KR102507270B1 - Encapsulating composition - Google Patents

Abstract

The present application relates to an encapsulant composition and an organic electronic device including the same, which effectively blocks moisture or oxygen flowing into the organic electronic device from the outside to secure the life of the organic electronic device, and implements a top emission type organic electronic device. An encapsulant composition that can be applied in an inkjet method, can provide a thin display, and can effectively prevent electromagnetic field interference due to its low dielectric constant.

Description

Sealing material composition {ENCAPSULATING COMPOSITION}

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

An organic electronic device (OED) refers to a device including an organic material layer generating an alternating charge using holes and electrons, examples of which include a photovoltaic device, a rectifier, and a transmitter and an organic light emitting diode (OLED).

Among the organic electronic devices, an Organic Light Emitting Diode (OLED) consumes less power and has a faster response speed than conventional light sources, and is advantageous for thinning a display device or lighting. In addition, OLED has excellent space utilization and is expected to be applied in various fields ranging from various portable devices, monitors, laptops and TVs.

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

As an example, a technique of forming a passivation film by repeatedly stacking an organic layer and an inorganic layer on the entire surface of an organic electronic device is well known, but forming an organic layer of a thin film according to thinning of OLED is a major research task, and a thin film Even if an organic layer is formed, since the organic layer of the thin film causes an electromagnetic field interference problem, a method to solve this problem is being studied.

The present application effectively blocks moisture or oxygen flowing into the organic electronic device from the outside to secure the lifespan of the organic electronic device, realizes a front-emitting organic electronic device, is applicable in an inkjet method, and is thin. A sealant composition capable of providing a display and effectively preventing electromagnetic field interference due to its low permittivity and an organic electronic device including the same are provided.

This application relates to a sealant composition. The encapsulant composition may be, for example, an encapsulant applied to encapsulate or encapsulate an organic electronic device such as an OLED. In one example, the sealant composition of the present application may be applied to encapsulate or encapsulate the entire surface of an organic electronic device. Therefore, after the sealant composition is applied for encapsulation, it may exist in the form of an organic layer that seals the front surface of the organic electronic device. In addition, the organic layer may be laminated on the organic electronic device together with a passivation layer and/or an inorganic layer to be described later to form an encapsulation structure.

In a specific embodiment of the present application, the present application relates to a sealant composition for encapsulating an organic electronic device applicable to an inkjet process, wherein the composition is designed to have appropriate physical properties when discharged onto a substrate using inkjet printing capable of non-contact patterning. can

In this specification, the term "organic electronic device" refers to an article or device having a structure including an organic material layer that generates an alternating charge using holes and electrons between a pair of electrodes facing each other. may include, but are not limited to, photovoltaic devices, rectifiers, transmitters and organic light emitting diodes (OLEDs). In one example of the present application, the organic electronic device may be an OLED.

Exemplary sealant compositions may be photocurable or thermosetting compositions. The sealant composition includes an epoxy compound, an oxetane compound and a photoinitiator. The photoinitiator may be an ionic photoinitiator or a photoinitiator containing a sulfonium salt. The epoxy compound may include, for example, a straight-chain monofunctional compound having 7 or more carbon atoms. In the present application, the monofunctional compound is included in the range of 25 to 81 parts by weight, 28 to 80.5 parts by weight, 33 to 70 parts by weight, 40 to 65 parts by weight, or 45 to 58 parts by weight based on 100 parts by weight of the total epoxy compound in the composition. can The sealing material composition of the present application may further include, as the epoxy compound, not only the monofunctional epoxy compound, but also an alicyclic compound or a linear or branched polyfunctional aliphatic compound, which will be described later. The entirety of the epoxy compound included in the composition When calculated as 100, the monofunctional epoxy compound may be included in the above weight ratio. In the present application, interference between circuits can be effectively prevented by adjusting the dielectric constant to a low level as well as forming an organic layer of a thin film through the above-described specific formulation of the sealing material composition.

In one example, the type of the straight-chain monofunctional compound having 7 or more carbon atoms is a compound having one epoxy group, and is not particularly limited. For example, the monofunctional compound is a linear compound and may not have a branched chain structure or a cyclic structure. In addition, the monofunctional compound is an aliphatic compound and may not include an aromatic structure. In addition, the monofunctional compound is a type of epoxy compound and includes a cyclic ether group, but may not include an ether group in its molecular structure. That is, the monofunctional compound of the present application may not include an ether group other than a cyclic ether group. The linear structure may have 7 to 30, 8 to 25, 9 to 20 or 10 to 15 carbon atoms. In the present application, by adjusting the sealing material composition to the above-described specific composition, it is possible to implement the coating characteristics of the sealing material composition, curing physical properties after curing, and physical properties of low dielectric constant. Hereinafter, in the present specification, the straight-chain monofunctional compound having 7 or more carbon atoms may be referred to as a monofunctional compound or a monofunctional epoxy compound.

