阅读说明：本技术 用于封装有机电子元件的组合物 (Composition for encapsulating organic electronic components ) 是由 李承民 金素映 梁世雨 于 2018-04-20 设计创作，主要内容包括：本申请涉及用于封装有机电子元件的组合物和包含其的有机电子器件,并且提供了封装组合物和包含其的有机电子器件,所述封装组合物可以形成能够有效地阻挡从外部引入至有机电子器件中的水分或氧的结构,从而确保有机电子器件的寿命,并且可以应用于顶部发射有机电子器件以在具有优异的光学特性和可加工性的同时防止有机电子元件的物理和化学损坏。(The present application relates to a composition for encapsulating an organic electronic element and an organic electronic device including the same, and provides an encapsulating composition that can form a structure capable of effectively blocking moisture or oxygen introduced into the organic electronic device from the outside, thereby securing the lifespan of the organic electronic device, and can be applied to a top emission organic electronic device to prevent physical and chemical damages of the organic electronic element while having excellent optical characteristics and processability, and an organic electronic device including the same.)

1. A composition for encapsulating an organic electronic component comprising a curable compound; a thermal initiator; and a hardening retarder, and satisfies the following equation 1:

[ equation 1]

0.03＜R/P＜0.6

Wherein R is a weight part of the hardening retarder with respect to 100 weight parts of the curable compound, and P is a weight part of the thermal initiator with respect to 100 weight parts of the curable compound.

2. A composition for encapsulating organic electronic elements according to claim 1, wherein the curable compound comprises at least one or more curable functional groups.

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

4. A composition for encapsulating an organic electronic element according to claim 1, wherein the curable compound comprises an epoxy compound having a cyclic structure in a molecular structure.

5. The composition for encapsulating organic electronic element according to claim 4, wherein the epoxy compound having a cyclic structure in a molecular structure has ring constituent atoms in the molecular structure in a range of 3 to 10.

6. The composition for encapsulating organic electronic element according to claim 4, wherein the epoxy compound having a cyclic structure in a molecular structure is an alicyclic epoxy compound.

7. A composition for encapsulating an organic electronic element according to claim 4, wherein the curable compound further comprises a compound having an oxetanyl group.

8. The composition for encapsulating organic electronic element according to claim 7, wherein the compound having an oxetanyl group is contained in a range of 3 parts by weight to 50 parts by weight with respect to 100 parts by weight of the epoxy compound.

9. A composition for encapsulating an organic electronic element according to claim 1, wherein the weight average molecular weight of the curable compound is 300g/mol or less.

10. A composition for encapsulating organic electronic elements according to claim 1, wherein the thermal initiator is a thermal cationic initiator.

11. The composition for encapsulating organic electronic elements according to claim 1, wherein the thermal initiator comprises a sulfonium salt, a phosphonium salt, a quaternary ammonium salt, a diazonium salt or an iodonium salt, the thermal initiator having BF4-, ASF6-, PF6-, SbF 6-or (BX4) -as anion, wherein X represents a phenyl group substituted with at least two fluorine or trifluoromethyl groups.

12. The composition for encapsulating organic electronic element according to claim 1, wherein the thermal initiator is contained in an amount of 0.01 to 1 part by weight with respect to 100 parts by weight of the curable compound.

13. The composition for encapsulating organic electronic elements according to claim 1, wherein the hardening retarder comprises one or more selected from the group consisting of: amine-based compounds, polyether-based compounds, boric acid, phenylboronic acid, salicylic acid, hydrochloric acid, sulfuric acid, oxamic acid, terephthalic acid, isophthalic acid, phosphoric acid, acetic acid, and lactic acid.

14. The composition for encapsulating organic electronic element according to claim 1, wherein when the hardening retarder is a polyether-based compound, R/P is in the range of more than 0.1 and less than 0.5, and when the hardening retarder is an amine-based compound, R/P is in the range of more than 0.03 and 0.1 or less.

15. The composition for encapsulating organic electronic element according to claim 1, wherein the hardening retarder is contained in an amount of 0.002 parts by weight to 0.12 parts by weight with respect to 100 parts by weight of the curable compound.

16. An organic electronic device comprising a substrate; an organic electronic element formed on the substrate; and a top encapsulation layer encapsulating the top surface of the organic electronic element and comprising the composition for encapsulating organic electronic elements according to claim 1.

17. The organic electronic device according to claim 16, further comprising a side encapsulation layer formed so as to surround a side surface of the organic electronic element on the substrate, wherein the side encapsulation layer and the top encapsulation layer exist on the same plane.

18. A method for fabricating an organic electronic device, comprising the steps of: applying the composition for encapsulating an organic electronic element according to claim 1 on a substrate having an organic electronic element formed thereon so as to seal a top surface of the organic electronic element; and curing the composition.

