KR20220160363A - Encapsulating composition and Organic electronic device comprising the same - Google Patents

Abstract

The present application provides: a sealant composition, which can effectively block moisture or oxygen flowing into an organic electronic device from the outside to secure the lifespan of the organic electronic device, realizes a top emission type organic electronic device, and is applicable by an inkjet method; a manufacturing method thereof; and an organic electronic device including the same. The sealant composition contains a cationically curable compound having at least one cationically curable functional group.

Description

Encapsulating composition and organic electronic device comprising the same

The present invention relates to an encapsulant composition and an organic electronic device including the same.

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

In particular, Organic Light Emitting Diode (OLED) is a self-luminous display device having a light emitting part that emits light. Compared to conventional light sources, organic light emitting diode (OLED) consumes less power and has a faster response speed, so it is currently used in various fields as a display device. is applied in

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

An object to be solved by the present invention is to provide a sealing material composition capable of implementing low dielectric constant characteristics. 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 make various changes and 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 should be understood to include all modifications, equivalents, and substitutes included in the spirit and scope of the present invention.

It will be appreciated that when an element such as a layer, region or substrate is referred to as being “on” another element, it may be directly on the other element or intervening elements may exist. .

Terms used in this application are only used to describe specific embodiments, and are not intended to limit the present invention. Singular expressions include plural expressions unless the context clearly dictates otherwise. In this application, the terms "include" or "have" are intended to designate that there is a feature, number, step, operation, component, part, or combination thereof described in the specification, but one or more other features It should be understood that the presence or addition of numbers, steps, operations, components, parts, or combinations thereof is not precluded.

Unless defined otherwise, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which the present invention belongs. Terms such as those defined in commonly used dictionaries should be interpreted as having a meaning consistent with the meaning in the context of the related art, and unless explicitly defined in this application, they should not be interpreted in an ideal or excessively formal meaning. don't

<Sealing material composition>

The present application relates to an organic electronic device sealing material composition. The sealant composition may be, for example, a sealant applied to encapsulate or encapsulate an organic electronic device such as an OLED. In one example, the sealant composition of the present application may be applied to encapsulate or encapsulate the entire surface of an organic electronic device. Therefore, after the sealant composition is applied for encapsulation, it may exist in the form of sealing the front surface of the organic electronic device.

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

As the present application provides an encapsulant composition applied on a top emission type organic electronic device to directly contact the device, it should have excellent optical properties after curing and prevent deterioration of the device due to outgas generated during curing of the composition. Should be. In addition, the sealant composition of the present application should have excellent ejectability, spreadability, and low viscosity in order to be applied to the inkjet process, and should be able to prevent damage due to the inorganic layer formation process in the sealing layer by implementing high surface hardness after curing. do.

In particular, as the sealing material composition according to the present application satisfies a certain level or less in shrinkage after curing, it should be able to have excellent reliability by minimizing the gap between the organic layer and the inorganic layer formed adjacent to the organic layer according to the curing of the sealing material composition. .

In addition, in the conventional organic electronic device, in order to prevent interference between circuits of the electronic device, the thickness of the organic layer constituting the organic electronic device is formed thick. However, according to the thinning trend of organic electronic devices, there is a limit to forming the organic layer thickly. Moreover, as the organic electronic device is enlarged and the area to which the organic layer is applied increases, it is necessary to implement a low dielectric constant in order to solve the problem of interference between circuits.

Accordingly, the present application can provide a composition for encapsulating an organic electronic device capable of simultaneously implementing excellent durability and low permittivity as well as the optical properties, low viscosity, and high hardness by using a specific compositional formulation as described below.

In the present application, the sealant composition may include a curable compound having at least one curable functional group, and the curable compound may be a photocurable or thermocurable compound. As an example, the sealing material composition according to the present application may include a cation-curable curable compound having a cation-curable functional group as a curable functional group.

In one embodiment, the sealant composition of the present application includes a cation-curable compound having at least one cation-curable functional group, and the cation-curable compound may include 10 to 43% by weight of the alicyclic epoxy compound (A). As an example, the alicyclic epoxy compound (A) is present in an amount of 11% by weight or more, 12% by weight or more, 13% by weight or more, 14% by weight or more, 15% by weight or more, 16% by weight or more, 17% by weight or more based on the sealing material composition. 18 wt% or more, 19 wt% or more, 20 wt% or more, 21 wt% or more, 22 wt% or more, 23 wt% or more, 24 wt% or more, 25 wt% or more, 27 wt% or more, 30 wt% or more, 35% by weight or more, or 37% by weight or more, 42% by weight or less, 41% by weight or less, 40% by weight or less, 35% by weight or less, 33% by weight or less, 30% by weight or less, 27% by weight or less or less, or 25% by weight or less. By including the alicyclic epoxy compound (A) within a specific range, the desired composition of the present invention can be implemented.

