KR20230032669A - Encapsulating composition and Organic electronic device comprising the same - Google Patents

Abstract

The present application provides an encapsulant composition which can secure a lifespan of an organic electronic device by effectively blocking moisture or oxygen flowing into the organic electronic device from the outside, enables the implementation of a top emission type organic electronic device, and is applicable to an inkjet method; a method for preparing the encapsulant composition; and an organic electronic device including the encapsulant composition. The encapsulant composition of the present application comprises a cation-curable compound having at least one cation-curable functional group, wherein the cation-curable compound includes an alicyclic epoxy compound (A) and an aliphatic epoxy compound (B), and the alicyclic epoxy compound (A) includes a compound represented by chemical formula 1, and has a dielectric constant of 2.7 or less at a temperature of 25℃ and at any frequency within 1 to 250 kHz after curing.

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.

In this specification, the term alicyclic hydrocarbon group means a cyclic hydrocarbon structure other than an aromatic ring structure unless otherwise specified. The alicyclic hydrocarbon group may be, for example, an alicyclic ring structure having 3 to 21, 3 to 18, 3 to 15, 3 to 12, 3 to 10, or 5 to 6 carbon atoms, unless otherwise specified. .

In the present specification, an alkylene group is a divalent group derived from an alkyl group, and the term alkylene group has 1 to 10 carbon atoms, 1 to 8 carbon atoms, 1 to 6 carbon atoms, 1 to 4 carbon atoms, or 1 to 4 carbon atoms, unless otherwise specified. It may mean an alkylene group of 2 to 3. The alkylene group may be a straight-chain, branched-chain, or cyclic alkylene group, and may be optionally substituted with one or more substituents.

In the present specification, the alkenylene group is a divalent unsaturated hydrocarbon group having at least one carbon-carbon double bond, and the alkynylene group is a divalent unsaturated hydrocarbon group having at least one carbon-carbon triple bond. , Unless otherwise specified, it may mean an alkenylene group or alkynylene group having 2 to 20 carbon atoms, 2 to 16 carbon atoms, 2 to 12 carbon atoms, 2 to 8 carbon atoms, or 2 to 4 carbon atoms. The alkenylene group or alkynylene group may be linear, branched, or cyclic, and may be optionally substituted with one or more substituents.

In this specification, the term single bond may mean a case in which no separate atom exists at the corresponding site. For example, in the structure represented by A-B-C, when B is a single bond, there is no separate atom at the site represented by B, and A and C are directly connected to form a structure represented by A-C. .

In this specification, the term alkyl group means an alkyl group having 1 to 10 carbon atoms, 1 to 8 carbon atoms, 1 to 6 carbon atoms, 1 to 4 carbon atoms, 1 to 3 carbon atoms, or 1 to 2 carbon atoms, unless otherwise specified. can The alkyl group may be straight-chain or branched, and may be optionally substituted with one or more substituents.

In the present application, as the substituent that may be optionally substituted with an alkylene group, an alkenylene group, an alkynylene group, or an alkyl group, an alkyl group, an alkenyl group, an alkynyl group, an alkylene group, an alkenylene group, an alkynylene group, and the like may be exemplified. However, it is not limited thereto.

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 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, as described later, includes a specific monomer or uses a specific composition even if it is a previously known monomer, so that the optical properties, low viscosity, and high hardness as well as excellent plasma resistance and low output It is possible to provide a composition for encapsulating an organic electronic device capable of realizing a gas amount and a low permittivity at the same time. In addition, apart from these, the sealant composition according to the present application can implement inkjetting properties such as excellent ejection property and spreadability.

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 may include a cation-curable compound having at least one cation-curable functional group, and the cation-curable compound may include an alicyclic epoxy compound (A) and an aliphatic epoxy compound (B). can

The alicyclic epoxy compound (A) may include a compound represented by Formula 1 below.

