阅读说明：本技术 封装组合物 (Packaging composition ) 是由 崔国铉 金俊衡 禹儒真 俞米林 于 2018-04-30 设计创作，主要内容包括：本申请涉及一种封装组合物、包含所述封装组合物的有机电子器件以及所述有机电子器件的制造方法,并且提供一种能有效阻挡湿气或氧气从外部引入到有机电子器件中以确保有机电子器件的寿命并在分配和储存时具有优异的储存稳定性的封装组合物。(The present invention relates to an encapsulation composition, an organic electronic device including the same, and a method of manufacturing the organic electronic device, and provides an encapsulation composition that can effectively block moisture or oxygen introduced into an organic electronic device from the outside to ensure the lifespan of the organic electronic device and has excellent storage stability upon distribution and storage.)

1. An encapsulating composition for encapsulating an organic electronic element, the encapsulating composition being a solvent-free photocurable encapsulating composition and comprising a curable compound, a photoinitiator containing a sulfonium salt, a photosensitizer, and a heat stabilizer,

Wherein the curable compound, the photoinitiator, the photosensitizer, and the thermal stabilizer are included in weight ratios 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.

2. An encapsulating composition for sealing an organic electronic element according to claim 1, wherein the curable compound comprises at least one curable functional group.

3. The encapsulating composition for sealing an organic electronic element according to claim 2, wherein the curable functional group is one or more selected from a glycidyl group, an oxetanyl group, an isocyanate group, a hydroxyl group, a carboxyl group, an amide group, an epoxy group, a sulfide group, an acetal group and a lactone group.

4. An encapsulating composition for sealing an organic electronic component according to claim 2, wherein the curable compound has at least bifunctionality.

5. An encapsulating composition for sealing an organic electronic element according to claim 1, wherein the curable compound comprises an epoxy compound; and a compound having an oxetanyl group.

6. The encapsulating composition for sealing an organic electronic element 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.

7. The encapsulating composition for sealing an organic electronic element according to claim 5, wherein the content of the compound having an oxetanyl group is 45 to 145 parts by weight with respect to 100 parts by weight of the epoxy compound.

8. The encapsulating composition for sealing an organic electronic element according to claim 6, wherein the content of the linear or branched aliphatic compound is 20 parts by weight or more and less than 205 parts by weight with respect to 100 parts by weight of the compound having a cyclic structure.

9. An encapsulating composition for sealing an organic electronic element according to claim 1, wherein the photoinitiator comprises a cationic photopolymerization initiator.

10. The encapsulating composition for sealing an organic electronic element according to claim 1, wherein the photoinitiator comprising a sulfonium salt has at least one cyclic structure in a molecular structure.

11. The encapsulating composition for sealing an organic electronic element according to claim 1, wherein the photosensitizer is a substance that absorbs a wavelength in a range of 200nm to 400 nm.

12. The encapsulation composition for sealing an organic electronic element according to claim 1, wherein the thermal stabilizer comprises 2, 6-di-tert-butyl-p-cresol, Phenothiazine (PTZ), methylene quinone, 2-dimethylaminomethanol or monomethyl ether hydroquinone.

13. The encapsulation composition for sealing an organic electronic element according to claim 1, wherein a content ratio of the photosensitizer to the photoinitiator is in a range of 0.1 to 0.8.

14. The encapsulating composition for sealing an organic electronic element according to claim 1, further comprising a surfactant.

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

16. a method for manufacturing an organic electronic device, comprising the step of forming an organic layer on a substrate having an organic electronic element formed thereon so that the encapsulating composition according to claim 1 seals the entire surface of the organic electronic element.

Technical Field

Cross Reference to Related Applications

The present application is based on the benefit of priority claim of korean patent application No.10-2017-0055101 filed on 28.4.2017, the disclosure of which is incorporated in its entirety by reference into the present specification.

Background

Organic Electronic Devices (OEDs) refer to devices including an organic material layer of alternating current that generates charges using holes and electrons, and examples thereof may include photovoltaic devices, rectifiers, emitters, Organic Light Emitting Diodes (OLEDs), and the like.

Organic Light Emitting Diodes (OLEDs) in organic electronic devices have lower power consumption and faster response speed than conventional light sources and are advantageous for thinning display devices or light emitters. In addition, the OLED has excellent space utilization, and thus is expected to be applied in various fields including various portable devices, displays, notebook computers, and televisions.