In addition, the sealant composition of the present application has a shrinkage rate different from Formula 1 of 10% or less, 8.5% or less, 8% or less, 7.5% or less, 7% or less, 6.5% or less, 6% or less, 5.5% or less, 5.3% or less , 5.1% or less, 4.9% or less, 4.7% or less, or 4.5% or less. Since there is no change according to the shrinkage rate, it has excellent durability, so it is meaningless to limit the lower limit, but as an example, it may be 0.01% or more.

[Formula 1]

Shrinkage rate (%) = (Volume of sealing material composition before curing - Volume of sealing material composition after curing) / Volume of sealing material composition before curing × 100

Here, the shrinkage rate refers to the change in volume before and after curing of the sealing material composition, and may be measured at 25°C. In detail, as described below, “encapsulant composition before curing” may mean a sealant composition including a cation-curable compound prior to curing, and “sealant composition after curing” is an aluminum plate or glass substrate on glass It may be obtained by applying a "sealant composition before curing" on top or coating by an inkjet printing method, and then UV curing with a light amount of about 1,000 mJ/cm ² .

As an example, a volume value of the "sealant composition before curing" may be obtained by measuring a certain volume of the sealant composition before curing, and after curing the composition, the "volume of the sealant composition after curing" may be calculated according to Archimedes' principle. The volume value of the "sealing material composition after curing" can be obtained by measuring. More specifically, for example, the volume of the sealing material composition after curing was determined using XS205 analytical balance manufactured by Mettler and a density measurement kit "solid and liquid density measurement kit", using the following general formula 2 to determine the volume of the sealing material composition after curing. The density (ρ) can be obtained, and the volume can be converted from this.

[Formula 2]

ρ=(α×ρ ₀ ) / (α-β)

In Formula 2, ρ is the density of the sealing material composition after curing, α is the mass of the sealing material composition after curing in the air, β is the mass of the sealing material composition after curing in the fluid, ρ ₀ is the density of the fluid at 25 ° C indicates

As described above, since the shrinkage rate of the sealing material composition according to the present invention is controlled to a certain level or less after curing, the clearance between the organic layer and the inorganic layer formed above or below the organic layer according to curing of the sealing material composition is minimized, resulting in better durability of the device. It is possible to further improve the reliability of the device by securing.

Here, the alicyclic epoxy compound (A) may mean an epoxy compound containing at least one epoxy group as a cation-curable functional group, not including an oxetane group or a vinyl ether group, and further having a cyclic structure in the molecular structure. In one example, the alicyclic epoxy compound (A) may have at least 2 or more and 10 or less cyclic structures in the molecular structure, and the cyclic structure is composed of 3 to 10, 4 to 8, or 5 to 7 ring atoms. It can be. As an example, the alicyclic epoxy compound (A) may include two or more different compounds, and the type is not particularly limited.

In one example, the alicyclic epoxy compound (A) may include a compound represented by Formula 1 below.

[Formula 1]

In Formula 1, X is a single bond, a linear or branched chain alkylene group having 1 to 18 carbon atoms, -CO-, -O-CO-O-, -COO-, -O- and -CONH-. It may be one or more selected species. R ₁ to R ₄ may each independently be a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

Examples of the alicyclic epoxy compound include epoxycyclohexylmethyl epoxycyclohexane carboxylate compounds; Epoxycyclohexane carboxylate-based compounds of alkanediol; Epoxy cyclohexylmethyl ester type compound of dicarboxylic acid; epoxycyclohexylmethyl ether-based compounds of polyethylene glycol; Epoxycyclohexylmethyl ether compounds of alkanediol; diepoxytrispiro-based compounds; diepoxymonospiro-based compounds; vinylcyclohexene diepoxide compounds; An epoxycyclopentyl ether compound or a diepoxy tricyclodecane compound or the like can be used. They may be stable even at high temperatures, colorless and transparent after curing, toughness, and excellent surface hardness.

In addition, the compound of Formula 1 may be exemplified by a compound represented by Formula 2 below. These can be synthesized by conventional methods, and commercially available products can also be used. By using the alicyclic epoxy compound, physical properties such as colorless transparency, low-temperature curability and chemical resistance, heat resistance and durability at high temperature and high humidity may be secured during curing of the curable composition according to the present application.