[Formula 1]

X ₁ - Y - X ₂

In Formula 1, X ₁ and X ₂ may each independently be an alicyclic epoxy group. In the present specification, an alicyclic epoxy group includes at least one epoxide ring and at least one alicyclic hydrocarbon group in a molecular structure, and in detail, two adjacent carbon atoms among carbon atoms constituting an alicyclic hydrocarbon are oxygen atoms and It means a group having a structure forming an epoxy ring. That is, in the present invention, the alicyclic epoxy compound (A) includes at least one epoxy group as a cation-curable functional group, but may include a cyclic structure in the molecular structure. Also, the alicyclic epoxy compound (A) may contain one compound or two or more different compounds. In the present invention, a low dielectric constant and a low outgassing content can be implemented through a sealing material composition having a combination of an alicyclic epoxy compound having the above specific structure and an aliphatic epoxy compound.

In Formula 1, Y may be an alkylene group, an alkenylene group, or an alkynylene group. That is, Y positioned between X ₁ and X ₂ in Formula 1 may include a separate organic group. In addition, in one example, the sealing material composition of the present application may not include an alicyclic epoxy compound in which Y in Formula 1 includes oxygen (O) as the alicyclic epoxy compound (A). As the alicyclic epoxy compound (A), Y in Formula 1 does not contain an alicyclic epoxy compound containing oxygen (O), so that the present application can provide a sealing material composition having excellent surface hardness while emitting a low outgassing amount. there is.

Although not limited thereto, the alicyclic epoxy compound (A) may be included in an amount of 20 to 70 parts by weight based on 100 parts by weight of the sealing material composition. As an example, based on 100 parts by weight of the sealing material composition, the lower limit of the alicyclic epoxy compound (A) is 23 parts by weight or more, 25 parts by weight or more, 27 parts by weight or more, 30 parts by weight or more, 32 parts by weight or more, 34 parts by weight or more. 35 parts by weight or more, 37 parts by weight or more, 40 parts by weight or more, 42 parts by weight or more, 44 parts by weight or more, 46 parts by weight or more, 48 parts by weight or more, 50 parts by weight or more, 52 parts by weight or more, or 54 parts by weight or more part or more, and the upper limit is 68 parts by weight or less, 66 parts by weight or less, 64 parts by weight or less, 62 parts by weight or less, 60 parts by weight or less, 58 parts by weight or less, 56 parts by weight or less, 54 parts by weight or less, 52 parts by weight or less parts by weight or less, 50 parts by weight or less, 47 parts by weight or less, 45 parts by weight or less, 43 parts by weight or less, 40 parts by weight or less, 37 parts by weight or less, or 36 parts by weight or less. In the present invention, by including the alicyclic epoxy compound (A) of a specific structure in the above range, it is possible to provide a sealing material composition suitable for a low dielectric constant and excellent hardness.

In one example, the alicyclic epoxy compound of Formula 1 may be represented by Formula 2 below.

[Formula 2]

In Formula 2, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ may each independently be hydrogen or an alkyl group, and n is an integer from 1 to 6, 1 to 4, or 1 to 3 .

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

[Formula 3]

In Formula 3, R ₁ , R ₂ , R ₃ , and R ₄ are each independently hydrogen or an alkyl group.

Specifically, 0.01 to 50 parts by weight of the compound represented by the following formula (3) may be included relative to 100 parts by weight of the compound represented by formula (2), for example, 3 to 45 parts by weight, 5 to 40 parts by weight, 7 to 40 parts by weight 37 parts by weight, 10 to 35 parts by weight, 12 to 33 parts by weight, 15 to 30 parts by weight, 17 to 27 parts by weight, or 20 to 25 parts by weight. Although not limited to this, the present application includes only the compound represented by Formula 2 as the alicyclic epoxy compound (A), or even when the compound represented by Formula 3 is included together, as desired in the present application, while having a low dielectric constant It is possible to provide a sealing material composition having excellent surface hardness and satisfying a low outgassing amount.