Technical Field

Cross Reference to Related Applications

The present application claims the benefit of priority based on korean patent application No. 10-2017-0051447 filed on 21/4/2017, the disclosure of which is incorporated herein by reference in its entirety.

Background

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

An Organic Light Emitting Diode (OLED) in an organic electronic device has lower power consumption and faster response speed than existing light sources, and is advantageous for thinning a display device or an illumination apparatus. In addition, the OLED has excellent space utilization, and thus is expected to be applied to various fields covering various portable devices, monitors, notebook computers, and televisions.

The OLED has an emission structure such as a bottom emission structure and a top emission structure. Among them, the top emission structure has a higher Aperture Ratio (Aperture Ratio) than the bottom emission structure, so that it is easily realized with ultra-high resolution, and an element having high brightness and excellent power consumption and life, etc. can be realized.

However, since the exit surface of the generated light must be colorless and transparent, the OLED has a limitation in that the sealing material must be colorless and transparent. Further, in order to form a uniform coating film, a sealing material used in an ODF (one drop filling) method at the time of sealing an OLED element must have low viscosity and small change with time, and it is necessary to provide an encapsulating composition capable of suppressing deterioration due to outgassing.

Disclosure of Invention

Technical problem

The present application provides an encapsulation composition that can form a structure capable of effectively blocking moisture or oxygen introduced into an organic electronic device from the outside, thereby ensuring the lifespan of the organic electronic device, and can be applied to a top emission organic electronic device to prevent physical and chemical damage of an organic electronic element while having excellent optical characteristics and processability, and an organic electronic device including the same.

Technical scheme

The present invention relates to compositions for encapsulating organic electronic components. The composition may be a pressure sensitive adhesive composition or an adhesive composition. The encapsulating composition may be, for example, an encapsulating material applied to seal or encapsulate an organic electronic device, such as an OLED. In one example, the encapsulation composition of the present application can be applied to seal or encapsulate the top surface of an organic electronic component. Thus, after the encapsulating composition is applied to the encapsulation, it may be in the form of a top surface of the encapsulated organic electronic device.

In the present specification, the term "organic electronic device" means an article or a device having a structure including an organic material layer that generates an alternating current of charges using holes and electrons between a pair of electrodes facing each other, 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.

Exemplary compositions for encapsulating organic electronic components may include a curable compound; a thermal initiator; and a hardening retarder. Here, the encapsulation composition may satisfy the following equation 1.

[ equation 1]

0.03＜R/P＜0.6

In equation 1, R is a weight part of the hardening retarder with respect to 100 weight parts of the curable compound, and P is a weight part of the thermal initiator with respect to 100 weight parts of the curable compound. In the present specification, parts by weight may mean a weight ratio between the respective components. Specifically, the R/P range may be in a range of 0.0305 to 0.550, 0.0307 to 0.530, 0.0308 to 0.500, or 0.0309 to 0.495.

Since the present application provides an encapsulating composition applied to directly contact a top-emitting organic electronic component on the component, the composition should have excellent optical characteristics after curing, prevent damage to the component due to outgassing generated when the composition is cured, and also have workability capable of securing a sufficient pot life while allowing a uniform coating film, and also require thermal stability during high temperatures. By providing a composition satisfying the above equation 1, the present application can provide a composition for encapsulating an organic electronic component that can simultaneously achieve optical characteristics, component reliability, processability, and thermal stability. In addition, in order to achieve the above effects, the present application may control the kind of the compound and the content of each composition, but is not limited thereto.

In one embodiment of the present application, the curable compound may be a cationically curable compound. Further, the curable compound may comprise at least one or more curable functional groups. The curable functional group may be, for example, one or more selected from glycidyl groups, isocyanate groups, hydroxyl groups, carboxyl groups, amide groups, epoxy groups, cyclic ether groups, thioether groups, acetal groups, and lactone groups. Further, the curable compound may be a monofunctional compound or a compound having bifunctional or higher functionality, and may be a combination of a monofunctional compound and a compound having bifunctional or higher functionality, or a combination of compounds having bifunctional or higher functionality. The curable compound achieves excellent heat resistance at high temperature and high humidity by achieving an appropriate degree of crosslinking to encapsulate an organic electronic element.

In one example, the curable compound may be included in the composition at a rate of 70 wt% or more, 75 wt% or more, 80 wt% or more, 85 wt% or more, 90 wt% or more, 95 wt% or more, or 98 wt% or more. The upper limit is not particularly limited, but may be 99.9 wt% or 99.8 wt%.

