KR20220032721A - Composition for encapsulating organic electronic element - Google Patents

Abstract

The present application relates to a composition for encapsulating an organic electronic device and an organic electronic apparatus comprising the same. The present invention provides the composition for encapsulation which secures the lifespan of the organic electronic apparatus by forming a structure that can effectively block moisture or oxygen flowing into the organic electronic apparatus from the outside and can prevent physical and chemical damage to the organic electronic device while having excellent optical properties and processability applied to the top emission type organic electronic apparatus, and an organic electronic apparatus including the composition.

Description

Composition for encapsulating organic electronic devices {COMPOSITION FOR ENCAPSULATING ORGANIC ELECTRONIC ELEMENT}

The present invention relates to a composition for encapsulating an organic electronic device, 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 that generates an exchange of charges using holes and electrons, and examples thereof 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, has a faster response speed, and is advantageous for thinning a display device or lighting compared to a conventional light source. In addition, OLED is expected to be applied in various fields including various portable devices, monitors, laptops and TVs because of its excellent space utilization.

The light emitting structure of the OLED includes a bottom emission structure and a top emission structure. Among them, the top emission structure (Top Emission) has a higher aperture ratio compared to the bottom emission structure, so it is easy to form a super high-resolution sphere, and it is possible to implement a device with high luminance and excellent power consumption and lifespan.

However, since the OLED having a top emission structure has to be colorless and transparent on the emitting surface of the generated light, there is a limitation that the sealing material must also be colorless and transparent. In addition, the curable composition used in the ODF (one drop filling) process when sealing the OLED device should have low viscosity and little change with time in order to form a uniform coating film. In addition, when an OLED is sealed using a curable composition, outgas is generated during light irradiation or heating and is filled in the device to accelerate the degradation of the device. It is required to provide a curable composition, and in particular, when using a one-component curable composition, it is very important to secure storage stability to ensure fairness.

Therefore, the problem to be solved by the present invention is that it is possible to form a structure that can effectively block moisture or oxygen flowing into the organic electronic device from the outside, thereby securing the life of the organic electronic device. A composition for encapsulation having excellent optical properties applied to a device, preventing deterioration of the device due to outgas generated during curing of the composition, realizing a low viscosity that can be applied to the ODF process, and also having excellent storage stability, and To provide an organic electronic device comprising the.

According to the present application, it is possible to form a structure that can effectively block moisture or oxygen flowing into the organic electronic device from the outside, thereby securing the lifespan of the organic electronic device, realizing a top emission type organic electronic device, and providing an organic electronic device. Provided are an encapsulation composition capable of preventing defects such as dark spots that may occur in a device, and an organic electronic device including the same.

The technical problems of the present invention are not limited to the technical problems mentioned above, and other technical problems not mentioned will be clearly understood by those skilled in the art from the following description.

Since the present invention can have various changes and can have various embodiments, specific embodiments are illustrated in the drawings and described in detail. However, this is not intended to limit the present invention to specific embodiments, and it should be understood to include all modifications, equivalents and substitutes included in the spirit and scope of the present invention.

<Composition for Encapsulation>

This application relates to a composition for encapsulating an organic electronic device. The composition may be a pressure-sensitive adhesive composition or an adhesive composition. The encapsulation composition may be, for example, an encapsulant applied to encapsulating or encapsulating an organic electronic device such as an OLED. In one example, the encapsulation composition of the present application may be applied to encapsulating or encapsulating the entire surface of the organic electronic device. Therefore, after the encapsulation composition is applied to the encapsulation, it may exist in the form of sealing the front surface of the organic electronic device.

As used herein, the term "organic electronic device" refers to an article or device having a structure including an organic material layer that generates an exchange of charges between a pair of electrodes facing each other by using holes and electrons, for example, may include, but are not limited to, a photovoltaic device, a rectifier, a transmitter, and an organic light emitting diode (OLED). In one example of the present application, the organic electronic device may be an OLED.

An exemplary composition for encapsulating an organic electronic device includes a curable compound (A), an initiator (B), and a curing retarder (C), the curing retarder (C) includes an amine-based compound, and the encapsulation composition After curing, the yellowness (ΔYI, yellow index) value measured according to ASTM D 1003 standard using a colorimeter may be 1 or less, and the lower limit thereof is not particularly limited, but may be -2 or more. As the composition according to the present application satisfies the yellowness value as described above, it may be particularly suitable for an OLED having a top emission structure in which the emission surface of the generated light must satisfy colorless and transparency.

In addition, the composition for encapsulating an organic electronic device may satisfy the following general formula (1).