The sealing material composition of the present application may also include a photoinitiator together with the epoxy compound and the oxetane compound. The photoinitiator may be, for example, an ionic photoinitiator. The photoinitiator may be a compound that absorbs a wavelength in the range of 200 nm to 400 nm. In the present application, by using the photoinitiator, excellent curing properties can be implemented in a specific composition of the present application.

In one example, the photoinitiator may be a cationic photopolymerization initiator. For the cationic photopolymerization initiator, a material known in the art may be used, and for example, a cationic portion including aromatic sulfonium, aromatic iodonium, aromatic diazonium, or aromatic ammonium, AsF ₆ ^- , SbF ₆ ^- , PF ₆ ^- , or a compound having an anionic moiety including tetrakis (pentafluorophenyl) borate. In addition, as the cationic photopolymerization initiator, an onium salt or organometallic salt based ionizing cationic initiator or an organic silane or latent sulfuric acid based or non-ionized cationic photopolymerization initiator may be exemplified. . As the onium salt-based initiator, diaryliodonium salt, triarylsulfonium salt, or aryldiazonium salt may be exemplified, and organometallic salt-based initiators Examples of the zero include iron arene and the like, and examples of the organic silane-based initiator include o-nitrobenzyl triaryl silyl ether, triaryl silyl peroxide Alternatively, acyl silane may be exemplified, and latent sulfuric acid-based initiators may include α-sulfonyloxy ketone or α-hydroxymethylbenzoin sulfonate, but are not limited thereto. .

In one example, the sealing material composition of the present application may include a photoinitiator including a sulfonium salt as a photoinitiator in the specific composition described above to be suitable for use in sealing an organic electronic device in an inkjet method. Even though the sealing material composition according to the above composition is directly sealed on the organic electronic device, chemical damage to the device can be prevented due to a small amount of outgas generation. In addition, a photoinitiator containing a sulfonium salt has excellent solubility and can be suitably applied to an inkjet process.

In an embodiment of the present application, the photoinitiator may be included in 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. The present application can minimize physical and chemical damage to the organic electronic device due to the nature of the sealant composition of the present application applied directly on the organic electronic device by adjusting the content range of the photoinitiator.

In a specific example of the present application, the sealant composition may have a dielectric constant of 3.05 or less, 3.05 or less, 3.0 or less, 2.95 or less, or 2.9 or less at 100 kHz to 400 kHz and 25 ° C. after curing into a thin film having a thickness of 20 μm or less. . The lower limit of the permittivity is not particularly limited and may be 0.01 or 0.1. In general, the permittivity decreases as the thickness increases, but the present application may have the above permittivity range even though the thickness of the thin film is 20 μm or less. The lower limit of the thickness may be, for example, 1 μm or 3 μm, and the encapsulant composition of the present application may have the dielectric constant range of the present application even when cured within the thickness range of the lower limit. After curing, the sealing material composition of the present application may be adjusted to a low permittivity within the above range.

In one example, the epoxy compound may be at least monofunctional or bifunctional. That is, one or two or more epoxy functional groups may be present in the compound, and the upper limit is not particularly limited, but may be 10 or less. In one example, the aforementioned monofunctional epoxy compound among the epoxy compounds may be monofunctional, the linear or branched polyfunctional aliphatic compound may be difunctional or more functional, and the alicyclic compound may be monofunctional or bifunctional. In the present specification, the linear or branched multifunctional aliphatic compound is distinguished from the alicyclic compound in that it does not have an alicyclic structure in its molecular structure. The epoxy compound implements an appropriate degree of crosslinking in the ink composition to realize excellent heat resistance and durability at high temperature and high humidity.

In an embodiment of the present application, the epoxy compound may further include an alicyclic compound and/or a linear or branched polyfunctional aliphatic compound. That is, the sealing material composition of the present application may further include, or may include together, at least one of an alicyclic compound and a linear or branched polyfunctional aliphatic compound as an epoxy compound. In one example, the alicyclic compound may have 3 to 10, 4 to 8, or 5 to 7 ring atoms in the molecular structure, and 1 or more, 2 or more, and 10 or less cyclic structures may exist in the compound. When the alicyclic compound and the linear or branched polyfunctional aliphatic compound are included together, the linear or branched aliphatic compound is present in an amount of 15 parts by weight or more, less than 205 parts by weight, or 20 parts by weight based on 100 parts by weight of the alicyclic compound. More 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 may be included in the sealing material composition. In the present application, by controlling the content range, the sealing material composition can prevent device damage in sealing the entire organic electronic device, have appropriate physical properties capable of inkjet, have excellent curing strength after curing, and also have excellent Moisture barrier properties can be realized together.

