KR20220098824A - Encapsulating composition and Organic electronic device comprising the same - Google Patents

Abstract

A sealing material composition according to the present invention comprises a radical curable compound having at least one radical curable functional group, wherein the radical curable compound includes a monofunctional alicyclic compound (X1) and has a shrinkage rate according to a general formula 1 of less than 10% so that a low dielectric constant can be realized.

Description

Encapsulating composition and organic electronic device comprising the same

The present invention relates to a sealing material composition and an organic electronic device including the same.

The touch sensor is a liquid crystal display (Liquid Crystal Display), a field emission display (FED), a plasma display panel (PDP), an electroluminescence device (EL), an electrophoretic display device. It refers to a type of input device installed in an image display device, such as a user, to input predetermined information by pressing (pressing or touching) a touch panel while viewing the image display device.

Recently, in accordance with the trend of enlargement and thinning of the display device, the form factor of the structure of the touch sensor used in the above-described display device is changing. Accordingly, a display device in which a touch sensor is directly formed on a sealing layer is being developed.

On the other hand, according to the thinning of the display device, the gap between the electrode for the touch sensor constituting the touch sensor and the upper electrode in the image display device becomes narrower, so a parasitic current may be generated to lower the touch sensitivity of the touch sensor.

Therefore, lowering the dielectric constant of the sealing layer to increase the user's touch sensitivity is a major problem to solve.

An object of the present invention is to provide a sealing material composition capable of realizing excellent touch sensitivity based on a characteristic of a low dielectric constant. The technical problems of the present invention are not limited to the technical problems mentioned above, and other technical problems not mentioned will be clearly understood by those skilled in the art from the following description.

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

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

The terms used in the present application are only used to describe specific embodiments, and are not intended to limit the present invention. The singular expression includes the plural expression unless the context clearly dictates otherwise. In the present application, terms such as “comprise” or “have” are intended to designate that a feature, number, step, operation, component, part, or combination thereof described in the specification exists, but one or more other features It is to be understood that this does not preclude the possibility of the presence or addition of numbers, steps, operations, components, parts, or combinations thereof.

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 this invention belongs. Terms such as those defined in a commonly used dictionary should be interpreted as having a meaning consistent with the meaning in the context of the related art, and should not be interpreted in an ideal or excessively formal meaning unless explicitly defined in the present application. does not

<Sealing material composition>

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

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

The present application provides a sealing material composition applied to directly contact the device on the top emission type organic electronic device, so it should have excellent optical properties after curing, and prevent device deterioration due to outgas generated during curing of the composition Should be. In particular, the sealing material composition of the present application should implement excellent ejection properties, spreadability and low viscosity in order to be applied to the inkjet process, and implement high surface hardness after curing to prevent damage due to the inorganic layer forming process in the sealing layer, It should be possible to realize excellent touch sensitivity in a thin-film organic electronic device based on the low dielectric constant characteristic. In addition, as the shrinkage rate after curing satisfies a certain level or less, the gap between the organic layer and the inorganic layer formed adjacent to the organic layer due to curing of the sealing material composition may be minimized to have excellent reliability.

Accordingly, the present application may provide a composition for encapsulating an organic electronic device capable of simultaneously implementing the above, optical properties, device reliability, low viscosity, and high hardness as well as low dielectric constant by using a specific composition as described below.

In the present application, the sealing material composition may include a radical curable compound. The radical curable compound refers to a composition that can be cured by radical polymerization according to light irradiation, and may have at least one radical curable functional group. The light irradiated here is, for example, electromagnetic waves such as microwaves, infrared (IR), ultraviolet (UV), X-rays or gamma rays, as well as alpha-particle beams and proton beams. ), a Neutron beam, and an electron beam may be irradiated with a particle beam. As an example, the radical curable functional group is not particularly limited, but may be a (meth)acrylic group, that is, an acryl group or a methacryl group. In more detail, the polyfunctional aliphatic compound described later is a polyfunctional aliphatic (meth)acrylic compound, the monofunctional alicyclic compound is a monofunctional alicyclic (meth)acrylic compound, and the polyfunctional alicyclic compound is a polyfunctional alicyclic (meth)acrylic compound. The compound, the monofunctional aliphatic compound, may be a monofunctional aliphatic (meth)acrylic compound.