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

Disclosure of Invention

Technical problem

The present application provides an encapsulation composition that can effectively block moisture or oxygen from being introduced into an organic electronic device from the outside to ensure the lifespan of the organic electronic device and has excellent storage stability upon distribution and storage.

Technical scheme

The present application relates to an encapsulating composition. The encapsulating composition may be an encapsulating material for encapsulating or encapsulating organic electronic devices such as OLEDs. In one example, the encapsulation composition of the present application is used to seal or encapsulate the entire surface of an organic electronic component. Thus, after the encapsulating composition is used for encapsulation, it may be present in the form of an organic layer that encapsulates the entire surface of the organic electronic component. Further, the organic layer may be alternately laminated on the organic electronic element together with an inorganic protective layer and/or an inorganic layer described below to form a sealing structure.

In one embodiment of the present application, the present application relates to an encapsulation composition for sealing organic electronic components that can be used in inkjet processes, wherein the composition can be designed to have appropriate physical properties when discharged onto a substrate using inkjet printing capable of non-contact patterning, and a method for preparing the same.

In the present specification, the term "organic electronic device" refers to an article or a device having a structure including an organic material layer that generates an alternating current of electric charges between a pair of electrodes facing each other using holes and electrons, and examples thereof may include a photovoltaic device, a rectifier, an emitter, an Organic Light Emitting Diode (OLED), and the like, but are not limited thereto. In one example of the present application, the organic electronic device may be an OLED.

An exemplary encapsulation composition is a solvent-free photocurable encapsulation composition that may include a curable compound, a photoinitiator, a photosensitizer, and a thermal stabilizer. The curable compound, the photoinitiator, the photosensitizer, and the thermal stabilizer may be included in the composition in weight ratios 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, and in another example, may be included in weight ratios of 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, respectively; 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; or an amount of 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 is included in the composition. By controlling the specific components to the limited content ranges, the present application can suppress side reactions in the dispensing and storage steps before applying the encapsulating composition to the organic electronic element, and can maintain the viscosity desired in the present specification, thereby maintaining the storage stability as an ink-jettable composition.

In one embodiment of the present application, the curable compound may comprise at least one curable functional group. The curable functional group may be, for example, one or more selected from an oxetane group, a glycidyl group, an isocyanate group, a hydroxyl group, a carboxyl group, an amide group, an epoxy group, a sulfide group, an acetal group, and a lactone group. The curable functional groups may have at least mono-functionality or di-functionality or higher functionality. By using the curable compound, the present application can achieve excellent endurance reliability, adhesive property, and moisture barrier property.

Exemplary curable compounds may include epoxy compounds and compounds having an oxetanyl group. In one embodiment of the present application, the content of the compound having an oxetanyl group may be in the range of 45 parts by weight to 145 parts by weight with respect to 100 parts by weight of the epoxy compound. The content of the compound having an oxetanyl group may be 45 to 145 parts by weight, 48 to 144 parts by weight, 63 to 143 parts by weight, or 68 to 142 parts by weight with respect to 100 parts by weight of the epoxy compound. In the present specification, the term "parts by weight" may refer to a weight ratio between the respective components. By controlling the specific components and the content ranges thereof, the present application is able to form an organic layer on an organic electronic element by an inkjet method, and provide an organic layer in which an applied encapsulation composition has excellent ductility in a short time and excellent hardening strength after curing. In addition, a specific content of the curable compound can achieve excellent storage stability, specifically, together with the above-mentioned photoinitiator, photosensitizer and heat stabilizer.

In one example, the encapsulation composition of the present application can have a contact angle with 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. By adjusting the contact angle to 30 ° or less, the present application can secure ductility in a short time in inkjet coating, thereby forming a thin organic layer. In the present application, the contact angle may be measured by applying a droplet of the encapsulation composition onto the glass using a sessile drop measurement method, which may be an average value measured after 5 applications.