In one example, the epoxy compound of the present application 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 oxetane compound and / or the epoxy compound has 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, 330 to 780 g / mol, 350 to 495 g /mol can be in the range. In the present application, by controlling the epoxy equivalent of the epoxy compound to a low level or the weight average molecular weight of the compound to a low level, the degree of completion of curing after curing of the sealing material is improved while preventing the viscosity of the composition from becoming too high to make the inkjet process impossible. It can provide moisture barrier properties and excellent curing sensitivity at the same time. In the present specification, the weight average molecular weight means a value in terms of standard polystyrene measured by GPC (Gel Permeation Chromatograph). In one example, a metal tube column 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 polystyrene beads. When a diluted solution of a substance to be measured in THF solvent is passed through a column, the weight average molecular weight can be measured indirectly according to the evacuation time. It can be detected by plotting the amount separated by size from the column by time. In addition, the epoxy equivalent in this specification is the number of grams (g/eq) of a resin containing an epoxy group of 1 gram equivalent, and can be measured according to the method specified in JIS K 7236.

In the specific example of the present application, the oxetane compound is 40 to 155 parts by weight, 42 to 150 parts by weight, 45 parts by weight to 145 parts by weight, 48 parts by weight to 144 parts by weight, 63 parts by weight based on 100 parts by weight of the epoxy compound part to 143 parts by weight or 68 parts by weight to 142 parts by weight. The term "parts by weight" in this specification may mean a weight ratio between each component. In the present application, an organic layer can be formed on an organic electronic device by an inkjet method by controlling the content ratio of the composition, the applied sealant composition has excellent spreadability in a short time, and an organic layer having excellent curing strength after curing. can provide

In one example, the boiling point of the oxetane compound may be within 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 controlling the boiling point of the compound within the above range, thereby achieving excellent printability even at high temperatures in an inkjet process, excellent water barrier properties from the outside, and suppressing outgas to prevent damage to the device. of can be provided. In this specification, the boiling point may be measured at 1 atm unless otherwise specified.

In the specific examples of the present application, the types of the above-mentioned epoxy compound and oxetane compound are not particularly limited.

In one example, the cycloaliphatic epoxy compound 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 addition, the linear or branched polyfunctional aliphatic epoxy compound is 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 or neopentylglycol diglycidyl ether It may include, but is not limited thereto.

In one example, the structure of the oxetane compound is not limited as long as it has the functional group, for example, TOAGOSEI's OXT-221, CHOX, OX-SC, OXT101, OXT121, or OXT212, or ETERNACOLL's EHO, OXBP, OXTP or OXMA may be exemplified.

In addition, in one example, the linear monofunctional compound having 7 or more carbon atoms is 1,2-epoxyoctane, 1,2-epoxydecane, 1,2-epoxydodecane, 1,2-epoxytetradecane, 1,2-epoxy-9-decene, 1,2-epoxyeicosane, 1,2-epoxyhexadecane or 1,2-epoxyoctadecane may be included, but is not limited thereto.

In an embodiment of the present application, the sealant composition may further include a surfactant. In one example, the surfactant may include a polar functional group, and the polar functional group may be present at the terminal 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 the specific embodiment of the present application, the surfactant may be a non-silicone-based surfactant or a fluorine-based surfactant. The non-silicone-based surfactant or fluorine-based surfactant is applied together with the above-described epoxy compound and oxetane compound to provide excellent coating properties on organic electronic devices. On the other hand, in the case of a surfactant containing a polar reactive group, since it has a high affinity with other components of the above-described sealant composition, it is possible to realize an excellent effect in terms of adhesion. In an embodiment of the present application, a hydrophilic fluorine-based surfactant or a non-silicone-based surfactant may be used to improve inkjet coating properties on a substrate.

Specifically, the surfactant may be a polymeric or oligomeric fluorochemical surfactant. Commercially available surfactants may be used, for example, Glide 100, Glide110, Glide 130, Glide 460, Glide 440, Glide450 or RAD2500 from TEGO, Megaface F-251, F-281 from DIC (DaiNippon Ink & Chemicals), F-552, F554, F-560, F-561, F-562, F-563, F-565, F-568, F-570 and F-571 or Asahi Glass Surflon S-111, S-112 , S-113, S-121, S-131, S-132, S-141 and S-145 or Sumitomo 3M'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, BYK-356, BYK-358N, BYK from BYK -359, BYK-361N, BYK-381, BYK-388, BYK-392, BYK-394, BYK-399, BYK-3440, BYK-3441, BYKETOL-AQ, selected from the group consisting of BYK-DYNWET 800, etc. that can be used

The surfactant is 0.1 part by weight to 10 parts by weight, 0.05 parts by weight to 10 parts by weight, 0.1 parts by weight to 10 parts by weight, 0.5 parts by weight to 8 parts by weight, or 1 to 4 parts by weight based on 100 parts by weight of the epoxy compound. can be included Within the above content range, the present application allows the sealant composition to be applied in an inkjet method to form a thin organic layer.