[General formula 1]

0.005 < R/P < 0.11

In General Formula 1, R is a weight part of the curing retarder (C) relative to 100 parts by weight of the curable compound (A), and P is a weight part of the thermal initiator (B) relative to 100 parts by weight of the curable compound (A). In the present specification, parts by weight may mean a weight ratio between each component. Specifically, the lower limit of R/P is 0.006 or more, 0.007 or more, 0.008 or more, 0.009 or more, 0.01 or more, 0.011 or more, 0.012 or more, 0.013 or more, 0.014 or more, 0.015 or more, 0.016 or more, 0.017 or more, 0.018 or more, 0.019 or more. , 0.02 or more, 0.021 or more, 0.022 or more, 0.023 or more, 0.024 or more, 0.025 or more, 0.026 or more, 0.027 or more, 0.028 or more, 0.029 or more, 0.03 or more, 0.04 or more, or 0.05 or more. In addition, the upper limit of R/P may be 0.1 or less, 0.098 or less, 0.096 or less, 0.094 or less, 0.092 or less, 0.09 or less, 0.088 or less, 0.086 or less, 0.7 or less, 0.6 or less, 0.5 or less, 0.4 or less, or 0.3 or less.

The present application provides an encapsulation composition applied to directly contact the device on the top emission type organic electronic device, so it should have excellent optical properties after curing, and prevent device deterioration due to outgas generated during curing of the composition It should be prevented, and a low viscosity that can be applied to the ODF process should be implemented, and storage stability should be secured. Accordingly, the present application provides a composition satisfying the aforementioned general formula 1 while including an amine-based compound as the curing retardant (C), thereby implementing various physical properties required of the composition for encapsulation, in particular, excellent curing degree, It is possible to implement a composition for encapsulating an organic electronic device that can simultaneously implement device reliability and storage stability. In addition, in order to implement the above effects, the present application may adjust the types of compounds and the content of each composition to be described later, but is not limited thereto.

(A) Curable compound

In an embodiment of the present application, the curable compound (A) may be a cation-curable compound. In addition, the curable compound may include at least one or more curable functional groups. The curable functional group may be a cation-curable functional group, for example, one selected from a glycidyl group, an isocyanate group, a hydroxyl group, a carboxyl group, an amide group, an epoxide group, a cyclic ether group, a sulfide group, an acetal group and a lactone group may be more than In addition, the curable compound may be a monofunctional compound or a bifunctional compound or more, and may be a combination of a monofunctional compound and a bifunctional compound or a combination of bifunctional or more functional compounds. The curable compound implements an appropriate degree of crosslinking to encapsulate an organic electronic device, thereby implementing excellent heat resistance and durability at high temperature and high humidity.

In one example, the curable compound (A) may include an epoxy compound having a cyclic structure in the molecular structure. The epoxy compound having a cyclic structure in the molecular structure may include 3 to 10, 4 to 8, or 5 to 7 ring constituent atoms in the molecular structure, and 1 or more or 2 or more cyclic structures in the compound; 10 or less may be included. Also, in one example, the epoxy compound having a cyclic structure in the molecular structure may include at least two or more different compounds. The type of the epoxy compound having a cyclic structure in the molecular structure is not particularly limited, but may include an alicyclic epoxy compound or an aromatic epoxy compound.

In one example, the cycloaliphatic epoxy compound may be an epoxy cyclohexane compound including a unit of Formula 1 below.

[Formula 1]

In Formula 1, R ₁ and R ₂ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and X represents an epoxy group-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 a linear or branched alkylene group having 1 to 18 carbon atoms, -CO-, -O-CO-O-, -COO-, -O- and -CONH- and R ₁ to R ₄ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

As said alicyclic epoxy compound, For example, an epoxycyclohexylmethyl epoxycyclohexanecarboxylate type compound; Epoxycyclohexane carboxylate compound of alkanediol; Epoxy cyclohexylmethyl ester compounds of dicarboxylic acids; Epoxycyclohexylmethyl ether compounds of polyethylene glycol; epoxycyclohexylmethyl ether compounds of alkanediol; diepoxytrispiro compounds; diepoxy monospiro compounds; vinylcyclohexene diepoxide compounds; An epoxycyclopentyl ether compound or a diepoxy tricyclodecane compound may be used. They are stable even at high temperatures, are colorless and transparent after curing, and have excellent toughness and surface hardness.

As the alicyclic epoxy compound as described above, for example, compounds represented by the following Chemical Formulas 3 to 7 may be exemplified.

[Formula 3]

In Formula 3, R ₁ to R ₄ 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, R ₁ to R ₄ 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, R ₁ to R ₄ 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, R ₁ to R ₄ 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, R ₁ to R ₄ 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 is bis(3,4-epoxycyclohexyl)oxalate, bis(3,4-epoxycyclohexylmethyl)adipate, bis(3,4-epoxy-6-methylcyclo Hexylmethyl) adipate, bis (3,4-epoxycyclohexylmethyl) pipelate, 3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate, 3,4-epoxycyclohexanecarboxyl Rate, 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)cyclohexanecarboxylate, 3,4-epoxy-5-methylcyclohexyl Methyl (3,4-epoxy-5-methyl) cyclohexanecarboxylate and caprolactone adducts thereof, limonene dioxide, vinylcyclohexene dioxide, seloxide manufactured by Daicel Corporation, 2021P, or 8000 can be cited as examples. and may be used in combination of two or more types. These may be synthesized by a conventional method, and a commercially available product may be used. When the curable composition according to the present application is cured by using the alicyclic epoxy compound, physical properties such as colorless transparency, low temperature curing and chemical resistance, and heat resistance at high temperature and high humidity can be secured.