In addition, the cation-curable compound may contain an aliphatic epoxy compound (B). The aliphatic epoxy compound (B) contains at least one epoxy group as a cation-curable functional group, and may not contain an oxetane group or a cyclic structure in its molecular structure. Furthermore, the aliphatic epoxy compound (B) may include two or more different compounds, and the type is not particularly limited. As an example, the aliphatic epoxy compound (B) may be a monofunctional epoxy compound, A polyfunctional epoxy compound having two or more epoxy groups may not be included.

In one example, the aliphatic epoxy compound (B) may include a monofunctional aliphatic epoxy compound having a straight or branched hydrocarbon group having 8 to 16, 10 to 14, or 11 to 13 carbon atoms. The sealing material composition according to the present invention may be suitable for realizing a low dielectric constant by including the long-chain aliphatic epoxy compound. As an example, it may not include a short-chain aliphatic epoxy compound having a hydrocarbon group of 8 or less carbon atoms.

Although not limited thereto, in one example, the aliphatic epoxy compound (B) may be included in 50 to 150 parts by weight based on 100 parts by weight of the alicyclic epoxy compound (A). As an example, relative to 100 parts by weight of the alicyclic epoxy compound (A), the lower limit of the aliphatic epoxy compound (B) is 53 parts by weight or more, 55 parts by weight or more, 57 parts by weight or more, 60 parts by weight or more, 63 parts by weight or more, 65 parts by weight or more, 67 parts by weight or more, 70 parts by weight or more, 72 parts by weight or more, 75 parts by weight or more, 77 parts by weight or more, 80 parts by weight or more, 83 parts by weight or more, 85 parts by weight or more, 87 parts by weight or more, 90 parts by weight or more, 93 parts by weight or more, 95 parts by weight or more, 97 parts by weight or more, 100 parts by weight or more, 105 parts by weight or more, 107 parts by weight or more, 110 parts by weight or more, or 113 parts by weight or more, and the upper limit thereof 147 parts by weight or less, 145 parts by weight or less, 140 parts by weight or less, 135 parts by weight or less, 130 parts by weight or less, 125 parts by weight or less, 120 parts by weight or less, 117 parts by weight or less, 115 parts by weight or less, 110 parts by weight or less , 105 parts by weight or less, 100 parts by weight or less, 97 parts by weight or less, 95 parts by weight or less, 93 parts by weight or less, 90 parts by weight or less, 87 parts by weight or less, 85 parts by weight or less, 83 parts by weight or less, 80 parts by weight or less , 77 parts by weight or less, 75 parts by weight or less, or 73 parts by weight or less. The encapsulant composition according to the present invention, by being included in the above specific range together with other compositions, may be advantageous in realizing a low permittivity while realizing inkjet properties.

Also, in one embodiment, the cation-curable compound may further include an oxetane compound (C). 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. Although not limited thereto, the oxetane compound (C) may include two or more different compounds, and the types are not particularly limited, but a monofunctional oxetane compound or a multifunctional oxetane containing two or more oxetane groups. It may include a compound, and as an example, may not include an aromatic oxetane compound containing at least one aromatic ring, and as another example, may not include an oxetane compound containing a hydroxyl group. there is.

Although not limited thereto, when the oxetane compound (C) is further included, the oxetane compound (C) may be included in an amount of 5 to 70 parts by weight based on 100 parts by weight of the alicyclic epoxy compound (A). As an example, based on 100 parts by weight of the alicyclic epoxy compound (A), the lower limit of the oxetane compound (C) is 6 parts by weight or more, 7 parts by weight or more, 8 parts by weight or more, 9 parts by weight or more, 10 parts by weight or more. , 13 parts by weight or more, 15 parts by weight or more, 18 parts by weight or more, 20 parts by weight or more, 23 parts by weight or more, 25 parts by weight or more, 28 parts by weight or more, 30 parts by weight or more, 33 parts by weight or more, 35 parts by weight or more , 38 parts by weight or more, 40 parts by weight or more, 43 parts by weight or more, 45 parts by weight or more, 48 parts by weight or more, 50 parts by weight or more, 53 parts by weight or more, 55 parts by weight or more, or 57 parts by weight or more, and The upper limit is 73 parts by weight or less, 70 parts by weight or less, 65 parts by weight or less, 63 parts by weight or less, 60 parts by weight or less, 58 parts by weight or less, 55 parts by weight or less, 50 parts by weight or less, 45 parts by weight or less, 40 parts by weight or less. 35 parts by weight or less, 30 parts by weight or less, 25 parts by weight or less, 20 parts by weight or less, 18 parts by weight or less, 17 parts by weight or less, 16 parts by weight or less, 15 parts by weight or less, 14 parts by weight or less, 13 parts by weight or less Or less, it may be 12 parts by weight or less, or 11 parts by weight or less. Even when the oxetane compound is further included as described above, the desired composition of the present invention can be implemented.