[Formula 2]

In Formula 2, Y may be an alkylene group having 1 to 4 carbon atoms. R ₁ to R ₄ may each independently be a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

In another example, the alicyclic epoxy compound (A) may include a compound represented by Formula 3 below.

[Formula 3]

In Formula 3, Q is a single bond; It may be a straight-chain or branched alkylene group having 1 to 8 carbon atoms, 1 to 6 carbon atoms, and 1 to 4 carbon atoms.

In one example, the alicyclic epoxy compound (A) may include a compound whose molar volume according to the following general formula 3 satisfies a range of 130 cm ³ /mol or more to 500 cm ³ /mol or less. As an example, in the case of the molar volume of the alicyclic epoxy compound (A), the lower limit is 140 cm ³ /mol or more, 150 cm ³ /mol or more, 160 cm ³ /mol or more, 170 cm ³ /mol or more, 180 cm ³ /mol or more, 190 cm ³ /mol or more, 200 cm ³ /mol or more, or 210 cm ³ /mol or more, and the upper limit is less than 450 cm ³ /mol, 400 cm ³ /mol or less, 350 cm ³ / mol or less, 300 cm ³ /mol or less, 250 cm ³ /mol or less, or 230 cm ³ /mol or less.

[Formula 3]

Molar volume of the curable compound (cm ³ /mol) = Molecular weight of the curable compound (g/mol) / Density of the curable compound (g/cm ³ )

In one embodiment, the cation-curable compound may include a multifunctional oxetane compound (B) including two or more oxetane groups. Here, the oxetane compound is a cation-curable functional group that includes an oxetanyl group, a 4-membered cyclic ether group, and may not include an epoxy group or a vinyl ether group. In addition, the multifunctional oxetane compound (B) may include two or more different compounds, and the types may not be particularly limited. As an example, a monofunctional oxetane compound having one oxetane group or an aromatic An aromatic oxetane compound containing at least one ring may not be included. Also, as an example, the oxetane compound (B) may not include an aromatic group.

In one example, the oxetane compound (B) may be represented by Formula 4 below.

[Formula 4]

In Formula 4, Z ₁ to Z ₂ may each independently be a straight-chain or branched-chain alkylene group having 1 to 4 carbon atoms or 1 to 2 carbon atoms. In addition, R ₅ to R ₆ are each independently a hydrogen atom; Alternatively, it may be a linear or branched alkyl group having 1 to 8, 1 to 6, or 1 to 4 carbon atoms.

In one example, the sealing material composition may include the multifunctional oxetane compound (B) in an amount of 30 to 400 parts by weight based on 100 parts by weight of the alicyclic epoxy compound (A), and for example, 40 parts by weight or more, 50 parts by weight or more, 60 parts by weight or more, 70 parts by weight or more, 80 parts by weight or more, 85 parts by weight or more, or 87 parts by weight or more, 300 parts by weight or less, 240 parts by weight or less, 230 parts by weight or less, 200 parts by weight or less parts by weight or less, 180 parts by weight or less, 160 parts by weight or less, 140 parts by weight or less, 120 parts by weight or less, 110 parts by weight or less, 100 parts by weight or less, 90 parts by weight or less, or 85 parts by weight or less. In the present application, by adjusting the content ratio of the multifunctional oxetane compound (B) to the above, it is possible to provide a composition capable of providing a uniform coating film and sufficiently securing pot life in the process of encapsulating the entire surface of an organic electronic device. In one embodiment, the cation-curable compound may include an aliphatic epoxy compound (C). The aliphatic epoxy compound (C) contains at least one epoxy group as a cation-curable functional group, and may not contain an oxetane group or a vinyl ether group. Further, the aliphatic epoxy compound (C) may include two or more different compounds, and the type is not particularly limited, but as an example, it may include a monofunctional aliphatic epoxy compound containing only one epoxy group, In this case, a polyfunctional epoxy compound having two or more epoxy groups may not be included. In addition, the aliphatic epoxy compound (C) may be a straight chain or branched chain having 8 to 16, 10 to 14, or 11 to 13 carbon atoms.

In one example, the sealant composition may include the aliphatic epoxy compound (C) in an amount of 45 to 300 parts by weight based on 100 parts by weight of the alicyclic epoxy compound (A), and for example, 47 parts by weight or more, 50 parts by weight or more, 60 parts by weight or more, 70 parts by weight or more, or 80 parts by weight or more, 250 parts by weight or less, 200 parts by weight or less, 150 parts by weight or less, 100 parts by weight or less, 80 parts by weight or less, 60 parts by weight or less, or 50 parts by weight It may be less than parts by weight. According to the present application, by controlling the content range, the sealing material composition can prevent device damage when sealing the entire surface of an organic electronic device, have appropriate physical properties capable of inkjetting, and realize low dielectric constant after curing.