In one example, the curable compound (A) may be a compound having a weight average molecular weight of 1,000 g/mol or less. The upper limit of the weight average molecular weight of the curable compound (A) may be 900 g/mol or less, 800 g/mol or less, 700 g/mol or less, 600 g/mol or less, or 500 g/mol or less, and the lower limit thereof is 50 g /mol or more, 100 g/mol or more, or 200 g/mol or more. The present application includes the curable compound of the above molecular weight, so that it is possible to form a uniform coating film after application while excellently implementing the coating properties of the encapsulation composition applied in the liquid phase. In the present specification, the weight average molecular weight means a value converted to standard polystyrene measured by gel permeation chromatograph (GPC).

In one example, the curable compound (A) is 70% by weight or more, 75% by weight or more, 80% by weight or more, 85% by weight or more, 90% by weight or more, 95% by weight or more in the composition for encapsulating an organic electronic device. Or it may be included in a proportion of 98% by weight or more. The upper limit is not particularly limited, but may be 99.9% by weight or 99.8% by weight.

(B) initiator

In an embodiment of the present application, the initiator (B) may be a thermal initiator, and more specifically, may be a thermal cationic initiator. As the thermal cationic initiator, BF ₄ ^- , ASF ₆ ^- , PF ₆ ^- , SbF ₆ ^- , or (BX ₄ ) ^- (provided that X represents a phenyl group substituted with at least two fluorine or trifluoromethyl groups) The anion may be a sulfonium salt, a phosphonium salt, a quaternary ammonium salt, a diazonium salt, or an iodonium salt.

Examples of the sulfonium salt include triphenylsulfonium boron tetrafluoride, triphenylsulfonium 6 antimony fluoride, triphenylsulfonium 6 arsenic fluoride, tri(4-methoxyphenyl)sulfonium 6 arsenic fluoride, and diphenyl (4-phenylthiophenyl). ) sulfonium hexafluoride and arsenic fluoride.

As said phosphonium salt, ethyl triphenylphosphonium 6 antimony fluoride, tetrabutyl phosphonium 6 antimony fluoride, etc. are mentioned.

Examples of the quaternary ammonium salt include dimethylphenyl(4-methoxybenzyl)ammonium hexafluorophosphate, dimethylphenyl(4-methoxybenzyl)ammonium hexafluoroantimonate, dimethylphenyl(4-methoxybenzyl) Ammonium tetrakis (pentafluorophenyl) borate, dimethylphenyl (4-methyl benzyl) ammonium hexafluoro hexafluoro phosphate, dimethylphenyl (4-methyl benzyl) ammonium hexafluoro antimonate, dimethylphenyl (4-methyl) Benzyl) ammonium hexafluoro tetrakis (pentafluorophenyl) borate, methyl phenyl dibenzyl ammonium, methyl phenyl dibenzyl ammonium hexafluoro antimonate hexafluoro phosphate, methylphenirzibenziranmonium thracis ( Pentafluoro phenyl) borate, phenyltribenzyl ammonium tetrakis (pentafluoro phenyl) borate, dimethylphenyl (3,4-dimethylbenzyl) ammonium tetrakis (pentafluoro phenyl) borate, N,N-dimethyl-N- Benzyl anilinium 6 antimony fluoride, N,N-diethyl-N-benzyl anilinium boron tetrafluoride, N,N-dimethyl-N-benzylpyridinium 6 antimony fluoride, N,N-diethyl-N-benzylpyridinium trifluoromethane sulfonic acid etc. are mentioned.

Examples of the iodonium ion include diphenyliodonium, di-p-tolyliodonium, bis(4-dodecylphenyl)iodonium, bis(4-methoxyphenyl)iodonium, (4-octyloxy Phenyl)phenyliodonium, bis(4-decyloxyphenyl)iodonium, 4-(2-hydroxytetradecyloxy)phenylphenyliodonium, 4-isopropylphenyl(p-tolyl)iodonium , isobutylphenyl (p-tolyl) iodonium, and the like.

In an embodiment of the present application, the thermal initiator (B) may include 0.01 to 5 parts by weight based on 100 parts by weight of the curable compound (A). In one example, the lower limit of the thermal initiator (B) is 0.02 parts by weight or more, 0.03 parts by weight or more, 0.04 parts by weight or more, 0.05 parts by weight or more, 0.06 parts by weight or more, 0.09 parts by weight or more, 0.12 parts by weight or more, or 0.18 parts by weight or more. It can be more than wealth. In addition, the upper limit of the thermal initiator (B) is 4.7 parts by weight or less, 4.3 parts by weight or less, 4 parts by weight or less, 3.8 parts by weight or less, 3.5 parts by weight or less, 3.2 parts by weight or less, 3 parts by weight or less, 2.8 parts by weight or less, 2.6 parts by weight or less, 2.4 parts by weight or less, 2.2 parts by weight or less, 2 parts by weight or less, 1.8 parts by weight or less, 1.6 parts by weight or less, 1.4 parts by weight or less, 1.2 parts by weight or less, 1 part by weight or less, 0.8 parts by weight or less; 0.5 parts by weight or less, 0.3 parts by weight or less, 0.25 parts by weight or less, 0.2 parts by weight or less, 0.19 parts by weight or less, 0.13 parts by weight or less, or 0.09 parts by weight or less. The composition for encapsulating an organic electronic device of the present application contains the thermal initiator (B) in the above weight ratio range, so that the hardness can be realized during curing. It is possible to provide an encapsulant having high durability reliability by suppressing out-gas.