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. Cationic photopolymerization initiators include, for example, aromatic sulfonium, aromatic iodonium, aromatic diazonium, or a cationic moiety containing aromatic ammonium and AsF ₆ ^- , SbF ₆ ^- , PF ₆ ^- , tris (pentafluoroethyl) tris fluorophosphate, or a compound having an anionic moiety including tetrakis (pentafluorophenyl) borate. In addition, as the cationic photopolymerization initiator, an onium salt or organometallic salt based ionizing cationic initiator or an organic silane or latent sulfuric acid based or non-ionized cationic photopolymerization initiator may be exemplified. . As the onium salt-based initiator, diaryliodonium salt, triarylsulfonium salt, or aryldiazonium salt may be exemplified, and organometallic salt-based initiators Examples of the zero include iron arene and the like, and examples of the organic silane-based initiator include o-nitrobenzyl triaryl silyl ether, triaryl silyl peroxide Alternatively, acyl silane may be exemplified, and the latent sulfuric acid-based initiator may include α-sulfonyloxy ketone or α-hydroxymethylbenzoin sulfonate, but is 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. and can be used.

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 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-553, F-554, F-555, F-556, F-557, F-558, F-559 , F-560, F-561, F-562, F-563, F-565, F-568, F-569, F-570, F-571, F-572, 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 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 2.7 or less, 2.69 or less, 2.68 or less, 2.67 or less, 2.66 or less, 2.65 or less, 2.64 or less, 2.63 or less, It may have a dielectric constant of 2.62 or less, 2.61 or less, 2.6 or less, 2.59 or less, 2.58 or less, 2.57 or less, 2.56 or less, 2.54 or less, or 2.53 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 surface hardness at 25 ° C after curing is 50 Mpa or more, 55 Mpa or more, 60 Mpa or more, 65 Mpa or more, 70 Mpa or more, 75 Mpa or more, 80 Mpa or more, 85 Mpa or more, 90 Mpa or more It may be 95 Mpa or more, 100 Mpa or more, 103 Mpa or more, 105 Mpa or more, 107 Mpa or more, or 110 Mpa or more, and the upper limit is not particularly limited, but may be 1,000 Mpa or less. As the above surface hardness is satisfied, it is possible to prevent damage to the organic layer, which is a cured product of the encapsulant composition, in a process such as CVD for forming an inorganic layer.

In one example, the sealing material composition of the present application has an amount of volatile organic compounds measured after curing of less than 40 ppm, less than 30 ppm, less than 25 ppm, less than 20 ppm, less than 15 ppm, less than 13 ppm, less than 10 ppm, or It may be 5 ppm or less, and the lower limit is not limited, but may be 0.0001 ppm or more. In the present specification, the volatile organic compound may be referred to as outgas. The volatile organic compound can be measured after curing the sealant composition, maintaining 120 mg of the cured product sample at 110 ° C for 30 minutes using Purge & Trap - Gas Chromatography / Mass Spectrometry there is. The measurement may be performed using a Purge & Trap sampler (JAI JTD-505III)-GC/MS (Agilent 7890b/5977a) instrument.

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, an encapsulation structure 36 including at least one organic layer and at least one inorganic layer may be included, and a touch sensor 37 formed on the encapsulation structure may be included. Such a laminated structure may be referred to as a touch on encapsulation (TOE) structure. In such a structure, an organic layer for an encapsulant having a low dielectric constant is required to increase touch sensitivity.