In one example, the curable compound including the epoxy compound and the compound having an oxetanyl group may be contained in an amount of 70% by weight or more, 75% by weight or more, 80% by weight or more, 85% by weight or more, or 89% by weight or more in the entire components of the encapsulating 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 have at least monofunctional functionality. That is, one or more, or two or more epoxy functional groups may be present in the compound, wherein the upper limit is not particularly limited, but may be 10 or less. The epoxy compound achieves excellent heat resistance and durability under high temperature and high humidity by achieving an appropriate degree of crosslinking with the adhesive.

In one embodiment of the present application, the epoxy compound may include a compound having a cyclic structure in a molecular structure and/or a linear or branched aliphatic compound. That is, the encapsulating composition of the present application may contain at least one of a compound having a cyclic structure and a linear or branched aliphatic compound in a molecular structure as an epoxy compound, and may contain them together. In one example, the compound having a cyclic structure in a molecular structure may have ring-forming atoms in the range of 3 to 10, 4 to 8, or 5 to 7 in the molecular structure, and one or more, two or more, 10 or less cyclic structures may be present in the compound. When the compound having a cyclic structure and the linear or branched aliphatic compound are included together, the content of the linear or branched aliphatic compound in the encapsulation composition may be in a range of 20 parts by weight or more, less than 205 parts by weight, or 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, relative to 100 parts by weight of the compound having a cyclic structure. By controlling the content range, the present application can provide the encapsulation composition with appropriate physical properties when sealing the organic electronic element, excellent curing strength after curing, and excellent moisture barrier properties.

In one example, the epoxy equivalent of the epoxy compound may be in a range of 50 to 350g/eq, 73 to 332g/eq, 94 to 318g/eq, or 123 to 298 g/eq. Also, the weight average molecular weight of the compound having an oxetanyl group may be in the range of 150g/mol to 1,000g/mol, 173g/mol to 980g/mol, 188g/mol to 860g/mol, 210g/mol to 823g/mol, or 330g/mol to 780 g/mol. By controlling the epoxy equivalent of the epoxy compound to be low or the weight average molecular weight of the compound having an oxetanyl group to be low, the present application can prevent the viscosity of the composition from becoming too high to perform the inkjet process, while improving the degree of completion of curing after curing of the encapsulating composition, and while providing moisture barrier properties and excellent curing sensitivity. In the present specification, the weight average molecular weight refers to a value converted into standard polystyrene as measured by GPC (gel permeation chromatography). In one example, a chromatography column made of metal tubing having a length of 250mm to 300mm and an inner diameter of 4.5mm to 7.5mm is packed with 3mm to 20mm polystyrene beads. When a solution diluted by dissolving the substance to be measured in a THF solvent was passed through a chromatography column, the weight average molecular weight was indirectly measured in terms of flow time. Monitoring was done by plotting the amount separated from the column by size each time. In the present specification, the epoxy equivalent is also the number of grams (g/eq) of a resin containing 1 gram equivalent of epoxy groups, which can be measured according to the method defined in JIS K7236.

The boiling point of the compound having an oxetanyl group may be in the range of 90 ℃ to 300 ℃, 98 ℃ to 270 ℃, 110 ℃ to 258 ℃ or 138 ℃ to 237 ℃. By controlling the boiling point of the compound to the above range, the present application can provide a sealing material having excellent external moisture barrier properties while achieving excellent printability even at high temperatures in an inkjet process, and preventing damage applied to elements due to suppression of outgassing. In this specification, unless otherwise specified, the boiling point may be measured at 1 atmosphere.

In one example, the compound having a cyclic structure in a molecular structure is exemplified by 3, 4-epoxycyclohexylmethyl 3 ', 4' -epoxycyclohexane carboxylate (EEC) and derivatives, dicyclopentadiene dioxide and derivatives, vinylcyclohexene dioxide and derivatives, or 1, 4-cyclohexanedimethanol bis (3, 4-epoxycyclohexane carboxylate) and derivatives, but is not limited thereto.

In one example, as long as the oxetanyl group-containing compound has the functional group, the structure thereof is not limited, and for example, it can be exemplified by OXT-221, CHOX, OX-SC, OXT101, OXT121, OXT221 or OXT212 from TOAGOSEI, or EHO, OXBP, OXTP or OXMA from ETERNACOLL. Also, the linear or branched aliphatic epoxy compound may include 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 neopentyl glycol diglycidyl ether, but is not limited thereto.