In the specific example of the present application, the sealant composition may further include a photosensitizer to compensate for curability in long-wavelength active energy rays of 300 nm or more. The photosensitizer may be a compound that absorbs wavelengths ranging from 200 nm to 400 nm, 250 nm to 400 nm, 300 nm to 400 nm, or 350 nm to 395 nm.

The photosensitizer may include anthracene-based 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-based compounds such as 9-fluorenone, 2-chloro-9-fluorenone, 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-based compounds; xanthone-based compounds such as xanthone and 2-methylxanthone; anthraquinone compounds such as anthraquinone, 2-methyl anthraquinone, 2-ethyl anthraquinone, t-butyl anthraquinone, and 2,6-dichloro-9,10-anthraquinone; 9-phenylacridine, 1,7-bis(9-acridinyl)heptane, 1,5-bis(9-acridinylpentane), 1,3-bis(9-acridinyl)propane, etc. acridine-based compounds; dicarbonyl compounds such as benzyl, 1,7,7-trimethyl-bicyclo[2,2,1]heptane-2,3-dione, and 9,10-phenanthrenequinone; phosphine oxide compounds such as 2,4,6-trimethylbenzoyl diphenylphosphine oxide and bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentyl phosphine oxide; benzoate compounds such as methyl-4-(dimethylamino)benzoate, ethyl-4-(dimethylamino)benzoate, and 2-n-butoxyethyl-4-(dimethylamino)benzoate; 2,5-bis(4-diethylaminobenzal)cyclopentanone, 2,6-bis(4-diethylaminobenzal)cyclohexanone, 2,6-bis(4-diethylaminobenzal)-4- amino synergists such as methyl-cyclopentanone; 3,3-carbonylvinyl-7-(diethylamino)coumarin, 3-(2-benzothiazolyl)-7-(diethylamino)coumarin, 3-benzoyl-7-(diethylamino)coumarin, 3 -benzoyl-7-methoxy-coumarin, 10,10-carbonylbis[1,1,7,7-tetramethyl-2,3,6,7-tetrahydro-1H,5H,11H-C1]-benzo coumarin compounds such as pyrano[6,7,8-ij]-quinolizin-11-one; chalcone compounds such as 4-diethylamino chalcone and 4-azidbenzalacetophenone; 2-benzoylmethylene; and 3-methyl-b-naphthothiazoline.

The photosensitizer may be included in the range of 28 parts by weight to 40 parts by weight, 31 parts by weight to 38 parts by weight, or 32 parts by weight to 36 parts by weight based on 100 parts by weight of the photoinitiator. In the present application, by adjusting the content of the photosensitizer, it is possible to prevent the photosensitizer from dissolving in the inkjet coating and thus deteriorating adhesion while realizing an increase in curing sensitivity at a desired wavelength.

The sealing material composition of the present application may further include a coupling agent. This application can improve the adhesiveness of the cured product of the sealing material composition with the adherend or the resistance to 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.

In the specific examples of the present application, as the silane coupling agent, specifically, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropyl (dimethyl epoxy-based silane coupling agents such as oxy)methylsilane and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane; mercapto-type 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 silane coupling agents such as N-(2-aminoethyl)-3-aminopropyltrimethoxysilane and N-(2-aminoethyl)-3-aminopropyldimethoxymethylsilane; vinyl silane coupling agents such as ureid-based silane coupling agents such as 3-ureidpropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, and vinylmethyldiethoxysilane; styryl silane coupling agents such as p-styryltrimethoxysilane; acrylate-based silane coupling agents such as 3-acryloxypropyltrimethoxysilane and 3-methacryloxypropyltrimethoxysilane; sulfide-based silane coupling agents such as isocyanate-based silane coupling agents such as 3-isocyanate propyltrimethoxysilane, bis(triethoxysilylpropyl) disulfide, and 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 part by weight to 10 parts by weight or 0.5 parts by weight to 5 parts by weight based on 100 parts by weight of the epoxy compound. Within the above range, the present application may implement an effect of improving adhesion by adding a coupling agent.

In one example, the sealant composition may further include an inorganic filler, if necessary. The specific type of filler that can be used in the present application is not particularly limited, and for example, one or a mixture of two or more types of clay, talc, alumina, calcium carbonate, or silica 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 epoxy compound. there is. In the present application, an inorganic filler may be preferably controlled to 1 part by weight or more, thereby providing an encapsulation structure having excellent moisture or moisture barrier properties and mechanical properties. In addition, by controlling the inorganic filler content to 50 parts by weight or less, the present invention can provide a cured product that exhibits excellent moisture barrier properties even when formed as a thin film.

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

The specific type of moisture adsorbent that can be used in the present application is not particularly limited. For example, in the case of a chemically reactive adsorbent, one kind or a mixture of two or more kinds of metal oxides, metal salts, or phosphorus pentoxide (P ₂ O ₅ ) may be mentioned. In the case of the physical adsorbent, zeolite, zirconia, or montmorillonite may be used.