The touch sensor 37 refers to a device capable of recognizing input information obtained through contact with a user, and may be a sensor known in the related art. For example, the touch sensor may include a capacitive sensor for recognizing a touch based on static electricity generated at a contact part of the user's body (eg, a hand) and a current change resulting therefrom; Alternatively, it may be a pressure-sensitive sensor that recognizes a touch based on a capacitance change generated when the conductive layers of the upper and lower panels of the touch sensor come into contact with a pressure applied by a user. A configuration of a sensor capable of recognizing a user's touch in each method may be known in the related art.

In one example, the touch sensor 37 may include a conductive layer (not shown) on one or both surfaces. The material of the conductive layer is not particularly limited, and for example, a transparent conductive film such as ITO or a metal nanowire may be used. The conductive layer may have a channel through which electricity flows and a non-channel region through which electricity does not flow. These regions may be formed through a method such as etching or photolithography.

In one example, the organic electronic device 3 may further include a cover substrate (not shown) on an uppermost surface. That is, the organic electronic device 3 according to the present invention may sequentially include an encapsulation structure 36, a touch sensor 37, and a cover substrate. At this time, the cover substrate and the touch sensor may be collectively referred to as the touch panel 37 . A TOE structure may be implemented by placing an encapsulant on the touch panel.

In one embodiment, the touch sensor 37 may be formed directly on the encapsulation structure 36 . That is, a separate adhesive layer or adhesive layer may not exist between the laminated components.

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 poly(methylmethacrylate) (PMMA), or a polyolefin film such as polyethylene (PE) or polypropylene (PP); 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, preferred experimental examples are presented to aid 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.

Examples 1 to 2

Compositions and contents according to Table 1 below (the contents are expressed as ratios) 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 3

Compositions according to Comparative Examples 1 to 3 were prepared by preparing compositions and contents according to Table 1 (the contents are expressed as ratios), and mixing at 25 ° C for 3 hours or more.

Furtherance Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Cycloaliphatic Epoxy (A) a-1 55 35 45 0 0 0 55 a-2 0 0 10 55 35 0 0 a-3 0 0 0 0 0 50 0 Aliphatic Epoxy (B) b 40 40 40 40 40 40 0 oxetane
(C) c-1 0 20 0 0 20 0 40 c-2 0 0 0 0 0 5 0 photoinitiator
(CPI-210S) 3 3 3 3 3 3 3 Sensitizer (DBA) One One One One One One One Surfactant (F-557) One One One One One One One a-1: A compound corresponding to Formula A below
a-2: a compound corresponding to formula B below
a-3: Celloxide 2021P (DAICEL; 3, 4, 3', 4'-DIEPOXY BICYCLOHEXYL)
b: 1,2-epoxytetradecane
c-1: OXT-212 (TOAGOSEI; 3-ethyl-3-[(2-ethylhexyloxy)methyl]oxetane)
c-2: OXT-221 (TOAGOSEI; bis[1-ethyl(3-oxetanyl)]methyl ether)

[Formula A]

[Formula B]

1. Permittivity

An Al plate (conductive plate) was deposited at 150 nm on the cleaned bare glass. Inkjet coating the sealant composition prepared in Examples and Comparative Examples on the surface of the deposited Al plate, and curing the coated composition with a light amount of 1000 mJ / cm ² through an LED UV lamp to form an organic layer having a thickness of 10 μm formed. On the organic layer, an Al plate (conductive plate) was again deposited with a thickness of 150 nm to prepare a specimen. Then, the permittivity of the specimens prepared at 250 kHz and 25 °C was measured using an impedance/gain-phase measuring instrument HP 4194A.