In one embodiment of the present application, the encapsulating composition may further comprise a photoinitiator. The photoinitiator may be a cationic photopolymerization initiator.

As the cationic photopolymerization initiator, those known in the art, for example, those having a cationic moiety comprising an aromatic sulfonium, aromatic iodonium, aromatic diazonium or aromatic ammonium ion and those comprising AsF, can be used₆ ^-、SbF₆ ^-、PF₆ ^-Or the anionic portion of tetrakis (pentafluorophenyl) borate. In addition, as a photopolymerization initiatorFor the hair agent, an onium salt or organic metal salt-based ionizing cationic initiator or an organosilane or latent sulfonic acid-based nonionic cationic photopolymerization initiator can be used. Diaryliodonium salts, triarylsulfonium salts, aryldiazonium salts, etc. can be given as examples of onium salt-based initiators, iron arenes, etc. can be given as examples of organic metal salt-based initiators, o-nitrobenzyl triarylsilyl ether, triarylsilyl peroxide, acylsilane, etc. can be given as examples of organosilane-based initiators, and α -sulfonyloxy ketone, α -hydroxymethylbenzoinsulfonate, etc. can be given as examples of latent sulfuric acid-based initiators.

In one example, a sulfonium salt may be included as a photoinitiator, taking into account the application of the present application particularly for sealing organic electronic components by an inkjet process and the fact that the curable compound is included with a photosensitizer and a thermal stabilizer. The present application can achieve superior storage stability by adjusting the content ratio between the respective components in a specific composition formula.

The photoinitiator comprising the sulfonium salt may have at least one cyclic structure in the molecular structure. The cyclic structure is a cyclic structure having ring-forming atoms in the range of 3 to 10, 4 to 8, or 5 to 7 in the molecular structure, and may be an aliphatic cyclic structure or an aromatic cyclic structure. In one embodiment of the present application, the sulfonium salt can comprise at least one aryl group, e.g., can comprise a phenyl group. The aryl group may be optionally substituted with one or more substituents, wherein the substituents may be exemplified by a halogen atom, a hydroxyl 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 methacryloyl group, an acryloyloxy group, a methacryloyloxy group, an aryl group, or an aromatic-substituted mercapto group such as a thiophenol group, etc., but is not limited thereto. In one example, the sulfonium salt may have at least one aryl group in which an aromatic-substituted mercapto group is present as a substituent. The photoinitiator may be contained 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, relative to 100 parts by weight of the total curable compounds in the composition. By including a specific photoinitiator, the long term reliability of the composition can be maintained together with a photosensitizer and a thermal stabilizer.

In one embodiment of the present application, the encapsulation composition may include a photosensitizer to supplement curing performance under a long wavelength activation energy beam of 300nm or more. The photosensitizer may be a compound that absorbs wavelengths in the range of 200nm to 400nm, 250nm to 400nm, 300nm to 400nm, 350nm to 398nm, or 375nm to 397 nm.

The photosensitizer may be one or more selected from the group consisting of: anthracene compounds such as anthracene, 9, 10-dibutoxyanthracene, 9, 10-dimethoxyanthracene, 9, 10-diethoxyanthracene, and 2-ethyl-9, 10-dimethoxyanthracene; benzophenone-based compounds such as benzophenone, 4, 4-bis (dimethylamino) benzophenone, 4, 4-bis (diethylamino) benzophenone, 2,4, 6-trimethylaminobenzophenone, methyl-o-benzoylbenzoate, 3-dimethyl-4-methoxybenzophenone, and 3,3,4, 4-tetrakis (t-butylperoxycarbonyl) benzophenone; ketone compounds such as acetophenone, dimethoxyacetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and acetone; a perylene; fluorene compounds such as 9-fluorenone, 2-chloro-9-propanone and 2-methyl-9-fluorenone; thioxanthone compounds such as thioxanthone, 2, 4-diethylthioxanthone, 2-chlorothioxanthone, 1-chloro-4-propoxythioxanthone, Isopropylthioxanthone (ITX), and diisopropylthioxanthone; xanthone compounds such as xanthone and 2-methylxanthone; anthraquinones such as anthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, tert-butylanthraquinone and 2, 6-dichloro-9, 10-anthraquinone; acridine compounds such as 9-phenylacridine, 1, 7-bis (9-acridinyl) heptane, 1, 5-bis (9-acridinylpentane), and 1, 3-bis (9-acridinyl) propane; 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-trimethylbenzoyldiphenylphosphine oxide and bis (2, 6-dimethoxybenzoyl) -2,4, 4-trimethylpentylphosphine oxide; benzoate compounds such as methyl-4- (dimethylamino) benzoate, ethyl-4- (dimethylamino) benzoate, and 2-n-butoxyethyl-4- (dimethylamino) benzoate; amino synergists such as 2, 5-bis (4-diethylaminobenzylidene) cyclopentanone, 2, 6-bis (4-diethylaminobenzylidene) cyclohexanone, and 2, 6-bis (4-diethylaminobenzylidene) -4-methyl-cyclopentanone; coumarins such as 3, 3-carbonylvinyl-7- (diethylamino) coumarin, 3- (2-benzothiazolyl) -7- (diethylamino) coumarin, 3-benzoyl-7-methoxy-coumarin, and 10, 10-carbonylbis [1,1,7, 7-tetramethyl-2, 3,6, 7-tetrahydro-1H, 5H,11H-Cl ] - [6,7,8-ij ] -quinolizin-11-one; chalcone compounds such as 4-diethylaminochalcone and 4-azidobenzylidene acetophenone; 2-benzoylmethylene; and 3-methyl-b-naphthothiazoline.