The sealing material composition of the present application includes 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, based on 100 parts by weight of the epoxy compound. Or it may be included in an amount of 14 to 23 parts by weight. In the sealant composition of the present application, the content of the moisture adsorbent is preferably controlled to 5 parts by weight or more, so that the sealant composition or a cured product thereof exhibits excellent moisture and moisture barrier properties. In addition, in the present application, by controlling the content of the moisture adsorbent to 150 parts by weight or less, it is possible to provide an encapsulation structure of a thin film while having inkjet-capable physical properties in combination with the above-described composition.

In addition, the moisture adsorbent has an average particle diameter of 10 to 15000 nm, 30 nm to 10000 nm, 50 nm to 8000 nm, 80 nm to 5 μm, 90 nm to 3 μm, 95 nm to 980 nm or 98 nm to 495 nm. It can be. In the present specification, the particle size may be measured by a known method using a D50 particle size analyzer. The moisture adsorbent having a size within the above range can effectively block moisture infiltrating from the outside by appropriately controlling the reaction rate with moisture, and also realizes excellent processability by preventing aggregation of the adsorbent in inkjetting.

As described above, the sealant composition of the present application may be an ink composition applied to an inkjet process. However, controlling the viscosity of an ink composition in an inkjet process and implementing a composition having physical properties capable of inkjetting through the control may correspond to a very detailed task. However, since the above-mentioned moisture adsorbent is included in the composition in the form of particles, for example, the adsorbent aggregates or has poor dispersibility in the composition, causing clogged nozzles or inability to perform uniform inkjetting in the inkjetting process. do. However, the present application can smoothly perform the inkjetting process even when the moisture adsorbent is included by providing the sealant composition having the above-described specific composition.

The sealing material composition according to the present application may include various additives in addition to the above-described components within a range that does not affect the effects of the above-described invention. For example, the sealant composition may include an antifoaming agent, a tackifier, a UV stabilizer, or an antioxidant in an appropriate range according to desired physical properties.

In one example, the sealant composition may be liquid at room temperature, for example, 25°C. In the specific example of the present application, the sealant composition may be in the form of a solvent-free liquid. The sealant composition may be applied to encapsulate an organic electronic device, and specifically, may be applied to encapsulate the entire surface of an organic electronic device. The sealant composition of the present application may have a specific composition and physical properties to enable inkjetting.

In one example, the sealant composition of the present application 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, but may be 1° or 3° or more. In the present application, by adjusting the contact angle to 15° 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 glass using a sessile drop measuring method, and may be measured by measuring an average value after applying 5 times.

In addition, the sealant composition of the present application may be an ink composition. The sealant composition of the present application may be an ink composition capable of an inkjetting process. The sealant composition of the present application may have a specific composition and physical properties to enable inkjetting.

In addition, in an embodiment of the present application, the sealing material composition has a viscosity of 50 cPs or less, 1 to 46 cPs, or 5 to 46 cPs, as measured by Brookfield's DV-3, at a temperature of 25 ° C., a torque of 90%, and a shear rate of 100 rpm. It can 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 realize physical properties capable of inkjetting at the time of application to an organic electronic device, and also 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 mN/m after curing. It can be within the range of mN/m. The surface energy can be measured by a known method in the art, for example, by the Ring Method. The present application can implement excellent coating properties within the above surface energy range.

In an embodiment of the present application, surface energy (γ ^surface , mN/m) can be calculated as γ ^surface = γ ^dispersion + γ ^polar . In one example, surface energy can be measured using a drop shape analyzer (DSA100 product of KRUSS). For example, the surface energy is measured by applying an encapsulant 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 an encapsulation film (spin coater), nitrogen After drying for about 10 minutes at room temperature in an atmosphere, UV curing is performed with an intensity of 1000 mW/cm ² and a light amount of 4000 mJ/cm ² . After curing, the process of dropping deionized water having a known surface tension on the film and obtaining the contact angle was repeated 5 times, and the average value of the obtained 5 contact angle values was obtained. Similarly, the surface tension was known. The process of dropping diiodomethane and obtaining the contact angle is repeated 5 times, and the average value of the obtained 5 contact angle values is obtained. Then, the surface energy can be obtained by substituting the surface tension value (Strom value) of the solvent by the Owens-Wendt-Rabel-Kaelble method using the average value of the contact angles for deionized water and diiodomethane.

In one example, the amount of volatile organic compounds measured after curing of the sealing material composition of the present application may be less than 50 ppm. In the present specification, the volatile organic compound may be referred to as outgas. The volatile organic compound may be measured after curing the sealant composition and maintaining the 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) device.

