the photoinitiator comprises a cationic photopolymerization initiator. The sealing material composition for sealing an organic electronic device according to claim 1, wherein the photoinitiator comprising a sulfonium salt has at least one cyclic structure in its molecular structure. The sealing material composition according to claim 1, wherein the photosensitizer is a material that absorbs a wavelength in the range of 200 nm to 400 nm. The sealing material composition of claim 1, wherein the thermal stabilizer comprises 2,6-di-tert-Butyl-p-cresol, phenothiazine (PTZ), Methylenequinones, 2-dimethyl amino methanol or mono methyl ether hydroquinone. . delete The sealing material composition for sealing an organic electronic device according to claim 1, further comprising a surfactant. Board; An organic electronic device formed on a substrate; And an organic layer that seals the entire surface of the organic electronic device and includes the sealing material composition according to claim 1. A method of manufacturing an organic electronic device comprising the step of forming an organic layer on a substrate having an organic electronic device formed thereon so that the sealing material composition of claim 1 seals the entire surface of the organic electronic device.

Images