Also, in one example, the aliphatic epoxy compound (C) may be included in 53 to 120 parts by weight based on 100 parts by weight of the oxetane compound (B). As an example, the lower limit of the aliphatic epoxy compound (C) relative to 100 parts by weight of the oxetane compound (B) is 55 parts by weight or more, 57 parts by weight or more, 60 parts by weight or more, 65 parts by weight or more, 70 parts by weight or more, 75 parts by weight or more 80 parts by weight or more, 85 parts by weight or more, 90 parts by weight or more, 95 parts by weight or more, or 100 parts by weight or more, and the upper limit is 115 parts by weight or less, 110 parts by weight or less, 100 parts by weight or less, 95 parts by weight or less, 90 parts by weight or less, 80 parts by weight or less, 70 parts by weight or less, or 60 parts by weight or less. In this way, by including both compounds in the above ratio, it is possible to implement a sealing material composition meeting the object of the present invention.

In one example, the cation-curable compound according to the present application may include a vinyl ether compound (D). The type of the vinyl ether compound (D) is not particularly limited as long as it has at least 1 or 2 or more and 10 or less vinyl ether groups as curable functional groups. In addition, the vinyl ether compound (D) may have a cyclic structure in its molecular structure, but is not limited thereto and may be straight-chain or branched-chain. In addition, when the vinyl ether compound (D) has a cyclic structure in its molecular structure, it can be distinguished from the curable compound having the above-described cyclic structure according to the presence or absence of vinyl ether, and thus, having the cyclic structure described above in the present specification. The curable compound may not include the vinyl ether group or the oxetane group described later.

When the vinyl ether compound (D) has a cyclic structure in its molecular structure, 3 to 10, 4 to 8, or 5 to 7 ring atoms may be present in the molecule. The cyclic structure may be an alicyclic or aromatic ring, but is not limited thereto. For example, the vinyl ether compound (D) is cyclohexyl vinyl ether, 1,4-cyclohexanedimethanol divinyl ether, butanediol monovinyl ether, triethylene glycol divinyl ether, or dodecyl vinyl ether. It may be, but is not limited thereto. By further including a vinyl ether group, the sealant composition according to the present invention realizes a composition applicable to an inkjet process, while further strengthening the curing network to exhibit a low permittivity even at a high temperature.

In addition, the sealing material composition may include 70 to 500 parts by weight of the vinyl ether compound (D) based on 100 parts by weight of the first epoxy compound (A), for example, 80 parts by weight or more, 90 parts by weight or more, 100 parts by weight It may be 110 parts by weight or more, or 120 parts by weight or more, and may include 400 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 150 parts by weight or less, or 130 parts by weight or less. The sealant composition according to the present invention may implement the physical properties desired by the present application by mixing the vinyl ether compound (D) with the above compositions in a specific amount.

In one embodiment, the sealant composition according to the present invention may include a photoinitiator. The photoinitiator may be a cationic photopolymerization initiator, and specific types may be appropriately selected in consideration of curing speed and the like. As the cationic photopolymerization initiator, for example, a cationic moiety containing aromatic sulfonium, aromatic iodonium, aromatic diazonium or aromatic ammonium and AsF ₆ ^- , SbF ₆ ^- , PF ₆ ^- , or tetrakis (pentafluorophenyl) It may include compounds having anionic moieties that include borates. In addition, as the cationic photopolymerization initiator, an onium salt or organometallic salt based ionizing cationic initiator or an organic silane or latent sulfuric acid based or non-ionized cationic photopolymerization initiator may be exemplified. . As the onium salt-based initiator, diaryliodonium salt, triarylsulfonium salt, or aryldiazonium salt may be exemplified, and organometallic salt-based initiators Examples of the zero include iron arene and the like, and examples of the organic silane-based initiator include o-nitrobenzyl triaryl silyl ether, triaryl silyl peroxide Alternatively, acyl silane may be exemplified, and latent sulfuric acid-based initiators may include α-sulfonyloxy ketone or α-hydroxymethylbenzoin sulfonate, but are not limited thereto. . Currently commercially available products include Irgacure 250, Irgacure 270, Irgacure 290, CPI-100P, CPI-101A, CPI-210S, Omnicat 440, Omnicat 550, and Omnicat 650, and these photopolymerization initiators are used alone or in combination of two or more. can be used by

In one example, the photoinitiator may be included in an amount of 0.01 to 10% by weight or less, specifically, 0.01 to 5% by weight based on the sealant composition. By adjusting the content range of the photoinitiator, it is possible to minimize physical and chemical damage to the organic electronic device due to the nature of the sealant composition of the present application applied directly on the device.