In one example, the curable compound may include an epoxy compound having a cyclic structure in a molecular structure. In the epoxy compound having a cyclic structure in a molecular structure, ring-constituting atoms in the molecular structure may be present in a range of 3 to 10, 4 to 8, or 5 to 7, and the cyclic structure in the compound may be present in a range of 1 or more, or 2 or more and 10 or less. Further, in one example, the epoxy compound having a cyclic structure in a molecular structure may include at least two or more compounds different from each other. The type of the epoxy compound having a cyclic structure in a molecular structure is not particularly limited, but may include an alicyclic epoxy compound or an aromatic epoxy compound.

In one example, the alicyclic epoxy compound may be an epoxycyclohexane compound including a unit of the following formula 1.

[ formula 1]

In formula 1, R1 and R2 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and X represents an epoxy-containing substituent.

In addition, the alicyclic epoxy compound may include a compound represented by the following formula 2.

[ formula 2]

In formula 2, Y is a single bond or one or more selected from the group consisting of linear or branched alkylene having 1 to 18 carbon atoms, -CO-, -O-CO-O-, -COO-, -O-, and-CONH-, and R1 to R4 each independently represent a hydrogen atom or an alkyl having 1 to 4 carbon atoms.

As the alicyclic epoxy compound, a compound based on epoxycyclohexylmethylcyclohexanecarboxylate; epoxycyclohexane carboxylate-based compounds of alkanediols; epoxycyclohexylmethyl ester-based compounds of dicarboxylic acids; epoxycyclohexylmethyl ether-based compounds of polyethylene glycol; epoxycyclohexylmethyl ether-based compounds of alkanediols; a diepoxetrispiro-ring-based compound; diepoxy-monoaspiro-based compounds; vinylcyclohexene diepoxide compounds; epoxy cyclopentyl ether compounds, diepoxy tricyclodecane compounds, and the like. They are stable even at high temperatures, colorless and transparent after curing, and have toughness and excellent surface hardness.

The alicyclic epoxy compounds described above may be exemplified by, for example, compounds represented by the following formulas 3 to 7, respectively.

[ formula 3]

In formula 3, R1 to R4 each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and Z represents an alkylene group having 1 to 4 carbon atoms.

[ formula 4]

In formula 4, R1 to R4 each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and n represents an integer of 1 to 20.

[ formula 5]

In formula 5, R1 to R4 each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and n represents an integer of 1 to 20.

[ formula 6]

In formula 6, R1 to R4 each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and m represents an integer of 1 to 20.

[ formula 7]

In formula 7, R1 to R4 each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and p represents an integer of 1 to 20.

More specifically, the component alicyclic epoxy compound may be exemplified by bis (3, 4-epoxycyclohexyl) oxalate, bis (3, 4-epoxycyclohexylmethyl) adipate, bis (3, 4-epoxy-6-methylcyclohexylmethyl) adipate, bis (3, 4-epoxycyclohexylmethyl) piperonate, 3, 4-epoxycyclohexylmethyl (3, 4-epoxy) cyclohexanecarboxylate, 3, 4-epoxycyclohexanecarboxylate, 6-methyl-3, 4-epoxycyclohexylmethyl (6-methyl-3, 4-epoxy) cyclohexanecarboxylate, 3, 4-epoxy-2-methylcyclohexylmethyl (3, 4-epoxy-2-methyl) cyclohexanecarboxylate, 3, 4-epoxy-3-methylcyclohexylmethyl (3, 4-epoxy-3-methyl) cyclohexanecarboxylic acid ester, 3, 4-epoxy-5-methylcyclohexylmethyl (3, 4-epoxy-5-methyl) cyclohexanecarboxylic acid ester and caprolactone adduct thereof, limonene dioxide, vinylcyclohexene dioxide, Celloxide, 2021P or 8000 from Dicel Corporation, or the like, and two or more thereof may be used in combination. These may be synthesized by a conventional method, or a commercially available product may also be used. By using the alicyclic epoxy compound, physical properties such as colorless transparency, low-temperature curability and chemical resistance, and heat resistance durability under high temperature and high humidity can be secured upon curing the curable composition according to the present application.

In one example, the curable compound may further include a compound having an oxetanyl group. In the present specification, the term compound having an oxetanyl group or an oxetane compound may mean a compound having at least one oxetanyl group, wherein the oxetanyl group may mean a quaternary cyclic ether group in a molecular structure.

As the oxetane compound, a compound having one oxetanyl group in the molecule (hereinafter referred to as "monofunctional oxetane") and a compound having two or more oxetanyl groups in the molecule (hereinafter referred to as "multifunctional oxetane") can be included as examples.

As the monofunctional oxetane, a monofunctional oxetane having an alkoxyalkyl group can be used, including, for example, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane; monofunctional oxetanes containing aromatic groups, such as 3-ethyl-3-phenoxymethyloxetane; a monofunctional oxetane containing a hydroxyl group such as 3-ethyl-3-hydroxymethyloxetane and the like.