(C) curing retardant

The curable composition according to the present application may include a curing retardant (C). The curing retardant (C) is composed of an amine compound, a polyether compound, boric acid, phenylboric acid, salicylic acid, hydrochloric acid, sulfuric acid, oxamic acid, tetraphthalic acid, isophthalic acid, phosphoric acid, acetic acid, and lactic acid. It may be at least one selected from the group.

In one example, in consideration of the objects and effects of the present invention described above, the curing retardant (C) may be an amine-based compound, in particular, an amine-based compound capable of providing an electron pair. Nitrogen present in the amine compound contains a lone pair of electrons, thereby providing electrons to the Bronsted acid formed from the thermal initiator, thereby implementing a delay effect on the cationic polymerization reaction.

In addition, the composition according to the present application does not include a thiol-based compound, and an amine-based compound was used as an initiator for the thiol-based compound, but the present application provides a curing retardant (C) for the curable compound (A). As such, an amine-based compound may be used.

In one example, the amine-based compound may satisfy a boiling point of 100 °C or higher, and as an example, may have a boiling point of 110 °C to 500 °C. The lower limit of the boiling point is 110 °C or more, 120 °C or more, 130 °C or more, 140 °C or more, 150 °C or more, 160 °C or more, 170 °C or more, 180 °C or more, 190 °C or more, 200 °C or higher, 210 °C or higher, 220 °C or higher, 230 °C or higher, 240 °C or higher, 250 °C or higher, or 260 °C or higher, and the upper limit of the boiling point is not limited, but 500 as an example °C or lower, 400 °C or lower, or 350 °C or lower. Furthermore, although an epoxy-based compound has been used as a curing retardant in the past, the epoxy-based compound has a low boiling point and is highly likely to be thermally decomposed, which may cause a large amount of outgas. On the other hand, as in the present application, when an amine-based compound satisfying the boiling point is used as a curing retardant that does not participate in the curing reaction, the cationic polymerization reaction is sufficiently delayed according to the electron pair providing ability of nitrogen as well as out due to thermal decomposition. It is possible to exert the effect of reducing the amount of gas emission.

In one example, the amine-based compound may not include an aromatic ring. When an amine-based compound containing an aromatic ring is used as a curing retardant, it may cause yellowing due to electron transition at high temperature, so the emission surface does not satisfy colorless and transparent properties. may be unsuitable for OLEDs with

In one example, the amine-based compound may satisfy a pKa of 9 or more at 25 °C. In the present specification, pKa is an acid dissociation constant for water, and when it is not known in the literature or the like, it is a calculated value obtained using Advanced Chemistry Development (ACD/Labs) Software. The lower limit of the pKa is 9.1 or more, 9.2 or more, 9.3 or more, 9.4 or more, 9.5 or more, 9.6 or more, 9.7 or more, 9.8 or more, 9.9 or more, 10 or more, 10.1 or more, 10.2 or more, 10.3 or more, 10.4 or more, 10.5 or more, 10.6 or greater, 10.7 or greater, 10.8 or greater, 10.9 or greater, or 11 or greater. When an amine-based compound having a pKa satisfying the above specific value is used as the curing retardant (C), it is possible to sufficiently implement the retardation effect on the cationic polymerization reaction due to the excellent electron pair providing ability of nitrogen, and as a result, according to the present application The composition for encapsulation can secure fairness according to excellent storage stability.

As an example, the amine-based compound that can be used as the curing retarder (C) of the present application is N,N-dicyclohexylmethylamine (N,N-dicyclohexyilmethylamine), dicyclohexylamine (dicyclohexylamine), dibutylamine (dibutylamine), cyclohexanemethylamine (cyclohexanemethylamine), etc. may be, but is not limited thereto.

In the embodiment of the present application, the curing retarder (C) may be included in an amount of 0.001 to 0.5 parts by weight based on 100 parts by weight of the curable compound. The lower limit (C) of the curing retardant is 0.002 parts by weight or more, 0.003 parts by weight or more, 0.004 parts by weight or more, 0.005 parts by weight or more, 0.006 parts by weight or more, 0.007 parts by weight or more, 0.008 parts by weight or more, or 0.009 parts by weight or more. can In addition, the upper limit (C) of the curing retarder is 0.4 parts by weight or less, 0.35 parts by weight or less, 0.3 parts by weight or less, 0.28 parts by weight or less, 0.26 parts by weight or less, 0.24 parts by weight or less, 0.22 parts by weight or less, 0.2 parts by weight or less. , 0.18 parts by weight or less, 0.16 parts by weight or less, 0.14 parts by weight or less, or 0.12 parts by weight or less. The present application can provide a composition for encapsulation capable of simultaneously implementing excellent storage stability while satisfying excellent optical properties and thermal stability by adjusting the content.