In one embodiment of the present application, the content ratio of the photosensitizer to 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. By controlling the contents of the photosensitizer and the photoinitiator, the present invention can achieve a synergistic effect of curing sensitivity at a desired wavelength, and also prevent the deterioration of reliability of the composition due to problems such as phase separation associated with the photoinitiator containing the above sulfonium salt.

As noted above, the encapsulation composition of the present application may comprise a thermal stabilizer. The heat stabilizer may be exemplified by a cresol compound, specifically, 2, 6-di-tert-butyl-p-cresol, and the like. In another example, the heat stabilizer includes a thiazine compound, a quinone compound, an amino alcohol, and the like, and specific examples thereof may include Phenothiazine (PTZ), methylene quinone, 2-dimethylaminomethanol, or monomethyl ether hydroquinone. In one embodiment of the present application, the content ratio of the thermal stabilizer to 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. The present application maintains physical properties of ink jettable property even during long-term dispensing or storage by controlling the contents of the thermal stabilizer and the photoinitiator, while preventing viscosity increase, gelation, or curing reaction due to unnecessary thermal energy in the above composition.

In one embodiment of the present application, the encapsulating composition may further comprise a surfactant. The encapsulating composition may be provided as a liquid ink having improved ductility by including a surfactant. In one example, the surfactant can include a polar functional group, and the polar functional group can be present at the terminal end of the compound structure of the surfactant. The polar functional group may include, for example, a carboxyl group, a hydroxyl group, a phosphate group, or a sulfonate group. Further, in one embodiment of the present application, the surfactant may be a non-silicone surfactant or a fluorine-based surfactant. Non-silicone based surfactants or fluorine based surfactants may be used with the above curable compounds to provide excellent coating properties on organic electronic components. On the other hand, in the case of a surfactant containing a polar reactive group, the surfactant may have high affinity with other components in the encapsulating composition, thereby achieving an excellent effect in adhesion. In one embodiment of the present application, a hydrophilic fluorine-based surfactant or a non-silicone-based surfactant may be used to improve the coating properties of the base material.

Specifically, the surfactant may be a fluorine-based surfactant of a polymer type or an oligomer type. As surfactants, commercially available products may be used, which may be selected from Glide 100, Glide 110, Glide 130, Glide460, Glide 440, Glide 450 or RAD 2500 from TEGO, MegafaceF-251, F-281, F-552, F554, F-560, F-561, F-562, F-563, F-565, F-568, F-570 and F-571 from DIC (DaiNippon Ink Chemicals), or Surflon S-111, S-112, S-113, S-121, S-131, S-132, S-141 and S-145 from Asahi Glass Co., Fluorad FC-93, FC-95, FC-98, FC-129, FC-135, FC-170C, FC-430 and FC-4430 from Sumitomo 3M Ltd, or from Duronyl-300 from Pogo, FSN, FSN-100 and FSO and BYK-350, BYK-354, BYK-355, BYK-356, BYK-358N, BYK-359, BYK-361N, BYK-381, BYK-388, BYK-392, BYK-394, BYK-399, BYK-3440, BYK-3441, BYKETOL-AQ, BYK-DYNFET 800 from BYK, etc.