As the polyfunctional oxetane, 3-ethyl-3- [ (3-ethyloxetan-3-yl) methoxymethyl ] oxetane, 1, 4-bis [ (3-ethyloxetan-3-yl) methoxymethyl ] benzene, 1, 4-bis [ (3-ethyloxetan-3-yl) methoxy ] benzene, 1, 3-bis [ (3-ethyloxetan-3-yl) methoxy ] benzene, 1, 2-bis [ (3-ethyloxetan-3-yl) methoxy ] benzene, 4 '-bis [ (3-ethyloxetan-3-yl) methoxy ] biphenyl, 2' -bis [ (3-ethyloxetan-3-yl) methoxy ] biphenyl, etc. can be used, 3,3',5,5' -tetramethyl-4, 4' -bis [ (3-ethyloxetan-3-yl) methoxy ] biphenyl, 2, 7-bis [ (3-ethyloxetan-3-yl) methoxy ] naphthalene, bis [4- { (3-ethyloxetan-3-yl) methoxy } phenyl ] methane, bis [2- { (3-ethyloxetan-3-yl) methoxy } phenyl ] methane, 2-bis [4- { (3-ethyloxetan-3-yl) methoxy } phenyl ] propane, a modified product of novolak-formaldehyde resin etherified with 3-chloromethyl-3-ethyloxetane, 3(4),8(9) -bis [ (3-ethyloxetan-3-yl) methoxymethyl ] -tricyclo [5.2.1.02,6] decane, 2, 3-bis [ (3-ethyloxetan-3-yl) methoxymethyl ] norbornane, 1,1, 1-tris [ (3-ethyloxetan-3-yl) methoxymethyl ] propane, 1-butoxy-2, 2-bis [ (3-ethyloxetan-3-yl) methoxymethyl ] butane, 1, 2-bis [ {2- (3-ethyloxetan-3-yl) methoxy } ethylthio ] ethane, bis [ {4- (3-ethyloxetan-3-yl) methylthio } phenyl ] sulfide, dimethyldithiocarbamate, 1, 6-bis [ (3-ethyloxetan-3-yl) methoxy ] -2,2,3,3,4,4,5, 5-octafluorohexane, a hydrolysis condensate of 3- [ (3-ethyloxetan-3-yl) methoxy ] propyltriethoxysilane, a condensate of tetrakis [ (3-ethyloxetan-3-yl) methyl ] silicate, and the like.

In one example, the curable compound may include an epoxy compound having a cyclic structure and/or a compound having an oxetanyl group in the above molecular structure. That is, the curable compound may be composed of an epoxy compound having a cyclic structure in a molecular structure alone without an oxetane compound, but is not limited thereto, and may further contain a compound having an oxetane group. When the compound having an oxetanyl group is further included, the compound having an oxetanyl group may be included in a range of 3 parts by weight to 50 parts by weight with respect to 100 parts by weight of an epoxy compound having a cyclic structure in a molecular structure. The lower limit of the content range may be 3.5 parts by weight or more, 4 parts by weight or more, 4.5 parts by weight or more, 5.1 parts by weight or more, 10 parts by weight or more, 20 parts by weight or more, 30 parts by weight or more, or 35 parts by weight or more. The lower limit of the content range may be within a range of 48 parts by weight or less, 45 parts by weight or less, 44 parts by weight or less, 43 parts by weight or less, 40 parts by weight or less, 35 parts by weight or less, 25 parts by weight or less, 15 parts by weight or less, or 8 parts by weight or less. The present application can provide a composition in which the pot life is sufficiently ensured while allowing a uniform coating film in the process of encapsulating the top surface of the organic electronic element by controlling the content ratio.

In one example, the curable compound may be a compound having a weight average molecular weight of 300g/mol or less. The weight average molecular weight of the compound can be in a range of 50g/mol to 295g/mol, 100g/mol to 288g/mol, or 120g/mol to 275 g/mol. The present application makes it possible to form a uniform coating film after coating while achieving excellent coating characteristics of the encapsulating composition to be applied in a liquid phase by containing a low-molecular weight curable compound.

In the present specification, the weight average molecular weight means a value converted with respect to standard polystyrene as measured by GPC (gel permeation chromatography).

in one embodiment herein, the thermal initiator may be a thermal cationic initiator. The thermal cationic initiator may comprise a sulfonium, phosphonium, quaternary ammonium, diazonium or iodonium salt having BF4-, ASF6-, PF6-, SbF 6-or (BX4) - (wherein X represents a phenyl group substituted with at least two fluorine or trifluoromethyl groups) as anion.