In addition to the above-described configuration, the composition for encapsulation according to the present application may include various additives within a range that does not affect the effects of the above-described invention. For example, the composition for encapsulation may include an antifoaming agent, a coupling agent, a tackifier, a UV stabilizer, or an antioxidant in an appropriate range according to desired physical properties. In one example, the composition for encapsulation may further include an antifoaming agent. In the present application, by including an antifoaming agent, in the application process of the above-described encapsulation composition, defoaming properties may be implemented, thereby providing a reliable encapsulation structure. In addition, as long as the physical properties of the composition for encapsulation required in the present application are satisfied, the type of the antifoaming agent is not particularly limited.

In one example, the composition for encapsulation may have excellent light transmittance in a visible light region after curing. In one example, the composition for encapsulation of the present application may exhibit a light transmittance of 80% or more according to JIS K7105 standard after curing. For example, the composition for encapsulation may have a light transmittance of 85% or more, 90% or more, 92% or more, or 93% or more with respect to the visible light region. In addition, the encapsulant of the present application may exhibit a low haze with excellent light transmittance. In one example, the encapsulation composition may have a haze measured according to the standard of JIS K7105 after curing of 5% or less, 4% or less, 3% or less, or 1% or less. The optical properties may be measured at 550 nm using a UV-Vis Spectrometer.

In one example, 300 mg of the composition for encapsulation is cured by heating at 100 °C for 1 hour, and Purge & Trap sampler (JAI JTD-505Ⅲ) - GC/MSD system (Agilent 7890B/5977A) measuring instrument Using, the sample was subjected to a purge and trap at 100 °C for 60 minutes, and then the total amount of outgas was measured using gas chromatography mass spectrometry. In this case, the measured outgas amount may be less than 1,000 ppm, and specifically, less than 700 ppm, less than 500 ppm, less than 400 ppm, less than 300 ppm, less than 200 ppm, less than 100 ppm, or less than 50 ppm. As can be seen, the composition for encapsulating organic electrons according to the present application uses one that satisfies the boiling point of a curing retardant that does not participate in the curing reaction above a specific range, thereby preventing volatile components from being generated in the device even in a high-temperature process. there is.

In one example, the composition for encapsulation may be liquid at room temperature, for example, about 25 °C. In an embodiment of the present application, the encapsulation composition may be a solvent-free type liquid. The composition for encapsulation may be applied to encapsulating an organic electronic device, and specifically, may be applied to encapsulating the entire surface of an organic electronic device. In the present application, since the composition for encapsulation has a liquid form at room temperature, the device can be encapsulated by applying the composition to the entire surface of the organic electronic device.

In one example, the composition for encapsulation has a viscosity of 1,500 cP or less, 1,000 cP or less, 500 cP or less, 350 cP or less, 300 cP or less, or 250 cP or less at a temperature of 25 °C and a rotation speed of 100 rpm. can The lower limit is not particularly limited, but may be 10 cP or more or 30 cP or more. The viscosity was measured according to the torque in the RV-63 spindle using a Brookfield viscometer (LV type). As the composition for encapsulation according to the present application satisfies the above viscosity, it may be suitable for the ODF process.

In one example, after sealing 40 g of the composition for sealing in a glass bottle, leaving it in an oven at 40 °C, the pot life ( When the pot-lofe) is measured, it may be 100 hours or more, 110 hours or more, 120 hours or more, 130 hours or more, or 140 hours or more. That is, the composition for encapsulation according to the present application has excellent storage stability, so that an encapsulant with excellent physical properties can be implemented.

<Organic Electronic Devices>

This application also relates to an organic electronic device. An exemplary organic electronic device includes, as shown in FIG. 1 , a substrate 21; an organic electronic device 23 formed on the substrate 21; and a front encapsulation layer 11 that seals the front surface of the organic electronic device 23 and includes the encapsulation composition described above. In addition, the exemplary organic electronic device may further include a side encapsulation layer 10 formed on the substrate 21 to surround the side surface of the organic electronic device 23 . Accordingly, the organic electronic device may have the encapsulation structure 1 including the front encapsulation layer 11 and the side encapsulation layer 10 .

The front encapsulation layer and the side encapsulation layer may exist on the same plane. In the above, "the same" may mean substantially the same. For example, substantially the same in the same plane means that there may be an error of ±5 μm or ±1 μm in the thickness direction. The front encapsulation layer may encapsulate an upper surface of the organic electronic device formed on the substrate, and may encapsulate not only the upper surface but also the side surfaces. The side encapsulation layer may be formed on the side surface of the device, but may not directly contact the side surface of the organic electronic device. For example, the front encapsulation layer may be encapsulated in direct contact with the top and side surfaces of the device. That is, the side encapsulation layer may be positioned on the periphery of the substrate in a plan view of the organic electronic device without contacting the device.