The content of the surfactant may be 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 with respect to 100 parts by weight of the curable compound. Within the content range, the present application may apply the encapsulation composition to an inkjet method to form a thin film organic layer.

The encapsulation composition of the present application may also comprise a coupling agent. The present application can improve the adhesion of the cured product of the encapsulating composition to adherends or the moisture permeation resistance of the cured product. The coupling agent may include, for example, a titanium-based coupling agent, an aluminum-based coupling agent, a silane coupling agent.

In one embodiment of the present application, the silane coupling agent may specifically include: epoxy-based silane coupling agents such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyl (dimethoxy) methylsilane, and 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane; mercapto silane coupling agents such as 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, and 11-mercaptoundecyltrimethoxysilane; amine silane coupling agents such as 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldimethoxymethylsilane, N-phenyl-3-aminopropyltrimethoxysilane, N-methylaminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane and N- (2-aminoethyl) -3-aminopropyldimethoxymethylsilane; ureide-based silane coupling agents such as 3-ureide propyltriethoxysilane; vinyl silane coupling agents such as vinyltrimethoxysilane, vinyltriethoxysilane, and vinylmethyldiethoxysilane; styryl silane coupling agents such as p-styryl trimethoxysilane; acrylic silane coupling agents such as 3-acryloxypropyltrimethoxysilane and 3-methacryloxypropyltrimethoxysilane; isocyanate-based silane coupling agents such as 3-isocyanatopropyltrimethoxysilane; sulfide-type silane coupling agents such as bis (triethoxysilylpropyl) disulfide and bis (triethoxysilylpropyl) tetrasulfide; phenyl trimethoxysilane; methacryloxypropyl trimethoxysilane; (ii) an imidazole silane; triazinylsilanes, and the like.

In the present application, the coupling agent may be contained in an amount of 0.1 to 10 parts by weight or 0.5 to 5 parts by weight, relative to 100 parts by weight of the curable compound. Within the above range, the present application can achieve the effect of improving adhesion by adding a coupling agent.

The encapsulating composition of the present application may contain a moisture absorbent, as needed. The term "moisture absorbent" is used to collectively refer to a component capable of absorbing or removing moisture or humidity introduced from the outside by a physical or chemical reaction or the like. That is, it means a moisture reactive absorbent or a physical absorbent, and a mixture thereof may be used.

The specific kind of the moisture absorbent usable in the present application is not particularly limited, and in the case of the moisture reactive absorbent, may include, for example, a metal oxide, a metal salt or phosphorus pentoxide (P)₂O₅) Etc., and in the case of a physical absorbent, may include zeolite, zirconia, montmorillonite, or the like.

The encapsulation composition of the present application may include the moisture absorbent in an amount of 5 parts by weight to 100 parts by weight, 5 parts by weight to 80 parts by weight, 5 parts by weight to 70 parts by weight, or 10 parts by weight to 30 parts by weight, relative to 100 parts by weight of the curable compound. Since the encapsulating composition of the present application preferably controls the content of the moisture absorbent to 5 parts by weight or more, the present application can allow the encapsulating composition or a cured product thereof to exhibit excellent moisture and humidity barrier properties. Further, the present application can provide a thin film sealing structure by controlling the content of the moisture absorbent to 100 parts by weight or less.

In one embodiment, the encapsulating composition may also include an inorganic filler, as desired. There is no particular limitation on the specific type of filler that can be used herein, and for example, one or a mixture of two or more of clay, talc, alumina, calcium carbonate, and silica can be used.

The encapsulation 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 the inorganic filler with respect to 100 parts by weight of the curable compound. The present application can provide a sealing structure having excellent moisture or humidity barrier properties and mechanical properties by controlling the inorganic filler preferably to 1 part by weight or more. Further, the present invention can provide a cured product exhibiting excellent moisture barrier properties even when a film is formed by controlling the content of the inorganic filler to 50 parts by weight or less.