Sulfonium salts can include triphenylsulfonium tetrafluoride, triphenylsulfonium hexafluoro, tris (4-methoxyphenyl) sulfonium hexafluoro, diphenyl (4-phenylthiophenyl) sulfonium hexafluoro, and the like.

The phosphorus salt may include ethyltriphenylphosphonium hexafluoroide, tetrabutylphosphonium hexafluoroide, and the like.

The quaternary ammonium salts may include dimethylphenyl (4-methoxybenzyl) ammonium hexafluorophosphate, dimethylphenyl (4-methoxybenzyl) ammonium hexafluoroantimonate, dimethylphenyl (4-methoxybenzyl) ammonium tetrakis (pentafluorophenyl) borate, dimethylphenyl (4-methylbenzyl) ammonium hexafluoroantimonate, dimethylphenyl (4-methylbenzyl) ammonium hexafluorotetrakis (pentafluorophenyl) borate, methylphenyldibenzylammonium methylphenyl hexafluoroantimonate, methylphenyldibenzylammonium tetrakis (pentafluorophenyl) borate, phenyltribenzylammonium tetrakis (pentafluorophenyl) borate, dimethylphenyl (3, 4-dimethylbenzyl) ammonium tetrakis (pentafluorophenyl) borate, N-dimethyl-N-benzylanilinium hexafluoro, N, N-diethyl-N-benzylanilinium boron tetrafluoride, N-dimethyl-N-benzylpyridinantimony hexafluoride, N-diethyl-N-benzylpyridintriflic acid, and the like.

The iodide ion may include diphenyliodide, di-p-tolyliodide, bis (4-dodecylphenyl) iodide, bis (4-methoxyphenyl) iodide, (4-octyloxyphenyl) phenyliodide, bis (4-decyloxyphenyl) iodide, 4- (2-hydroxytetradecyloxy) phenylphenyliodide, 4-isopropylphenyl (p-tolyl) iodide, isobutylphenyl (p-tolyl) iodide, and the like.

In one embodiment of the present application, the thermal initiator may include 0.01 parts by weight to 1 part by weight with respect to 100 parts by weight of the curable compound. In one example, the lower limit of the thermal initiator may be 0.02 parts by weight or greater, 0.03 parts by weight or greater, 0.04 parts by weight or greater, 0.05 parts by weight or greater, 0.06 parts by weight or greater, 0.09 parts by weight or greater, 0.12 parts by weight or greater, or 0.18 parts by weight or greater. Further, the upper limit of the thermal initiator may be 1 part by weight or less, 0.8 part by weight or less, 0.5 part by weight or less, 0.3 part by weight or less, 0.25 part by weight or less, 0.2 part by weight or less, 0.19 part by weight or less, 0.13 part by weight or less, or 0.09 part by weight or less. The composition for encapsulating an organic electronic element according to the present application can achieve hardness upon curing by including a thermal initiator in the above-described weight ratio range, whereby an encapsulating material having sufficient curing performance at the time of encapsulating the top surface of the element and having high endurance reliability due to suppression of outgassing at high temperature after curing can be provided. Generally, the main components of the outgas are the uncured compound and the initiator residue, but the present application provides an encapsulating composition capable of simultaneously achieving optical characteristics, element stability, processability and thermal stability in the combined formulation of the present application by combining the above-mentioned specific curable compound and the initiator, provided that the content ratio of the initiator and the hardening retarder is controlled as in the above-mentioned equation 1.

The curable composition according to the present application may comprise a hardening retarder. The hardening retarder may be one or more selected from the group consisting of: amine-based compounds, polyether-based compounds, boric acid, phenylboronic acid, salicylic acid, hydrochloric acid, sulfuric acid, oxamic acid, terephthalic acid, isophthalic acid, phosphoric acid, acetic acid, and lactic acid. In one example, the hardening retarder may have a cyclic structure in a molecular structure in consideration of the objects and effects of the present invention as described above. In the cyclic structure, the ring-constituting atoms within the molecular structure may be present in a range of 3 to 40, 4 to 35, or 5 to 30, and the cyclic structure in the compound may be present in 1 or more, or 2 or more and 10 or less. The cyclic structure may be alicyclic or aromatic, but is not limited thereto.

In one example, the polyether-based compound may be a polyethylene glycol, a polypropylene glycol, a polybutylene glycol, or a crown ether compound, and preferably may be a crown ether compound. The crown ether compound may be 12-crown-4-ether, 15-crown-5-ether, 18-crown-6-ether or 24-crown-8-ether, but is not limited thereto. The amine-based compound may be exemplified by aniline or benzylamine, but is not limited thereto.

Here, the hardening retarder may be a compound having a structure represented by the following formula 11.