In one embodiment, the sealing material composition according to the present invention includes a radical-curable compound having at least one radical-curable functional group, and the radical-curable compound includes a monofunctional alicyclic compound (X1), according to the following general formula 1 The shrinkage may be less than 10%, less than 9%, less than 8%, less than 7%, less than 6%, less than 5%, less than 4%, less than 3%, less than 2.8%, or less than 2.6%, the lower limit of which is not limited. However, it may be 0.1% or more. The shrinkage ratio refers to the volume change before and after curing of the sealing material composition, and may be measured under an atmosphere of 25°C.

[General formula 1]

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

The “sealing material composition before curing” includes a radical curable compound, etc., as described below, and may mean a composition before curing. In addition, the “sealing material composition after curing” may be obtained by applying the “sealing material composition before curing” on glass or coating the “sealing material composition before curing” on an aluminum plate or a glass substrate by an inkjet printing method, and then UV curing with a light quantity of about 1,000 mJ/cm ² It may be obtained. .

That is, the volume of the “sealing material composition before curing” is obtained by measuring a certain volume of the sealing material composition before curing, and after curing the composition, the “volume of the sealing material composition after curing” can be obtained according to the Archimedes principle. More specifically, for example, the volume of the sealing material composition after curing is determined by using an XS205 analytical balance manufactured by Mettler and a density measurement kit "solid and liquid density measurement kit", and the density (ρ) of the sealing material composition after curing by the following formula can be obtained, and it can be measured by converting the volume therefrom.

ρ=(α×ρ ₀ )/(α-β)

In the above formula, ρ is the density of the sealing material composition after curing, α is the mass of the sealing material composition after curing in the atmosphere, 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 .

As described above, in the sealing material composition according to the present invention, the shrinkage rate after curing is controlled below a certain level, thereby minimizing the gap between the organic layer and the inorganic layer formed above or below the organic layer due to curing of the sealing material composition, so that the device has better durability can be obtained

Here, the alicyclic compound may mean a monomer having at least one cyclic structure in the molecular structure of an alicyclic hydrocarbon-based monomer, and may not include an aromatic group. The monofunctional alicyclic compound (X1) is an alicyclic compound and means having one functional group in a molecule. As an example, the monofunctional alicyclic compound (X1) is 4-t-butylcyclohexyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, 3,3,5-trimethyl cyclohexane (meth) acrylate, norbornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, and the like, but is not limited thereto.

In one example, the boiling point of the radical curable compound included in the sealing material composition according to the present invention may be 250 °C or more, and the upper limit thereof is not particularly limited, but may be 1,000 °C or less. In this way, by controlling the boiling point of the radical curable compound to a specific temperature or higher, deterioration of the device due to outgas generated during curing of the composition can be prevented, and furthermore, the flatness of the organic layer obtained by curing the composition can be secured while maintaining the level of the organic layer. Shrinkage is suppressed, and durability of the device can be further secured. Moreover, the drying phenomenon of a nozzle can be suppressed in an inkjet process, and process stability can be ensured.

In one example, the monofunctional alicyclic compound (X1) may be included in an amount of 25 to 70 wt% based on the radical curable compound. More specifically, the lower limit of the monofunctional alicyclic compound (X1) is 26 wt% or more, 27 wt% or more, 28 wt% or more, 29 wt% or more, 30 wt% or more, 31 wt% or more, based on the radical curable compound. , 32 wt% or more, 33 wt% or more, 34 wt% or more, 35 wt% or more, 36 wt% or more, 38 wt% or more, 40 wt% or more, 42 wt% or more, or 44 wt% or more, The upper limit is 65 wt% or less, 63 wt% or less, 60 wt% or less, 57 wt% or less, 55 wt% or less, 53 wt% or less, 50 wt% or less, 47 wt% or less, 45 wt% or less, 43 wt% or less or less, 40 wt% or less, 37 wt% or less, or 35 wt% or less. Since the monofunctional alicyclic compound (X1) is included in the above range, the sealing material composition according to the present invention may have an excellent curing rate and device reliability, and at the same time have a low dielectric constant.