As used herein, the term “peripheral portion” refers to an edge portion of the periphery. That is, in the above, the periphery of the substrate may mean an edge portion of the periphery of the substrate.

The organic electronic device of the present application may further include a cover substrate 22 present on the front encapsulation layer. The material of the substrate or the cover substrate is not particularly limited, and a material known in the art may be used. For example, the substrate or the cover substrate may be glass or a polymer film. The polymer film is, for example, a polyethylene terephthalate film, a polytetrafluoroethylene film, a polyethylene film, a polypropylene film, a polybutene film, a polybutadiene film, a vinyl chloride copolymer film, a polyurethane film, an ethylene-vinyl acetate film, ethylene -Propylene copolymer film, ethylene-ethyl acrylate copolymer film, ethylene-methyl acrylate copolymer film, polyimide film, etc. can be used.

The material constituting the side encapsulation layer is not particularly limited, and may be an adhesive composition or a pressure-sensitive adhesive composition. The side encapsulation layer may include an encapsulation resin, wherein the encapsulation resin is an acrylic resin, an epoxy resin, a silicone resin, a fluororesin, a styrene resin, a polyolefin resin, a thermoplastic elastomer, a polyoxyalkylene resin, a polyester resin, or a polyvinyl chloride. Resin, polycarbonate resin, polyphenylene sulfide resin, polyamide resin, or mixtures thereof may be exemplified. Components constituting the side encapsulation layer may be the same as or different from the above-described composition for encapsulation.

In one example, the organic electronic device includes a reflective electrode layer (or transparent electrode layer) formed on a substrate, an organic layer formed on the reflective electrode layer (or transparent electrode layer) and including at least a light emitting layer, and a transparent electrode layer formed on the organic layer ( or a reflective electrode layer).

In the present application, the organic electronic device 23 may be an organic light emitting diode.

In one example, the organic electronic device according to the present application may be a top emission type, but is not limited thereto, and may also be applied to a bottom emission type.

The organic electronic device may further include a protective layer for protecting the electrode and the light emitting layer of the device. The passivation layer may have a structure in which an organic layer and an inorganic layer are alternately stacked. The protective layer may be a protective layer by chemical vapor deposition (CVD), and the material may be a known inorganic material, for example, silicon nitride (SiNx) may be used. In one example, silicon nitride (SiNx) used as the passivation layer may be deposited to a thickness of 0.01 μm to 5 μm.

The above-described composition for encapsulation may be in direct contact with the electrode of the organic electronic device or the protective film.

<Method for manufacturing organic electronic device>

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

In one example, the manufacturing method includes applying the above-described encapsulating composition on the substrate 21 on which the organic electronic device 23 is formed to seal the entire surface of the organic electronic device 23; and curing the composition. The step of applying the encapsulation composition may be a step of forming the aforementioned front encapsulation layer 11 .

In the above, the substrate 21 on which the organic electronic device 23 is formed, for example, a reflective electrode or a transparent electrode is formed on the substrate 21 such as glass or 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. Next, a second electrode is further formed on the organic material layer. The second electrode may be a transparent electrode or a reflective electrode. Then, the aforementioned front encapsulation layer 11 is applied to cover the entire surface of the organic electronic device 23 on the substrate 21 . In this case, the method of forming the front encapsulation layer 11 is not particularly limited, and processes such as screen printing and dispenser application of the above encapsulation composition on the entire surface of the substrate 21 may be used. In addition, a side sealing layer 10 for sealing the side surface of the organic electronic device 23 may be applied. As a method of forming the front encapsulation layer 11 or the side encapsulation layer 10, a method known in the art may be applied, for example, a liquid crystal drop filling process may be used.

Also, in the present invention, a curing process may be performed on the front or side encapsulation layer encapsulating the organic electronic device, and this curing process (main curing) may be performed, for example, in a heating chamber. Conditions for main curing may be appropriately selected in consideration of the stability of the organic electronic device.

In one example, after the above-described encapsulation composition is applied to form a front encapsulation layer, thermal curing may be performed. 40 °C to 200 °C, 50 °C to 180 °C, 60 °C to 170 °C, 70 °C to 160 °C, 80 °C to 150 °C or 90 °C to the above encapsulation composition It may include thermal curing at a temperature of 130 °C for 1 hour to 24 hours, 1 hour to 20 hours, 1 hour to 10 hours, or 1 hour to 5 hours. Through the step of applying the heat, the composition for encapsulation may undergo main curing.

As described above, the composition for encapsulation according to embodiments of the present invention is applied to a top emission type organic electronic device, has excellent optical properties and processability, and satisfies the viscosity applicable to the ODF process. It is possible to prevent deterioration of the device and ensure thermal stability.

However, the effects of the present invention are not limited to the above-mentioned effects, and other effects not mentioned will be clearly understood by those skilled in the art from the following description.

1 is a cross-sectional view illustrating an organic electronic device according to an exemplary embodiment of the present invention.