In one embodiment, the sealant composition may include a surfactant. The surfactant is not limited thereto, but silicone-based surfactants, fluorine-based surfactants, or acrylic surfactants are preferred.

Specific examples of the silicone-based surfactant include BYK-077, BYK-085, BYK-300, BYK-301, BYK-302, BYK-306, BYK-307, BYK-310, BYK-320, and BYK-322 manufactured by BYK-Chemie. , BYK-323, BYK-325, BYK-330, BYK-331, BYK-333, BYK-335, BYK-341v344, BYK-345v346, BYK-348, BYK-354, BYK-355, BYK-356, BYK -358, BYK-361, BYK-370, BYK-371, BYK-375, BYK-380 or BYK-390, and specific examples of the fluorine-based surfactant include F-114 manufactured by DIC (DaiNippon Ink & Chemicals) , F-177, F-410, F-411, F-450, F-493, F-494, F-443, F-444, F-445, F-446, F-470, F-471, F -472SF, F-474, F-475, F-477, F-478, F-479, F-480SF, F-482, F-483, F-484, F-486, F-487, F-172D , MCF-350SF, TF-1025SF, TF-1117SF, TF-1026SF, TF-1128, TF-1127, TF-1129, TF-1126, TF-1130, TF-1116SF, TF-1131, TF1132, TF1027SF, TF -1441 or TF-1442, but is not limited thereto. In order to control the surface tension of the sealant composition according to the present invention, the surfactant added in the composition may be included in an amount of 0.1 to 1% by weight based on the sealant composition.

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

In an embodiment of the present application, the sealant composition of the present application may be liquid at room temperature, for example, 25°C. As one specific example, the sealant composition may be a non-solvent type liquid. Here, the non-solvent type means containing 0.05% or less of a solvent. Also, in one embodiment, the sealant composition may be an ink composition. That is, the sealant composition according to the present application may be designed to have appropriate physical properties when ejected onto a substrate using inkjet printing capable of non-contact patterning.

In one example, the sealant composition has a viscosity of 50 cP or less, 1 to 46 cP, or 3 to 44 cP as measured by Brookfield's DV-3 at a temperature of 25 ° C, a torque of 90% and a shear rate of 20 rpm. , 4 to 38 cP, 5 to 33 cP or 14 to 24 cP. In the present application, by controlling the viscosity of the composition within the above range, it is possible to realize physical properties capable of inkjetting at the time of application to an organic electronic device, and also to provide a thin film encapsulant by improving coating properties.

In one example, the sealing material composition has a frequency of 1 to 250 kHz and 25 ° C temperature conditions after curing of 2.8 or less, 2.75 or less, 2.7 or less, 2.68 or less, 2.66 or less, 2.64 or less, 2.62 or less, 2.6 or less, Or it may have a permittivity of 2.58 or less, and the lower limit is not particularly limited, but may be 1 or more. As an example, the permittivity may be measured at any one frequency of 100 to 250 kHz, and more specifically, it may be measured at a frequency of 250 kHz.

As will be described in detail below, the sealant composition may form an organic layer by inducing crosslinking with light irradiation. Irradiating the light is to irradiate light having a wavelength range of about 250 to about 450 nm or about 300 to about 450 nm with a light amount of 300 to 6,000 mJ/cm ² or a light amount of 500 to 4,000 mJ/cm ² can include

In this case, as described below, the organic layer may have a thickness of 25 μm or less. For example, the thickness may be 23 μm or less, 22 μm or less, 21 μm or less, or 20 μm or less, and the lower limit thereof may be 1 μm or more or 2 μm or more. The present application can provide a thin organic electronic device by providing a thin organic layer.

In an embodiment of the present application, the sealing material composition has a surface tension of 10 to 50 mN/m, 12 to 45 mN/m, 15 to 40 mN/m, 18 to 35 mN/m, or 20 mN/m to 20 mN/m after curing. It can be in the range of 30 mN/m. The surface tension may be measured by a method known in the art, for example, by a ring method or the like. As the present application satisfies the surface tension range, ejection from an inkjet head may be facilitated in an inkjet process.

The surface tension may mean a value measured by the ring method with a dynamic wettability tester at 25 ° C. As an example, a surface tension tester (Tensiometer) from Kruss may be used, and in detail, after dipping a ring made of platinum or platinum-iridium into the sealing material composition, the ring is placed in a vertical direction. ), and when the force applied to the ring reaches its maximum, the contact angle becomes 0, and the surface tension value calculated by the force at this time and the distance the ring moves is ) and can be measured.