Also, in one embodiment, the radical-curable compound may include a polyfunctional aliphatic compound (Y2) having a straight-chain or branched alkyl group. In the present specification, the aliphatic compound having a straight-chain or branched alkyl group is an aliphatic hydrocarbon-based monomer having a straight-chain or branched alkyl group in the molecular structure, and may not have a cyclic structure or an aromatic group. The polyfunctional aliphatic compound (Y2) is an aliphatic compound, and means having at least two functional groups in a molecule.

In one example, the polyfunctional aliphatic compound (Y2) may have at least a difunctional or more radically curable functional group. As an example, hexanediol di(meth)acrylate, tripropylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropaneethoxy tri(meth) ) acrylate, glycerin propoxylated tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol hexa(meth)acrylate, tripentaeryth and ritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, and the like, but is not limited thereto. In particular, in order to implement the object of the present invention, the polyfunctional aliphatic compound (Y2) may include trifunctional to 8 functional, tetrafunctional to 7 functional, or pentafunctional to hexafunctional.

In one example, the polyfunctional aliphatic compound (Y2) may be included in an amount of 1 to 48 parts by weight based on 100 parts by weight of the polyfunctional alicyclic compound (X1). As an example, the polyfunctional aliphatic compound (Y2) is 2 parts by weight or more, 3 parts by weight or more, 4 parts by weight or more, 5 parts by weight or more, 6 parts by weight or more, 7 parts by weight or more, based on 100 parts by weight of the polyfunctional alicyclic compound (X1) 47.5 parts by weight or less, 47 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 25 parts by weight or more, 30 parts by weight or more, 40 parts by weight or more, or 45 parts by weight or more. parts by weight or less, 46.5 parts by weight or less, 46 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, 15 parts by weight or less, or 10 parts by weight or less can do. By including the composition in a specific range, the sealing material composition according to the present invention exhibits a low dielectric constant characteristic, thereby increasing the touch sensitivity of the touch sensor adjacent to the sealing layer of the present invention.

Also, in one embodiment, the radical-curable compound may include a polyfunctional alicyclic compound (X2). Here, the polyfunctional alicyclic compound (X2) is an alicyclic compound, which means having at least two functional groups in a molecule, and for example, 1,4-cyclohexanedimethyldi(meth)acrylate, tricyclodecanedimethyl Old-di(meth)acrylate, 1,4-cyclohexanedimethyloldi(meth)acrylate, norbornanedimethyloldi(meth)acrylate, etc. may be used, but the present invention is not limited thereto.

In one example, the polyfunctional alicyclic compound (X2) may be included in an amount of 1 to 100 parts by weight based on 100 parts by weight of the monofunctional alicyclic compound (X1). Specifically, the lower limit of the polyfunctional alicyclic compound (X2) is 2 parts by weight or more, 3 parts by weight or more, 4 parts by weight or more, 5 parts by weight or more, 6 parts by weight based on 100 parts by weight of the monofunctional alicyclic compound (X1). or more, 15 parts by weight or more, 20 parts by weight or more, 25 parts by weight or more, 30 parts by weight or more, 35 parts by weight or more, 40 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. parts, and the upper limit of the polyfunctional alicyclic compound (X2) is 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, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, or 10 parts by weight or less. By including the polyfunctional alicyclic compound (X2) in the above range, it is possible to implement a low dielectric constant.

Further, in one example, the polyfunctional aliphatic compound (Y2) may be included in an amount of 1 to 400 parts by weight based on 100 parts by weight of the polyfunctional alicyclic compound (X2). Specifically, the lower limit of the polyfunctional aliphatic compound (Y2) is 2 parts by weight or more, 3 parts by weight or more, 4 parts by weight or more, 5 parts by weight or more, 6 parts by weight or more based on 100 parts by weight of the polyfunctional alicyclic compound (X2). , 7 parts by weight or more, 8 parts by weight or more, 50 parts by weight or more, 100 parts by weight or more, 200 parts by weight or more, or 300 parts by weight or more, and the lower limit thereof is 390 parts by weight or less, 380 parts by weight or less, 370 parts by weight or more. or less, 365 parts by weight or less, 300 parts by weight or less, 250 parts by weight or less, 200 parts by weight or less, 150 parts by weight or less, 110 parts by weight or less, 50 parts by weight or less, or 10 parts by weight or less. As such, the composition according to the present invention includes the polyfunctional alicyclic compound (X2) and the polyfunctional aliphatic compound (Y2) in the above range, thereby obtaining the sealing material composition desired by the present application.