2. Surface hardness

Each of the sealant compositions prepared according to Examples and Comparative Examples was formed on a glass substrate to a predetermined thickness and cured under UV conditions of 1000 mJ/cm ² through an LED UV lamp, so that both the width and length were 20 cm and the thickness was 20 cm. A specimen having 8 μm was prepared. Experimental mode: Indentation Mode (using Berkovitz), Control mode: Force control, Maximum force: 2 mN, 250 kHz, and 25 ° C conditions, specimens were applied to hardened specimens with nano indenter HM-2000 (Fisher). The measurement was performed by loading for 5 seconds, holding for 2 seconds, and then unloading for 5 seconds.

3. Outgas measurement

The sealing material composition prepared in Examples and Comparative Examples was cured to a thickness of 8 μm on bare glass by irradiating UV of 1 J/cm ² at an intensity of 1000 mW/cm ² , and then cut into 1 cm × 1 cm in size to contain 120 mg of After maintaining the cured product sample at 110 °C for 30 minutes using Purge & Trap - Gas Chromatography/Mass Spectrometry, the amount of volatile organic compounds was measured. The measurement was performed using a Purge & Trap sampler (JAI JTD-505III - GC/MS (Agilent 7890b/5977a) instrument.

Table 2 below summarizes the results according to the above experimental examples.

Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 permittivity 2.53 2.53 2.59 2.73 2.85 3.1 2.75 surface hardness
(MPa) 110 100 100 105 100 95 60 outgas
(ppm) 4.1 11.8 4.2 4.1 12.5 15.5 43.8

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 (18)

A cation-curable compound having at least one cation-curable functional group, wherein the cation-curable compound includes an alicyclic epoxy compound (A) and an aliphatic epoxy compound (B),
The alicyclic epoxy compound (A) includes a compound represented by Formula 1 below,
A sealing material composition having a permittivity of 2.7 or less at a frequency of any one of 1 to 250 kHz and a temperature of 25 ° C after curing:
[Formula 1]
X ₁ - Y - X ₂
In Formula 1, X ₁ and X ₂ are each independently an alicyclic epoxy group, and Y is an alkylene group, an alkenylene group, or an alkynylene group. According to claim 1,
A sealing material composition comprising 20 to 70 parts by weight of an alicyclic epoxy compound (A) based on 100 parts by weight of the sealing material composition. According to claim 1,
Chemical Formula 1 is a sealant composition represented by the following Chemical Formula 2:
[Formula 2]

In Formula 2, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are each independently hydrogen or an alkyl group, and n is an integer between 1 and 6. According to claim 3,
The alicyclic epoxy compound (A) further comprises 0.01 to 50 parts by weight of a compound represented by the following formula (3) based on 100 parts by weight of the compound represented by the formula (2):
[Formula 3]

In Formula 3, R ₁ , R ₂ , R ₃ , and R ₄ are each independently hydrogen or an alkyl group. According to claim 1,
The sealing material composition in which the aliphatic epoxy compound (B) is a monofunctional compound. According to claim 1,
The aliphatic epoxy compound (B) is a sealing material composition having 8 to 16 carbon atoms and being a linear or branched monofunctional compound. According to claim 1,
A sealing material composition comprising 50 to 150 parts by weight of an aliphatic epoxy compound (B) based on 100 parts by weight of the alicyclic epoxy compound (A). According to claim 1,
The cation-curable compound further comprises an oxetane compound (C). According to claim 8,
A sealing material composition comprising the oxetane compound (C) in an amount of 5 to 70 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 surfactant. According to claim 1,
A sealant composition further comprising a photoinitiator. According to claim 1,
A sealant composition having a viscosity of 50 cP or less measured at 25°C and 90% torque. According to claim 1,
A sealing material composition that is a solvent-free type ink composition. According to claim 1,
A sealant composition having a surface hardness of 50 MPa or more at 25°C after curing. According to claim 1,
After curing, the amount of volatile organic compounds measured after maintaining at 110 ° C for 30 minutes using Purge & Trap-Gas Chromatography / Mass Spectrometry for 120 mg of the cured product was measured, and the sealing material composition was less than 40 ppm. . 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 15 to seal the front surface of the organic electronic device. 17. The method of claim 16,
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 15 seals the front surface of the organic electronic device. .

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