This application also relates to an organic electronic device. As shown in FIG. 1, the exemplary organic electronic device 3 includes a substrate 31; an organic electronic device 32 formed on the substrate 31; and an organic layer 33 sealing the front surface of the organic electronic device 32 and including the above-described sealing material composition.

In the 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 a light emitting 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 this application, the organic electronic device 32 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 protecting the electrode and the light emitting layer of the device. The protective layer 35 may be an inorganic protective layer. The protective film may be a protective layer by chemical vapor deposition (CVD), and its material may be the same as or different from the inorganic layer described below, and a known inorganic material may be used. For example, the passivation layer may use silicon nitride (SiNx). 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 aforementioned passivation layer. In addition, the inorganic layer 34 may be formed in the same way as the protective layer 35 . 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 inorganic layer may have a thickness of 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 with a dopant. The dopant that may 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 within a range of 20 μm or less, 2 μm to 20 μm, 2.5 μm to 15 μm, and 2.8 μm to 9 μm. The present application can 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 layer, , the organic layer and the inorganic layer may be repeatedly laminated. For example, the organic electronic device may have a structure of substrate/organic electronic device/protective layer/(organic layer/inorganic layer)n, and n may be a number in the range of 1 to 100. 1 is a cross-sectional view exemplarily showing 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 materials known in the art may be used. For example, the substrate or cover substrate may be a glass, metal substrate or polymer film. Polymer films include, for example, polyethylene terephthalate film, polytetrafluoroethylene film, polyethylene film, polypropylene film, polybutene film, polybutadiene film, vinyl chloride copolymer film, polyurethane film, ethylene-vinyl acetate film, ethylene - A propylene copolymer film, an ethylene-ethyl acrylate copolymer film, an ethylene-methyl acrylate copolymer film, or a polyimide film may be used.

In addition, the organic electronic device 3 of the present application, as shown in FIG. 2, the encapsulation film 37 present between the cover substrate 38 and the substrate 31 on which the organic electronic element 32 is formed may additionally be included. 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 is, for example, an adhesive film that is solid at room temperature in an uncured state. Or it may be an adhesive film, but is not limited thereto. The encapsulation film 37 may seal the entire surface of the encapsulation structure 36 of the organic layer and the inorganic layer stacked on the organic electronic device 32 .

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

In one example, the manufacturing method includes forming an organic layer 33 on the substrate 31 on which the organic electronic device 32 is formed so that the above-described sealant composition seals the front surface of the organic electronic device 32. can 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 the substrate 31 such as glass or polymer film by a method such as vacuum deposition or sputtering, and the It may 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, a light emitting 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 a protective film 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 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-described sealant composition is applied to the entire surface of the substrate 31 by inkjet printing, gravure coating, spin coating, screen printing, or reverse offset printing. A process such as coating (reverse offset) may be used.

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

In one example, after forming the front organic layer by applying the above-described sealant composition, crosslinking may be induced by irradiating the composition with light. Irradiating the light may include irradiating light having a wavelength range of 250 nm to 450 nm or 300 nm to 450 nm with an amount of light of 0.3 to 6 J/cm ² or an amount of light of 0.5 to 5 J/cm ² .

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

The present application effectively blocks moisture or oxygen flowing into the organic electronic device from the outside to secure the lifespan of the organic electronic device, realizes a front-emitting organic electronic device, is applicable in an inkjet method, and is thin. A sealant composition capable of providing a display and effectively preventing electromagnetic field interference due to its low permittivity and an organic electronic device including the same are provided.

1 and 2 are cross-sectional views showing an organic electronic device according to one 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 1

As an epoxy compound at room temperature, an alicyclic epoxy compound (Daicel Co., Ltd. Celloxide 2021P), an aliphatic multifunctional epoxy compound (HAJIN CHEM TECH Co., Ltd., DE203) and a monofunctional epoxy compound (1,2-Epoxydecane), an oxetane compound (TOAGOSEI OXT- 101), a photoinitiator containing a sulfonium salt (CPI-310B from San-Apro) and a fluorine-based surfactant (F552 from DIC) at 20:7.5:15:50:1.5:1.0 (Celloxide2021P: DE203: 1,2-Epoxydecane) : OXT-101: CPI-310B: F552) was added to the mixing container in a weight ratio.

A uniform sealant composition was prepared using the mixing container by 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 photoinitiator was changed to BASF's I290 as a photoinitiator containing a sulfonium salt.

Example 3

A sealing material composition was prepared in the same manner as in Example 1, except that the photoinitiator was changed to BASF's GSID26-1 as a photoinitiator containing a sulfonium salt.

Comparative Example 1

An alicyclic epoxy compound, an aliphatic multifunctional epoxy compound, a monofunctional epoxy compound, an oxetane compound, a photoinitiator and a surfactant were mixed at 10:1.5:50:31:1.5:1.0 (Celloxide2021P: DE203: 1,2-Epoxydecane: OXT- 101: CPI-310B: F552) was added to the mixing container in the weight ratio, but the sealing material composition was prepared in the same manner as in Example 1.