In addition to the above constitution, the encapsulating composition according to the present application may contain various additives within a range that does not affect the above effects of the present invention. For example, the encapsulating composition may contain an antifoaming agent, a tackifier, an ultraviolet stabilizer, an antioxidant, or the like in an appropriate content range according to desired physical properties.

In one embodiment, the encapsulating composition may be in a liquid phase at room temperature, e.g., at about 25 ℃. In one embodiment of the present application, the encapsulating composition may be a solvent-free liquid phase. The encapsulation composition may be used to seal an organic electronic component, and in particular, may be used to seal the entire surface of an organic electronic component. Since the encapsulating composition has a liquid form at room temperature, the present application seals the organic electronic element by applying the composition to the side of the element. Furthermore, the present application has a solvent-free form, and thus the content of volatile organic compounds and/or moisture can be adjusted.

Also, the encapsulating composition of the present application may be an ink composition. The encapsulating composition of the present application may be an ink composition capable of performing an inkjet process. The encapsulating composition of the present application may have a specific composition and physical properties to facilitate ink jetting.

Further, in one embodiment of the present application, the viscosity of the encapsulating composition as measured by Brookfield DV-3 at a temperature of 25 ℃, a torque of 90%, and a shear rate of 100rpm may be in a range of less than 50cPs, from 1cPs to 46cPs, or from 5cPs to 44 cPs. By controlling the viscosity of the composition within the above range, the present application can realize physical properties that can be performed and improve coating properties when applied to an organic electronic component to provide a sealing material for a thin film.

In one embodiment, the surface energy of the cured product of the encapsulating composition after curing may be in the range of 5mN/m to 45mN/m, 10mN/m to 40mN/m, 15mN/m to 35mN/m, or 20mN/m to 30 mN/m. The surface energy can be measured by methods known in the art, for example, by the torus method. The present application can achieve excellent coating properties within the above surface energy range.

In one embodiment of the present application, the surface energy (γ)^{Surface of}mN/m) can be calculated as gamma^{Surface of}＝γ^Dispersing+γ^Polarity. In one embodiment, the surface energy may be measured using a droplet shape analyzer (DSA 100 product from KRUSS). For example, an encapsulation composition for measuring surface energy is applied to a SiNx substrate to a thickness of about 50 μm and 4cm²(width: 2cm, height: 2cm) of the coating area after forming a sealing film (spin coater), dried at room temperature for about 10 minutes under a nitrogen atmosphere, and then passed through a vacuum of 4000mJ/cm²The amount of light of (2) is 1000mW/cm²Is UV cured. The operation of dropping deionized water having a known surface tension on the cured film and obtaining the contact angle thereof was repeated five times to obtain an average value of the five obtained contact angle values, and likewise, the operation of dropping diiodomethane having a known surface tension on the film and obtaining the contact angle thereof was repeated five times to obtain an average value of the five obtained contact angle values. Then, the surface energy was obtained by substituting the obtained average value of the contact angles of deionized water and diiodomethane into the value (Strom value) regarding the surface tension of the solvent in the Owens-Wendt-Rabel-Kaelble method.

Further, in one embodiment of the present application, the encapsulation composition may have a light transmittance in the visible region of 90% or more, 92% or more, or 95% or more after curing. Within the above range, the present application provides an organic electronic device having high resolution, low power consumption, and long lifetime by applying the encapsulation composition to the top emission type organic electronic device. Further, the haze of the encapsulating composition of the present application after curing according to jis k7105 standard test may be 3% or less, 2% or less, or 1% or less, and the lower limit is not particularly limited, but may be 0%. Within the haze range, the encapsulant composition can have excellent optical properties after curing. In the present specification, the above-mentioned light transmittance or haze may be measured in a state where the encapsulating composition is cured into an organic layer, and may be an optical characteristic measured when the thickness of the organic layer is any of 2 μm to 50 μm. In one embodiment of the present application, the above moisture absorbent or inorganic filler may not be included in order to achieve the optical characteristics.

The application also relates to an organic electronic device. As shown in fig. 1, an exemplary organic electronic device 3 may include a substrate 31; an organic electronic element 32 formed on the substrate 31; and an organic layer 33 sealing the entire surface of the organic electronic element 32 and comprising the above encapsulation composition.