In addition, in the specific example of the present application, the sealant composition may have a light transmittance of 90% or more, 92% or more, or 95% or more in the visible light region after curing. Within the above range, the present application provides an organic electronic device with high resolution, low power consumption and long lifespan by applying the encapsulant composition to a top emission type organic electronic device. In addition, the sealing material composition of the present application may have a haze of 3% or less, 2% or less, or 1% or less according to the JIS K7105 standard test after curing, and the lower limit is not particularly limited, but may be 0%. Within the haze range, the sealant composition may have excellent optical properties after curing. In the present specification, the above-described light transmittance or haze may be measured in a state in which the sealant composition is cured into an organic layer, and may be an optical property measured when the thickness of the organic layer is any one of 2 to 20 μm. In the specific example of the present application, in order to implement the above optical properties, the aforementioned moisture adsorbent or inorganic filler may not be included.

<Organic electronic device>

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

In the specific example of the present application, the organic electronic device 32 may include a first electrode layer, an organic material layer formed on the first electrode layer and including at least a light emitting layer, and a second electrode layer formed on the organic material layer. . The first electrode layer may be a transparent electrode layer or a reflective electrode layer, and the second electrode layer may also be a transparent electrode layer or a reflective electrode layer. More specifically, the organic electronic device 32 may include a reflective electrode layer formed on a substrate, an organic material layer formed on the reflective electrode layer and including at least a light emitting layer, and a transparent electrode layer formed on the organic material layer.

In this application, the organic electronic device 32 may be an organic light emitting diode.

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

The organic electronic device 3 protects the electrode and the light emitting layer of the organic electronic device 32 and may further include an inorganic layer 35 between the organic electronic device 32 and the organic layer. The inorganic layer 35 may be a protective layer by chemical vapor deposition (CVD). For example, the inorganic layer 34 may be one or more metal oxides or nitrides selected from the group consisting of Al, Zr, Ti, Hf, Ta, In, Sn, Zn, and Si. The inorganic layer may have a thickness of 10 to 70 nm or about 20 to about 60 nm. In one example, the inorganic layer 34 of the present application may be an inorganic material without a dopant or an inorganic material with a dopant. The dopant that may be doped is one or more elements selected from the group consisting of Ga, Si, Ge, Al, Sn, Ge, B, In, Tl, Sc, V, Cr, Mn, Fe, Co, and Ni, or the element It may be an oxide of, but is not limited thereto.

As an example, the organic electronic device 3 may further include an inorganic layer 34 formed on the organic layer 33 . The inorganic layer 34 may use the same material as or a different material from the inorganic layer 35 formed between the organic electronic device 32 and the organic layer, and the inorganic layer 34 is formed in the same manner as the protective film 35. It can be.

Also, the organic layer may have a thickness of 25 μm or less. One yellow, the thickness may be 23 μm or less, 22 μm or less, 21 μm or less, or 20 μm or less, and the lower limit may be 1 μm or more or 2 μm or more. The present application can provide a thin organic electronic device by providing a thin organic layer.

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

In one embodiment, it may include an encapsulation structure 36 including at least one organic layer and at least one inorganic layer.

In one example, the organic electronic device 3 of the present application may further include a cover substrate (not shown) present on the organic layer 33 . The material of the substrate and/or the cover substrate is not particularly limited, and materials known in the art may be used. For example, the substrate or cover substrate may be a glass, metal substrate or polymer film. Polymer films include, for example, polyethylene terephthalate film, polytetrafluoroethylene film, polyethylene film, polypropylene film, polybutene film, polybutadiene film, vinyl chloride copolymer film, polyurethane film, ethylene-vinyl acetate film, ethylene - A propylene copolymer film, an ethylene-ethyl acrylate copolymer film, an ethylene-methyl acrylate copolymer film, or a polyimide film may be used. The cover substrate may have light transmittance, such as, for example, a visible light transmittance of 80% or more. In the case of light transmission, the type of material included in the cover substrate is not particularly limited. For example, the cover substrate may include a polymer resin or a glass component. In one example, when imparting flexible properties is required, the cover substrate may include a polymer resin. Although not particularly limited, for example, the cover substrate may be, for example, a polyester film such as PC (Polycarbonate), PEN (poly(ethylene naphthalate)) or PET (poly(ethylene terephthalate)); An acrylic film such as PMMA (poly(methylmethacrylate)), or a polyolefin film such as PE (polyethylene) or PP (polypropylene); a polyimide film; Or a polyamide film or the like may be included.