Comparative Example 2

An alicyclic epoxy compound, an aliphatic multifunctional epoxy compound, a monofunctional epoxy compound, an oxetane compound, a photoinitiator and a surfactant were mixed at 25:7.5:10:50:1.5:1.0 (Celloxide2021P: DE203: 1,2-Epoxydecane: OXT- 101: CPI-310B: F552) was added to the mixing container in the weight ratio, but the sealing material composition was prepared in the same manner as in Example 1.

Comparative Example 3

An alicyclic epoxy compound, an aliphatic multifunctional epoxy compound, a monofunctional epoxy compound, an oxetane compound, a photoinitiator and a surfactant were mixed at 25:18:0:49.5:1.5:1.0 (Celloxide2021P: DE203: 1,2-Epoxydecane: OXT- 101: CPI-310B: F552) was added to the mixing container in the weight ratio, but the sealing material composition was prepared in the same manner as in Example 1.

Comparative Example 4

A sealing material composition was prepared in the same manner as in Example 1, except that the monofunctional epoxy compound was changed to 1,2-Epoxybutane.

Comparative Example 5

A sealing material composition was prepared in the same manner as in Example 1, except that the monofunctional epoxy compound was changed to O-cresyl glycidyl ether.

Comparative Example 6

A sealing material composition was prepared in the same manner as in Example 1, except that the monofunctional epoxy compound was changed to 2-ethylhexyl ether.

Comparative Example 7

A sealing material composition was prepared in the same manner as in Example 1, except that the photoinitiator was changed to TOKYO CHEMICAL INDUSTRY (TCI)'s WPI170 as a photoinitiator containing an iodonium salt.

Comparative Example 8

A sealing material composition was prepared in the same manner as in Example 1, except that the photoinitiator was changed to TETRACHEM's UV692 as a photoinitiator containing an iodonium salt.

Comparative Example 9

A sealing material composition was prepared in the same manner as in Example 1, except that the photoinitiator was changed to BASF's Irgacure PAG 103 as a nonionic photoinitiator.

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

1. Contact angle measurement (spreadability)

For the sealing material compositions prepared in Examples and Comparative Examples, contact angles with respect to glass were measured at 25°C. After injecting the sealing material composition into a syringe and dropping one drop in a volume of 5 μl, it is measured by taking a picture with a CCD camera. The average value of 5 times was used, and the equipment used was KRUSS's DSA100. When the adhesion angle was less than 10 °, spreadability was excellent, and when the contact angle was 10 ° to 30 °, it was classified as △, and when the contact angle exceeded 30 °, it was classified as X.

2. Organic Layer Thickness

When inkjetting the sealing material compositions prepared in Examples and Comparative Examples, when an organic layer is formed with a thickness of 20 μm or less, it can be judged to be good (O), and when an organic layer is formed with a thickness of 40 μm or less, normal (Δ) , When the organic layer is formed with a thickness of 60 μm or less, it is classified as defective (X). As shown in Table 1 below, in the case of Comparative Example 2, it was practically impossible to form an organic layer of a thin film of 20 μm or less.

3. Curing Sensitivity Measurement

The sealing material compositions prepared in Examples and Comparative Examples were irradiated with UV at an intensity of 1000 mW/cm ² and 1 J/cm ² , and then the tack free time of the adhesive was measured. First, the sealant composition is applied by spin coating to a thickness of 10 μm and cured. When the surface of the sealing material is touched immediately after curing, the time until the tacky feeling disappears and there is no bleeding of the sealing material is defined as the tack free time and measured. When the tack free time was less than 1 second, it was classified as ◎, when it was less than 1 minute, it was classified as O, when it was 5 minutes or more, △, and when it was 30 minutes or more, it was classified as X.

4. Measurement of permittivity

An Al plate (conductive plate) was deposited at 500 Å on the cleaned bare glass. Inkjet coating the sealant composition prepared in Example and Comparative Example on the surface of the deposited Al plate, and curing the coated composition with an amount of light of 1000 mJ/cm ² through an LED UV lamp to form an organic layer having a thickness of 8 μm. did An Al plate (conductive plate) was again deposited on the organic layer with a thickness of 500 Å.

After that, the capacitance value of the Al plate was measured at 100 kHz and 25 ° C using an impedance measuring instrument Agilent 4194A. Through the measured value, the permittivity of the organic layer was calculated using the following formula.

C = εr εo A/D (C: Capacitance of Al plate, εr: Permittivity of organic layer, εo: Permittivity in vacuum, A: Area of Al plate, D: Distance between two Al plates)

In this application, the dielectric constant is a relative value (ratio) to the dielectric constant in the vacuum when the dielectric constant in the vacuum is set to 1.