In one embodiment, it may include a monofunctional aliphatic compound (Y1) having a straight-chain or branched alkyl group. Here, the monofunctional aliphatic compound (Y1) having a straight-chain or branched alkyl group is an aliphatic compound and means having one functional group in a molecule.

In one example, the monofunctional aliphatic compound (Y1) may include an aliphatic compound having an alkyl group having 8 to 16 carbon atoms, for example, n-octyl (meth) acrylate, isooctyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, n-decyl (meth) acrylate, Isodecyl (meth) acrylate, lauryl (meth) acrylate, undecyl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, stearyl (meth) acrylate and the like may be included, but is not limited thereto. In this way, by introducing an aliphatic compound having a long chain skeleton, it is possible to reduce the polarity of the entire molecule to realize low dielectric constant of the composition.

In one example, the monofunctional aliphatic compound (Y1) may be included in an amount of 30 to 200 parts by weight based on 100 parts by weight of the monofunctional alicyclic compound (X1). Specifically, the lower limit of the monofunctional aliphatic compound (Y1) is 31 parts by weight or more, 32 parts by weight or more, 33 parts by weight or more, 34 parts by weight or more, 35 parts by weight or more, 50 parts by weight based on 100 parts by weight of the alicyclic compound (X1). It may be at least 70 parts by weight, at least 90 parts by weight, at least 100 parts by weight, at least 120 parts by weight, at least 130 parts by weight, or at least 140 parts by weight, and the upper limit thereof is 190 parts by weight or less, 180 parts by weight or less, 170 parts by weight or less, 160 parts by weight or less, 155 parts by weight or less, 150 parts by weight or less, 140 parts by weight or less, 120 parts by weight or less, 100 parts by weight or less, 80 parts by weight or less, 60 parts by weight or less, or 40 parts by weight or less. can

In addition, in one example, the sum total of parts by weight of the polyfunctional aliphatic compound (Y2) and the monofunctional aliphatic compound (Y1) may be included in an amount of 75 to 250 parts by weight based on 100 parts by weight of the monofunctional alicyclic compound (X1). Specifically, the sum of parts by weight of the polyfunctional aliphatic compound (Y2) and the monofunctional aliphatic compound (Y1) is 76 parts by weight or more, 77 parts by weight or more as the lower limit, relative to 100 parts by weight of the monofunctional alicyclic compound (X1), 78 parts by weight or more, 79 parts by weight or more, 80 parts by weight or more, 81 parts by weight or more, 90 parts by weight or more, 100 parts by weight or more, 120 parts by weight or more, 140 parts by weight or more, or 160 parts by weight or more, and the upper limit thereof 230 parts by weight or less, 210 parts by weight or less, 190 parts by weight or less, 180 parts by weight or less, 170 parts by weight or less, 167 parts by weight or less, 165 parts by weight or less, 150 parts by weight or less, 130 parts by weight or less, 110 parts by weight or less , 100 parts by weight or less, or 90 parts by weight or less.

In one embodiment, the sealing material composition according to the present invention may include a photoinitiator. The photoinitiator may be a radical photoinitiator, and a specific type may be appropriately selected in consideration of a curing rate and the like. For example, a benzoin type, hydroxy ketone type, amino ketone type, or phosphine oxide type photoinitiator can be used, and specifically, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether. , benzoin n-butyl ether, benzoin isobutyl ether, acetophenone, dimethyl anino acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2 -Hydroxy-2-methyl-1-phenylpropan-1one, 1-hydroxycyclohexylphenylketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propane-1- One, 4- (2-hydroxyethoxy) phenyl-2- (hydroxy-2-propyl) ketone, benzophenone, p-phenylbenzophenone, 4,4'-diethylaminobenzophenone, dichlorobenzophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 2-aminoanthraquinone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2,4 -Dimethylthioxanthone, 2,4-diethylthioxanthone, benzyldimethylketal, acetophenone dimethylketal, p-dimethylamino benzoic acid ester, oligo[2-hydroxy-2-methyl-1-[4-(1-methyl) vinyl) phenyl] propanone] and 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, and the like, and the photoinitiator may be used alone or in combination of two or more.