[ formula 11]

In formula 11, at least one of R1 to R12 represents an alkyl group having 1 to 20 carbon atoms and the remainder represents hydrogen, wherein the alkyl group may be substituted with one or more functional groups selected from: linear or branched alkoxy groups having 1 to 20 carbon atoms, halogen atoms, -OH, -COOH and-COO-alkyl ester groups (provided that the alkyl moiety is a linear or branched residue having 1 to 20 carbon atoms).

Further, the crown ether compound may comprise a cyclohexyl group. The crown ether compound including a cyclohexyl group may be a compound having a structure of the following formula 12.

[ formula 12]

In this specification, when the expression is used, the case where no element is indicated may mean carbon, and the case where no element bonded to carbon is indicated may mean hydrogen.

In one example, the present application may vary the ratio of the above equation 1 according to the kind of the hardening retarder. For example, when the hardening retarder is a polyether-based compound, R/P may be in a range of greater than 0.1, less than 0.5, 0.15 to 0.495, 0.2 to 0.493, 0.3 to 0.45, or 0.35 to 0.42. Further, when the hardening retarder is an amine-based compound, R/P may be in a range of greater than 0.03, 0.1 or less, or 0.031 to 0.05. In the present application, the initiator and the retarder may be selected according to the kind of the curable compound, and an appropriate content ratio in the composite formulation of the present application may be adjusted according to the kind of the hardening retarder. The present application provides an encapsulation composition capable of simultaneously achieving optical characteristics, element stability, processability and thermal stability by controlling the content ratio.

In one embodiment of the present application, the hardening retarder may include 0.002 parts by weight to 0.12 parts by weight with respect to 100 parts by weight of the curable compound. The lower limit of the hardening retarder may be 0.004 parts by weight, 0.006 parts by weight, 0.008 parts by weight, 0.01 parts by weight, 0.02 parts by weight, 0.023 parts by weight, or 0.025 parts by weight. Further, the upper limit of the hardening retarder may be 0.11 parts by weight, 0.10 parts by weight, 0.09 parts by weight, 0.08 parts by weight, 0.07 parts by weight, 0.045 parts by weight, or 0.023 parts by weight. In addition, the content of the hardening retarder may be variously set according to the kind of the hardening retarder, and in particular, when the hardening retarder is a polyether-based compound, the hardening retarder may be included in an amount of 0.008 parts by weight to 0.12 parts by weight, and when the hardening retarder is an amine-based compound, the hardening retarder may be included in an amount of 0.004 parts by weight to 0.08 parts by weight.

In one example, the encapsulating composition may have excellent light transmittance in the visible light region after curing. In one example, the encapsulation composition of the present application may exhibit a light transmittance of 90% or more according to JIS K7105 after curing. For example, the encapsulation composition may have a light transmittance of 92% or more or 93% or more in the visible light region. In addition, the encapsulating material of the present application may exhibit low haze and excellent light transmittance. In one example, the encapsulation composition, after curing, can have a haze of 5% or less, 4% or less, 3% or less, or 1% or less, as measured according to JIS K7105. The optical properties can be measured using a UV-Vis spectrometer at 550 nm.

If necessary, the encapsulating composition of the present application may contain a moisture adsorbent. The moisture adsorbent may impart the haze property and the light diffusion property thereto after the encapsulating composition is cured, and in this case, the haze range may be higher than the above range. The term "moisture adsorbent" may be used to collectively refer to a component capable of adsorbing 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 adsorbent or a physical adsorbent, and a mixture thereof may also be used.

The moisture-reactive adsorbent chemically reacts with moisture, humidity, or oxygen introduced into the encapsulating composition or a cured product thereof to adsorb the moisture or humidity. The physical adsorbent can increase the movement path of moisture or humidity permeating the resin composition or its cured product to inhibit permeation, and maximize the barrier property against moisture and humidity by interaction with the matrix structure of the resin composition or its cured product, the moisture-reactive adsorbent, and the like.

The specific kind of the moisture adsorbent that can be used in the present application is not particularly limited, and for example, in the case of a moisture reactive adsorbent, it may include one or a mixture of two or more of metal oxide, metal salt, phosphorus pentoxide (P2O5), or the like, and in the case of a physical adsorbent, it may include zeolite, zirconia, montmorillonite, or the like.