5. Outgas measurement

After curing the sealing material composition prepared in Examples and Comparative Examples by irradiating UV of 1J/cm ² at an intensity of 1000mW/cm ² , 50mg of the cured product sample was subjected to Purge & Trap-Gas Chromatography/Mass After maintaining at 110° C. for 30 minutes using an analytical method, the amount of volatile organic compounds was measured. The measurement was performed using a Purge & Trap sampler (JAI JTD-505III)-GC/MS (Agilent 7890b/5977a) instrument. When the measured amount was less than 50 ppm, it was marked with ◎, when it was less than 100 ppm, it was marked with O, and when it was over 100 ppm, it was marked with X.

6. Dark spot measurement

The sealing material composition prepared in Examples and Comparative Examples was applied on an organic electronic device having an inorganic deposition film (chemical vapor deposition film) film formed thereon. Thereafter, curing was performed by irradiating UV light at an intensity of 1000 mW/cm ² and 1 J/cm ² . After the cured organic layer was allowed to stand for 300 hours in an environment of 85° C. and 85% RH, the emission form was observed. It was classified as O when there was no dark spot caused by a foreign substance, △ when 1-2 dark spots were observed, and X when light emission was impossible due to the occurrence of 3 or more dark spots.

spreadability thickness curing sensitivity permittivity outgas dark spot Example 1 O O ◎ 2.94 ◎ O Example 2 O O ◎ 2.93 O O Example 3 O O O 2.94 O △ Comparative Example 1 O O △ 2.56 X X Comparative Example 2 △ △ O 3.09 O O Comparative Example 3 O O O 3.46 ◎ O Comparative Example 4 O O ◎ 3.43 ◎ O Comparative Example 5 O O ◎ 3.08 ◎ O Comparative Example 6 O O ◎ 3.12 ◎ O Comparative Example 7 O O O 2.97 X X Comparative Example 8 O O O 2.94 X X Comparative Example 9 O O O 2.95 X X

Comparative Examples 1 and 7 to 9 showed relatively low permittivity, but a large amount of outgas was generated and a large amount of dark spots were observed. Comparative Examples 2 to 6 had good outgas and dark spots at the level of the examples, but the permittivity was measured high. Therefore, Comparative Examples did not simultaneously satisfy the low dielectric constant characteristics, outgas requirements and dark spot suppression.

3: organic electronic device
31: substrate
32: organic electronic device
33: organic layer
34: inorganic layer
35: Shield
36: Encapsulation structure
37: sealing film
38: cover substrate

Claims (18)

An ionic photoinitiator including an epoxy compound, an oxetane compound and a sulfonium salt, wherein the epoxy compound includes a linear monofunctional compound having 7 or more carbon atoms,
The monofunctional compound is included in the range of 25 to 81 parts by weight based on 100 parts by weight of the total epoxy compound in the composition,
The oxetane compound is included in the range of 40 parts by weight to 155 parts by weight based on 100 parts by weight of the epoxy compound sealing material composition. The sealing material composition according to claim 1, which has a permittivity of 3.05 or less at 100 kHz to 400 kHz and 25° C. after curing into a thin film having a thickness of 20 μm or less. The sealant composition according to claim 1, wherein the monofunctional compound does not have a branched chain structure. The sealant composition according to claim 1, wherein the monofunctional compound does not have an ether group except for a cyclic ether group. The sealant composition according to claim 1, wherein the epoxy compound further comprises an alicyclic compound and/or a linear or branched polyfunctional aliphatic compound. [Claim 6] The sealant composition according to claim 5, wherein the alicyclic compound has 3 to 10 ring atoms in its molecular structure. The sealing material composition according to claim 5, wherein the linear or branched polyfunctional aliphatic compound is included in an amount of 15 parts by weight or more and less than 205 parts by weight based on 100 parts by weight of the alicyclic compound. delete The sealing material composition according to claim 1, wherein the epoxy compound or the oxetane compound has a weight average molecular weight in the range of 150 to 1,000 g/mol. The sealing material composition of claim 1, 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. The sealant composition according to claim 1, further comprising a surfactant. The sealant composition according to claim 11, wherein the surfactant contains a polar functional group. The sealing material composition according to claim 11, wherein the surfactant is included in an amount of 0.01 part by weight to 10 parts by weight based on 100 parts by weight of the epoxy compound. The sealant composition according to claim 1, which is a solvent-free ink composition. Board; organic electronic devices formed on the substrate; and an organic layer sealing the front surface of the organic electronic device and including the sealant composition according to claim 1 . 16. The organic electronic device according to claim 15, wherein the organic layer has a thickness of 20 [mu]m or less. A method of manufacturing an organic electronic device, comprising forming an organic layer on a substrate on which an organic electronic device is formed, so that the sealant composition of claim 1 seals the entire surface of the organic electronic device. 18. The method of claim 17, wherein the forming of the organic layer comprises inkjet printing, gravure coating, spin coating, screen printing, or reverse offset coating.

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