In one embodiment of the present application, an organic electronic element 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 element 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 element 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 element may further include a protective layer 35 for protecting the electrode and the light-emitting layer of the element. The protective layer 35 may be an inorganic protective layer. The protective layer may be a protective layer by Chemical Vapor Deposition (CVD), in which a known inorganic material may be used as a material, for example, silicon nitride (SiNx) may be used. In one example, silicon nitride (SiNx) used as a protective layer may be deposited to a thickness of 0.01 μm to 50 μm.

In one embodiment 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 protective layer described above. In one example, the inorganic layer may be a metal oxide or nitride of one or more selected from Al, Zr, Ti, Hf, Ta, In, Sn, Zn, and Si. The thickness of the inorganic layer may be 0.01 μm to 50 μm, 0.1 μm to 20 μm, or 1 μm to 10 μm. In one example, the inorganic layer of the present application may be an inorganic material without any dopant, or may be an inorganic material containing a dopant. The dopant that may be doped may be one or more elements selected from Ga, Si, Ge, Al, Sn, Ge, B, In, Tl, Sc, V, Cr, Mn, Fe, Co, and Ni, or oxides of the elements, but is not limited thereto.

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

The organic electronic device 3 of the present application may include a sealing structure including the organic layer 33 and the inorganic layer 34 as described above, wherein the sealing structure may include at least one or more organic layers and at least one or more inorganic material layers, and 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 element/protective layer/(organic layer/inorganic layer) n, where n may be a number ranging from 1 to 100. Fig. 1 is a cross-sectional view exemplarily showing a case where 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 glass, a metal substrate, or a polymer film. As the polymer film, for example, a polyethylene terephthalate film, a polytetrafluoroethylene film, a polyethylene film, a polypropylene film, a polybutylene film, a polybutadiene film, a vinyl chloride copolymer film, a polyurethane film, an ethylene-vinyl acetate film, an ethylene-propylene copolymer film, an ethylene-ethyl acrylate copolymer film, an ethylene-methyl acrylate copolymer film, a polyimide film, or the like can be used.

Further, as shown in fig. 2, the organic electronic device 3 may further include a sealing film 37 present between the cover substrate 38 and the substrate 31 on which the organic electronic element 32 is formed. The sealing film 37 may be used for the purpose of adhering the substrate 31 on which the organic electronic element 32 is formed and the cover substrate 38, and may be, for example, a pressure-sensitive adhesive film or an adhesive film, but is not limited thereto. The sealing film 37 may seal the entire surface of the sealing structure 36 of the organic layer and the inorganic layer laminated on the organic electronic element 32 described above.

The application also relates to a method of manufacturing an organic electronic device.

In one example, the manufacturing method may include a step of forming an organic layer 33 on the substrate 31 having the organic electronic element 32 formed thereon, such that the above-described encapsulation composition seals the entire surface of the organic electronic element 32.

Here, the organic electronic element 32 may be prepared by forming a reflective electrode or a transparent electrode on a substrate 31 such as glass or a polymer film as the substrate 31, and forming an organic material layer on the reflective electrode, such as a vacuum deposition or sputtering method. 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 the step of forming an inorganic protective layer 35 on the first electrode, the organic material layer, and the second electrode formed on the substrate 31. The organic layer 33 described above is then used to cover the entire surface of the organic electronic component 32 on the substrate 31. Here, the step of forming the organic layer 33 is not particularly limited, and the above encapsulation composition may be applied onto the entire surface of the substrate 31 using a process such as inkjet printing, gravure coating, spin coating, screen printing, or reverse offset coating.

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

In one example, after the encapsulation composition described above is applied to form the upper organic layer, the composition is irradiated with light to initiate crosslinking. The irradiating of the light may include irradiating with light in a wavelength region of 250nm to 450nm or 300nm to 450nm at 0.3J/cm²To 6J/cm²Light quantity of (2) or 0.5J/cm²To 5J/cm²Light irradiation of the amount of light.

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

Advantageous effects

The present application provides an encapsulation composition that can effectively block moisture or oxygen introduced into an organic electronic device from the outside to ensure the lifespan of the organic electronic device and excellent storage stability upon distribution and storage, and an organic electronic device including the same.

Drawings

Fig. 1 and 2 are cross-sectional views showing an organic electronic device according to an embodiment of the present invention.

Detailed Description

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