Here, specific examples of the metal oxide may include lithium oxide (Li2O), sodium oxide (Na2O), barium oxide (BaO), calcium oxide (CaO), magnesium oxide (MgO), or the like, and examples of the metal salt may include a sulfate such as lithium sulfate (Li2SO4), sodium sulfate (Na2SO4), calcium sulfate (CaSO4), magnesium sulfate (MgSO4), cobalt sulfate (CoSO4), gallium sulfate (Ga2(SO4)3), titanium sulfate (Ti (SO4)2), or nickel sulfate (NiSO 4); metal halides, such as calcium chloride (CaCl2), magnesium chloride (MgCl2), strontium chloride (SrCl2), yttrium chloride (YCl3), copper chloride (CuCl2), cesium fluoride (CsF), tantalum fluoride (TaF5), niobium fluoride (NbF5), lithium bromide (LiBr), calcium bromide (CaBr2), cesium bromide (CeBr3), selenium bromide (SeBr4), vanadium bromide (VBr3), magnesium bromide (MgBr2), barium iodide (BaI2), or magnesium iodide (MgI 2); or a metal chlorate such as barium perchlorate (Ba (ClO4)2) or magnesium perchlorate (Mg (ClO4)2), etc., but is not limited thereto.

In the present application, a moisture adsorbent such as a metal oxide may be compounded into the composition in an appropriate processed state. For example, a pulverization process of the moisture adsorbent may be required, and a process such as three-roll milling, bead milling or ball milling may be used to pulverize the moisture adsorbent.

The encapsulation composition of the present application may include a moisture adsorbent in an amount of 5 to 100 parts by weight, 5 to 80 parts by weight, 5 to 70 parts by weight, or 10 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 adsorbent to 5 parts by weight or more, the encapsulating composition or a cured product thereof can exhibit excellent moisture and humidity barrier characteristics. In addition, when the content of the moisture adsorbent is controlled to 100 parts by weight or less to form a thin film encapsulation structure, the composition may exhibit excellent moisture barrier properties.

In addition to the above-described constitution, the encapsulating composition according to the present application may further contain various additives in a range that does not affect the above-described effects of the present invention. For example, the encapsulating composition may contain an antifoaming agent, a coupling agent, an adhesion promoter, a uv stabilizer, an antioxidant, or the like in an appropriate content range according to desired physical properties. In one example, the encapsulating composition may also include an antifoaming agent. The present application can achieve defoaming characteristics during the above-described coating process of the encapsulation composition by including a defoaming agent to provide a reliable encapsulation structure. The kind of the defoaming agent is not particularly limited as long as the physical properties of the encapsulating composition required in the present application are satisfied.

In one example, the encapsulating composition may be in a liquid state 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 encapsulating composition may be applied to encapsulate an organic electronic element, and in particular, may be applied to encapsulate a top surface of an organic electronic element. Since the encapsulation composition has the form of a liquid phase at room temperature, the present application can encapsulate an organic electronic component by applying the composition to the top surface of the component.

In one example, the viscosity of the encapsulation composition at a temperature of 25 ℃ and a rotational speed of 100rpm can be 500cP or less, 350cP or less, 200cP or less, 180cP or less, 150cP or less, 100cP or less, or 90cP or less. The lower limit thereof is not particularly limited, but may be 10cP or more, or 30cP or more. The viscosity is measured using a Brookfield viscometer (model LV) with a torque on the RV-63 spindle.

Further, in one example, the b value of the encapsulant composition of the present application in CIE LAB color space after curing can be in a range of 0.1 to 0.4, 0.15 to 0.35, 0.2 to 0.3, 0.2 to 0.26, or 0.2 to 0.24. Here, the upper limit may be more specifically 0.225 or less, or 0.215 or less. In the present specification, the term "CIE (international commission on illumination) LAB color space" means a color space defined by CIE so as to easily express an error range and a direction of a color of an object. The CIE LAB color space represents color space in L, a, and b, where L represents reflectance (brightness), which may be expressed in decimal units in the span of 0 to 100. a and b are chromaticity diagrams, wherein + a denotes a red direction, -a denotes a green direction, + b denotes a yellow direction, and-b denotes a blue direction.

The application also relates to an organic electronic device. As shown in fig. 1, an exemplary organic electronic device may include a substrate 21; an organic electronic element 23 formed on the substrate 21; and a top encapsulation layer 11 encapsulating the top surface of the organic electronic component 23 and comprising the above-described encapsulation composition. In addition, the exemplary organic electronic device may further include a side encapsulation layer 10 formed on the substrate 21 so as to surround the side surface of the organic electronic element 23. Thus, the organic electronic device may have an encapsulation structure 1 consisting of a top encapsulation layer 11 and a side encapsulation layer 10.

The top encapsulation layer and the side encapsulation layer may exist on the same plane. Here, "the same" may mean substantially the same. For example, "substantially the same on the same plane" means that it may have an error of ± 5 μm or ± 1 μm in the thickness direction. The top encapsulation layer may encapsulate the upper surface of the organic electronic element formed on the substrate, and may also encapsulate the side surfaces as well as the upper surface together. The side encapsulation layer may be formed on the side surfaces of the element, but may not directly contact the side surfaces of the organic electronic element. For example, the component may be packaged such that the top packaging layer directly contacts the top and side surfaces of the component. That is, in a plan view of the organic electronic device, the side encapsulation layer may be located around the substrate without contacting the element.