Hereinafter, a preferred experimental example (example) is presented to help the understanding of the present invention. However, the following experimental examples are only for helping understanding of the present invention, and the present invention is not limited by the following experimental examples.

Example 1

As a curable compound at room temperature, an alicyclic epoxy compound (Celloxide2021P from DAICEL) was added to the container in a weight ratio of 100. Based on 100 parts by weight of the curable compound, 0.7 parts by weight of a thermal cationic initiator (CXC-1821 manufactured by King industry) and 0.01 parts by weight of a curing retardant dicyclohexylamine were added to the container. The mixture was stirred to prepare a uniform composition solution.

Example 2

As a curable compound at room temperature, an alicyclic epoxy compound (Celloxide2021P from DAICEL) was added to the container in a weight ratio of 100. Based on 100 parts by weight of the curable compound, 0.7 parts by weight of a thermal cationic initiator (CXC-1821 manufactured by King Industry Co., Ltd.) and 0.02 parts by weight of a curing retardant dicyclohexylamine were added to the container. The mixture was stirred to prepare a uniform composition solution.

Example 3

As a curable compound at room temperature, an alicyclic epoxy compound (Celloxide2021P from DAICEL) was added to the container in a weight ratio of 100. Based on 100 parts by weight of the curable compound, 0.7 parts by weight of a thermal cationic initiator (CXC-1821 manufactured by King industry) and 0.03 parts by weight of a curing retardant dicyclohexylamine were added to the container. The mixture was stirred to prepare a uniform composition solution.

Example 4

As a curable compound at room temperature, an alicyclic epoxy compound (Celloxide2021P from DAICEL) was added to the container in a weight ratio of 100. Based on 100 parts by weight of the curable compound, 0.7 parts by weight of a thermal cationic initiator (CXC-1821 manufactured by King industry) and 0.04 parts by weight of a curing retardant dicyclohexylamine were added to the container. The mixture was stirred to prepare a uniform composition solution.

Example 5

As a curable compound at room temperature, an alicyclic epoxy compound (Celloxide2021P from DAICEL) was added to the container in a weight ratio of 100. Based on 100 parts by weight of the curable compound, 0.7 parts by weight of a thermal cationic initiator (CXC-1821 manufactured by King industry) and 0.06 parts by weight of a curing retardant dicyclohexylamine were added to the container. The mixture was stirred to prepare a uniform composition solution.

Example 6

As a curable compound at room temperature, an alicyclic epoxy compound (Celloxide2021P from DAICEL) was added to the container in a weight ratio of 100. Based on 100 parts by weight of the curable compound, 1.4 parts by weight of a thermal cationic initiator (CXC-1821 manufactured by King industry) and 0.04 parts by weight of a curing retardant dicyclohexylamine were added to the container. The mixture was stirred to prepare a uniform composition solution.

Comparative Example 1

As a curable compound at room temperature, an alicyclic epoxy compound (Celloxide2021P from DAICEL) was added to the container in a weight ratio of 100. Based on 100 parts by weight of the curable compound, 0.7 parts by weight of a thermal cationic initiator (CXC-1821 manufactured by King industry) and 0.08 parts by weight of a curing retardant dicyclohexylamine were added to the container. The mixture was stirred to prepare a uniform composition solution.

Comparative Example 2

As a curable compound at room temperature, an alicyclic epoxy compound (Celloxide2021P from DAICEL) was added to the container in a weight ratio of 100. Based on 100 parts by weight of the curable compound, 0.7 parts by weight of a thermal cationic initiator (CXC-1821 manufactured by King Industry Co.) and 0.1 parts by weight of a curing retardant dicyclohexylamine were added to the container. The mixture was stirred to prepare a uniform composition solution.

Comparative Example 3

As a curable compound at room temperature, an alicyclic epoxy compound (Celloxide2021P from DAICEL) was added to the container in a weight ratio of 100. Based on 100 parts by weight of the curable compound, 0.7 parts by weight of a thermal cationic initiator (CXC-1821 manufactured by King industry) and 0.01 parts by weight of a curing retardant benzylamine were added to the container. The mixture was stirred to prepare a uniform composition solution.

Comparative Example 4

As a curable compound at room temperature, an alicyclic epoxy compound (Celloxide2021P from DAICEL) was added to the container in a weight ratio of 100. Based on 100 parts by weight of the curable compound, 0.7 parts by weight of a thermal cationic initiator (CXC-1821 manufactured by King industry) and 0.04 parts by weight of a curing retardant benzylamine were added to the container. The mixture was stirred to prepare a uniform composition solution.

Comparative Example 5

As a curable compound at room temperature, an alicyclic epoxy compound (Celloxide2021P from DAICEL) was added to the container at a weight ratio of 100. Based on 100 parts by weight of the curable compound, 0.7 parts by weight of a thermal cationic initiator (CXC-1821 manufactured by King industry) and 0.08 parts by weight of a curing retardant benzylamine were added to the container. The mixture was stirred to prepare a uniform composition solution.