<Method of manufacturing organic electronic device>

This application also relates to a method for manufacturing an organic electronic device.

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

In the above, as the substrate 31 of the organic electronic device 32, for example, a reflective electrode or a transparent electrode is formed on the substrate 31 such as glass or polymer film by a method such as vacuum deposition or sputtering, It may be manufactured by forming an organic material layer on the reflective electrode. The organic material layer may include a hole injection layer, a hole transport layer, a light emitting layer, an electron injection layer, and/or an electron transport layer. Subsequently, a second electrode is further formed on the organic material layer. The second electrode may be a transparent electrode or a reflective electrode.

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

The manufacturing method may further include irradiating light to the organic layer. In the present invention, a curing process may be performed on the organic layer encapsulating the organic electronic device, and this curing process may be performed in, for example, a heating chamber or a UV chamber, preferably in a UV chamber. In one example, an organic layer may be formed by applying the above-described sealant composition by an inkjet printing method and inducing crosslinking of the applied sealant composition by irradiation of light, which, as described above, has a wavelength range of 250 to 450 nm and a wavelength range of 300 nm. to 6,000 mJ/cm ² by irradiating light in a light amount range to form an organic layer.

The manufacturing method of the present application may further include forming an inorganic layer 34 on the organic layer 33 . In the step of forming the inorganic layer 34, a method known in the art may be used, and may be the same as or different from the method of forming the protective film (35 in FIG. 1) described above.

The present application provides an encapsulant composition capable of securing the lifespan of an organic electronic device by effectively blocking moisture or oxygen flowing into the organic electronic device from the outside. However, the effects of the present invention are not limited to the effects mentioned above, and other effects not mentioned will be clearly understood by those skilled in the art from the description below.

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

Hereinafter, with reference to the accompanying drawings, preferred embodiments of the present invention will be described in more detail. In order to facilitate overall understanding in the description of the present invention, the same reference numerals are used for the same components in the drawings, and redundant descriptions of the same components are omitted.

Experimental example

1. Shrinkage rate

Shrinkage means the change in volume of the sealing material composition before and after curing, and was calculated by the following general formula 1.

[Formula 1]

Shrinkage rate (%) = (Volume of sealing material composition before curing - Volume of sealing material composition after curing) / Volume of sealing material composition before curing × 100

The shrinkage rate is measured in an atmosphere of 25 ° C. A volume of the “sealant composition before curing” is obtained by measuring a certain volume of the sealant composition before curing, and after curing the composition, according to Archimedes’ principle, “after curing” The volume of the sealant composition" was obtained. In addition, the “sealant composition after curing” is obtained by coating or coating the “sealant composition before curing” on an aluminum plate or glass substrate by using an inkjet printing method, and then UV curing with a light intensity of about 1,000 mJ/cm ² .

2. Permittivity

An Al plate (conductive plate) was deposited with a thickness of 50 nm on the cleaned bare glass. Each of the sealing material compositions prepared according to Examples and Comparative Examples was inkjet-coated on the surface of the deposited Al plate, and the coated composition was cured with a light amount of 1,000 mJ/cm ² through an LED UV lamp to a thickness of 20 μm. An organic layer with a thickness of A specimen was prepared by depositing an Al plate (conductive plate) with a thickness of 50 nm on the organic layer again. Then, the permittivity of the prepared specimens was measured at a frequency of 250 kHz and a temperature of 25 °C using an impedance/gain-phase measuring instrument HP 4194A.

3. Reliability

A SiOx inorganic layer was coated on the organic light emitting device to a thickness of 550 nm, and the encapsulant composition prepared according to Examples and Comparative Examples was coated on the inorganic layer with an inkjet device and then cured to form an organic layer. Then, a SiOx inorganic layer was coated on the formed organic layer to a thickness of 550 nm so as to cover the entire organic layer to obtain a specimen. After exposing the specimen for 100 hours in an 85 ° C environment, the emission state was checked, and dark spots were described as NG, and dark spots were uniformly emitted.

Example

Examples 1 to 2

Compositions and contents according to Table 1 below (listing for each weight ratio) were prepared, and the compositions according to Examples 1 and 2 were prepared by mixing at 25 ° C for 3 hours or more.

Comparative Examples 1 to 6

Compositions according to Comparative Examples 1 to 6 were prepared by preparing compositions and contents according to Table 1 (listing each weight ratio), and mixing at 25 ° C for 3 hours or more.

Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 alicyclic
Epoxy (A) a-1 25 20 5 45 20 - 30 35 a-2 - 20 - - - - - - a-3 - - - - - 9 - - oxetane
(B) b-1 20 35 40 - - - - - b-2 - - - - - 39 - 30 b-3 - - - - 50 - - - b-4 - - - - - - 35 - aliphatic
Epoxy (C) c-1 20 20 20 20 15 43 30 - c-2 - - - - 7.5 1.5 - - vinyl ether
(D) d 30 - 30 30 - - - 30 photoinitiator
(CPI-210S, San Apro) 3 3 3 3 3 3 3 3 Sensitizer (DBA) One One One One One One One One Surfactant (BYK-333) One One One One One One One One a-1: CELLOXIDE 2021P (DAICEL; 3, 4, 3', 4'-DIEPOXY BICYCLOHEXYL)
a-2: Compound corresponding to Formula 5 (Cas No. 14513-43-0)
a-3: CELLOXIDE 3000 (DAICEL; Cas No. 29616-43-1)
b-1: OXT-221 (TOAGOSEI; bis[1-ethyl(3-oxetanyl)methyl ether)
b-2: OXT-212 (TOAGOSEI; 3-ethyl-3-[(2-ethylhexyloxy)methyl]oxetane)
b-3: OXT-101 (TOAGOSEI; 3-ethyl-3-hydroxymethyl-oxetane)
b-4: OXT-121 (TOAGOSEI; 1,4-bis[(3-etyl-3-oxetanylmethoxy)metyl]benzene)
c-1: 1,2-EPOXYTETRADECANE
c-2: DE203 (Hajin Comtech; Neopentyl glycol diglycidyl ether)
d: CYCLOHEXYL VINYL ETHER

[Formula 5]

Table 2 below summarizes experimental data according to the above Examples and Comparative Examples.

Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Shrinkage (%) 6.1 4.5 13.2 11.5 16.1 18.9 7.2 15.3 Permittivity (250 kHz, 25 °C) 2.6 2.58 2.97 2.9 3.01 2.71 2.85 2.98 reliability OK OK NG NG NG NG NG NG

Although described with reference to the above embodiments, those skilled in the art will understand that the present invention can be variously modified and changed without departing from the spirit and scope of the present invention described in the claims below. You will be able to.

3: organic electronic device
31: Substrate
32: organic electronic device
36: bag structure
35: inorganic layer
33: organic layer
34: inorganic layer

Claims (15)

Including a cation-curable compound having at least one cation-curable functional group,
The cation-curable compound contains 10 to 43% by weight of an alicyclic epoxy compound (A),
After curing, it has a permittivity of 2.8 or less at a frequency of any one of 1 to 250 kHz and a temperature of 25 ° C,
A sealant composition having a shrinkage rate of 10% or less according to the following general formula 1:
[Formula 1]
Shrinkage rate (%) = (Volume of sealing material composition before curing - Volume of sealing material composition after curing) / Volume of sealing material composition before curing × 100 According to claim 1,
The cation-curable compound further comprises a polyfunctional oxetane compound (B) containing two or more oxetane groups. According to claim 2,
A sealing material composition comprising a polyfunctional oxetane compound (B) in an amount of 30 to 400 parts by weight based on 100 parts by weight of the alicyclic epoxy compound (A). According to claim 1,
The cation-curable compound further comprises an aliphatic epoxy compound (C). According to claim 4,
The aliphatic epoxy compound (C) is a sealing material composition having 8 to 16 carbon atoms and a linear or branched monofunctional compound. According to claim 4,
A sealing material composition comprising an aliphatic epoxy compound (C) in an amount of 45 to 300 parts by weight based on 100 parts by weight of the alicyclic epoxy compound (A). According to claim 1,
The cation-curable compound further comprises a vinyl ether compound (D). According to claim 7,
A sealing material composition comprising a vinyl ether compound (D) in an amount of 70 to 500 parts by weight based on 100 parts by weight of the alicyclic epoxy compound (A). According to claim 1,
A sealant composition further comprising a photoinitiator. According to claim 1,
A sealant composition further comprising a surfactant. According to claim 1,
A sealant composition having a viscosity of 50 cP or less measured at 25°C, 90% torque and a shear rate of 20 rpm. According to claim 1,
A sealing material composition that is a solvent-free type ink composition. Board; organic electronic devices formed on the substrate; and an organic layer formed of the sealant composition according to any one of claims 1 to 12 to seal the front surface of the organic electronic device. According to claim 13,
An organic electronic device including an inorganic layer formed between the organic electronic element and the organic layer or on the organic layer. A method of manufacturing an organic electronic device comprising forming an organic layer on a substrate having an organic electronic device formed thereon so that the sealant composition according to any one of claims 1 to 12 seals the front surface of the organic electronic device. .

Images