In the present specification, the term "peripheral" means a peripheral edge portion. That is, the periphery of the substrate may mean a peripheral edge portion in the substrate.

The organic electronic device of the present application may also include a cover substrate 22 present on the top encapsulation layer. The material of the substrate 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 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.

The material constituting the side sealing layer is not particularly limited, and may be an adhesive composition or a pressure-sensitive adhesive composition. The side sealing layer may include a sealing resin, wherein the sealing resin may be exemplified by acrylic resin, epoxy resin, silicone resin, fluorine resin, styrene resin, polyolefin resin, thermoplastic elastomer, polyoxyalkylene resin, polyester resin, polyvinyl chloride resin, polycarbonate resin, polyphenylene sulfide resin, polyamide resin, or a mixture thereof, and the like. The components constituting the side encapsulating layer may be the same as or different from the encapsulating composition described above.

In one example, the organic electronic element may include a reflective electrode layer (or a transparent electrode layer) formed on a substrate, an organic layer formed on the reflective electrode layer (or the transparent electrode layer) and including at least a light emitting layer, and a transparent electrode layer (or a reflective 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 also be applied to a bottom emission type.

The organic electronic element may further include a protective film for protecting the electrode and the light-emitting layer of the element. The protective film may have a structure in which organic films and inorganic films are alternately laminated. The protective film may be a protective layer formed by Chemical Vapor Deposition (CVD), in which a known inorganic material may be used as the material, and silicon nitride (SiNx), for example, may be used. In one example, silicon nitride (SiNx) used as a protective film may be deposited to a thickness of 0.01 to 5 μm.

The encapsulating composition described above may be in direct contact with an electrode or a protective film of an organic electronic component.

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

In one example, the manufacturing method may include the steps of: applying the above-mentioned encapsulating composition on the substrate 21 having the organic electronic element 23 formed thereon so as to seal the top surface of the organic electronic element 23; and curing the composition. The step of applying the encapsulating composition may be a step of forming the above-described top encapsulation layer 11.

Here, the substrate 21 on which the organic electronic element 23 is formed may be manufactured by: a reflective electrode or a transparent electrode is formed on a substrate 21, for example, glass or a film, by a method such as vacuum deposition or sputtering, and then an organic material layer is formed on the reflective electrode. The organic material layer may include a hole injection layer, a hole transport layer, a light emitting layer, an electron injection layer, and/or an electron transport layer. Then, a second electrode is further formed on the organic material layer. The second electrode may be a transparent electrode or a reflective electrode. The top encapsulation layer 11 described above is then applied to cover the top surface of the organic electronic component 23 on the substrate 21. At this time, a method of forming the top encapsulation layer 11 is not particularly limited, and the above sealing composition may be applied to the top surface of the substrate 21 using a process such as screen printing or dispenser application. In addition, a side encapsulation layer 10 for sealing the side surface of the organic electronic element 23 may be applied. The method of forming the top encapsulation layer 11 or the side encapsulation layer 10 may be applied by a method known in the art, and for example, a liquid crystal dropping (drop injection) method may be used.

Furthermore, in the present invention, the top encapsulation layer or the side encapsulation layer encapsulating the organic electronic device may also be subjected to a curing process, wherein the curing process (final curing) may be performed, for example, in a heated chamber. The conditions for final curing may be appropriately selected in consideration of the stability of the organic electronic device and the like.

In one example, the above-described encapsulant composition may be applied to form a top encapsulant layer, followed by thermal curing. It may include thermally curing the encapsulation composition at a temperature of 40 ℃ to 200 ℃, 50 ℃ to 180 ℃, 60 ℃ to 170 ℃, 70 ℃ to 160 ℃, 80 ℃ to 150 ℃, or 90 ℃ to 130 ℃ for 1 hour to 24 hours, 1 hour to 20 hours, 1 hour to 10 hours, or 1 hour to 5 hours. The encapsulating composition may be subjected to a final cure by the step of applying heat.

Advantageous effects

When the composition for encapsulating an organic electronic element is applied to an organic electronic device, the present application may form a structure capable of effectively blocking moisture or oxygen introduced into the organic electronic device from the outside, thereby ensuring the lifespan of the organic electronic device. In addition, the composition may be applied to a top emission organic electronic device to prevent physical and chemical damage of an organic electronic element even though it is applied in direct contact with the organic electronic element while having excellent optical characteristics and processability.

Drawings

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

[ description of reference numerals ]

1: packaging structure

10: side packaging layer

11: top packaging layer

21: substrate

22: cover substrate

23: organic electronic component

Detailed Description

Hereinafter, the present invention will be described in more detail with reference to 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 following examples.