Table 1 below summarizes the weight ratio of the curable compound, and parts by weight of the thermal cationic initiator and the curing retarder with respect to 100 parts by weight of the curable compound.

[Table 1]

The physical properties of Examples and Comparative Examples were evaluated as follows, and the evaluation results are summarized in Table 2.

1. Pot-Life Measurements

40 g of the compositions prepared in Examples and Comparative Examples were sealed in a glass bottle, and then left in an oven at 40 °C, and the time required to increase the viscosity by 10% compared to the initial viscosity just before sealing was recorded.

2. Measurement of reaction initiation temperature

About 5 mg of the compositions prepared in Examples and Comparative Examples were put in a dedicated pan, and a differential scanning calorimeter (DSC Q2000 from TA Instruments) was used from 30 °C to 300 °C at a temperature increase rate of 10 °C/min. to measure the calorific value.

3. Measurement of the degree of hardening

The encapsulation composition prepared in Examples and Comparative Examples was coated on a glass substrate to a thickness of 100 µm and cured at 100 °C for 1 hour to prepare a cured specimen. When the cured specimen was touched while wearing gloves, if there was no liquid or semi-solid substance on the hand, it was classified as OK, otherwise, it was classified as NG.

4. Measurement of yellowness (YI, yellow index)

After injecting the encapsulation compositions prepared in Examples and Comparative Examples to a thickness of 50 μm and leaving them at 40 °C for 5 days, using a colorimeter (COH-400 from Nippon Denshoku), the yellowness ( ΔYI, yellow index) values were measured. If the yellowness (ΔYI) was 1 or less, it was classified as OK, and if it was more than 1, it was classified as NG.

[Table 2]

Although it has been described with reference to the above embodiments, it will be understood by those skilled in the art that various modifications and changes can be made to the present invention without departing from the spirit and scope of the present invention as set forth in the claims below. will be able

1: bag structure
10: side encapsulation layer
11: Front encapsulation layer
21: substrate
22: cover substrate
23: organic electronic device

Claims (15)

A composition comprising a curable compound (A), an initiator (B), and a curing retarder (C), wherein the curing retardant (C) includes an amine compound,
After curing the composition, the yellowness (ΔYI, yellow index) value measured according to ASTM D 1003 standard using a colorimeter is 1 or less,
A composition for encapsulating an organic electronic device satisfying the following general formula 1:
[General formula 1]
0.005 < R/P < 0.11
In General Formula 1, R is a weight part of the curing retarder (C) relative to 100 parts by weight of the curable compound (A), and P is a weight part of the thermal initiator (B) relative to 100 parts by weight of the curable compound (A). The method of claim 1,
The curing retardant (C) is an amine-based compound that does not contain an aromatic ring, an organic electronic device encapsulation composition. The method of claim 1,
The curing retardant (C) is contained in an amount of 0.001 to 0.5 parts by weight based on 100 parts by weight of the curable compound (A). The method of claim 1,
The curable compound (A) is an organic electronic device encapsulation composition comprising at least one curable functional group. 5. The method of claim 4,
The curable functional group is at least one selected from a glycidyl group, an isocyanate group, a hydroxyl group, a carboxyl group, an amide group, an epoxide group, a cyclic ether group, a sulfide group, an acetal group and a lactone group. The method of claim 1,
The curable compound (A) is an organic electronic device encapsulation composition comprising an epoxy compound having a cyclic structure in the molecular structure. 7. The method of claim 6,
The epoxy compound having a cyclic structure in the molecular structure is a composition for encapsulating an organic electronic device in which the ring constituent atoms in the molecular structure are in the range of 3 to 10. 7. The method of claim 6,
The epoxy compound having a cyclic structure in the molecular structure is an alicyclic epoxy compound, an organic electronic device encapsulation composition. The method of claim 1,
The initiator (B) is a thermal cationic initiator, an organic electronic device encapsulation composition. The method of claim 1,
_The initiator ( _B ) is ^a sulfonium salt ^, phosphonium salt ^, _quaternary ammonium salt ^, _{diazonium salt} ^, or A composition for encapsulating an organic electronic device containing an iodonium salt, wherein X represents phenyl substituted with at least two fluorine or trifluoromethyl groups. The method of claim 1,
The initiator (B) is an organic electronic device encapsulation composition comprising 0.01 to 5 parts by weight based on 100 parts by weight of the curable compound. The method of claim 1,
The composition for encapsulating an organic electronic device has a transmittance of 80% or more in the visible light region according to JIS K7105 standard after curing. Board; an organic electronic device formed on the substrate; and a front encapsulation layer that seals the front surface of the organic electronic device and includes the composition for encapsulating an organic electronic device according to claim 1 . 14. The method of claim 13,
An organic electronic device further comprising a side encapsulation layer formed on a substrate to surround a side surface of the organic electronic device, wherein the side encapsulation layer and the front encapsulation layer are on the same plane. applying the organic electronic device encapsulation composition of claim 1 on the substrate on which the organic electronic device is formed to seal the entire surface of the organic electronic device; and curing the composition.

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