In one example, the photoinitiator may be included in an amount of 0.01 to 10% by weight or less, for example, 0.01 to 5% by weight or less, based on the sealing material composition. By controlling the content range of the photoinitiator, physical and chemical damage to the device can be minimized in view of the characteristics of the sealing material composition of the present application applied directly on the organic electronic device.

In one embodiment, the sealing material composition may include a surfactant. The surfactant is not limited thereto, but a silicone-based surfactant, a fluorine-based surfactant, or an acrylic surfactant may be used.

Specific examples of the silicone-based surfactant include BYK-Chemie's BYK-077, BYK-085, BYK-300, BYK-301, BYK-302, BYK-306, BYK-307, BYK-310, BYK-320, BYK-322 , 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, etc., and specific examples of the fluorine-based surfactant include DIC (DaiNippon Ink & Chemicals) F-114 , 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 sealing material composition according to the present invention, the surfactant added in the composition may be included in an amount of 0.1 to 1 wt% based on the sealing material composition.

In addition to the above-described configuration, the sealing material composition according to the present application may include various additives within a range that does not affect the effects of the above-described invention. For example, the sealing material composition may include 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 sealing material composition of the present application may be liquid at room temperature, for example, 25 °C. In one embodiment, the sealing material composition may be a solvent-free type liquid. Here, the solvent-free type means containing a solvent in an amount of 0.05% or less. Also, in one embodiment, the sealing material composition may be an ink composition. That is, the sealing material composition according to the present application may be designed to have appropriate physical properties when discharged to a substrate using inkjet printing capable of non-contact patterning.

In one example, the sealant composition has a viscosity of 50 cP or less, 1-46 cP, 3-44 cP, as measured by a Brookfield 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 in the above range, it is possible to implement ink jetting properties at the time of application to an organic electronic device, and also to provide a thin film encapsulant with excellent coating properties.

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

In this case, as will be described later, 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 thickness of the organic layer.

In an embodiment of the present application, the sealing material composition has a surface energy 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 30 of the cured product after curing. It can be in the range of mN/m. It can be measured by a method known in the art of the measurement of the surface energy, for example, it can be measured by the Ring Method method. As the present application satisfies the above surface energy range, ejection from the inkjet head may be easy in the inkjet process.

As an example, the surface energy (γsurface, mN/m) may be calculated as γsurface = γdispersion + γpolar, and may be measured using a drop shape analyzer (Drop Shape Analyzer, DSA100 manufactured by KRUSS). For example, the surface energy is measured by applying the sealing material composition to be measured on a SiNx substrate with a thickness of about 50 μm and a coating area of 4 cm ² (width: 2 cm, length: 2 cm) to form an encapsulant (spin coater), nitrogen After drying for about 10 minutes at room temperature under an atmosphere, UV curing is performed through a light quantity of 4000 mJ/cm ² with an intensity of 1000 mW/cm ² . After curing, drop deionized water with a known surface tension on the membrane and repeat the process of obtaining the contact angle 5 times to obtain the average value of the obtained five contact angle values, and similarly, the surface tension is known Drop the diiodomethane and repeat the process of obtaining the contact angle 5 times to obtain the average value of the obtained 5 contact angle values. Then, the surface energy can be obtained by substituting the numerical value (Strom value) for the surface tension of the solvent by the Owens-Wendt-Rabel-Kaelble method using the obtained average value of the contact angles for deionized water and diiodomethane.

In an embodiment of the present application, after curing into a thin film having a thickness of 20 μm, the sealing material composition is 2.7 or less, 2.69 or less, 2.68 or less, 2.67 or less, at a frequency of 1 to 250 kHz and a temperature of 25°C or less, It may have a dielectric constant of 2.66 or less, 2.65 or less, 2.64 or less, 2.63 or less, 2.62 or less, 2.61 or less, or 2.6 or less, and the lower limit thereof is not limited, but may be 1 or more. As an example, each dielectric constant may be measured at any one frequency of 100 to 250 kHz, more specifically, it may be measured at a frequency of 250 kHz.

As an example, for the dielectric constant, aluminum is deposited on glass to be about 50 nm, and the sealing material composition is coated thereon by an inkjet printing method and UV-cured with an amount of light of about 1,000 mJ/cm ² An organic layer having a thickness of about 20 μm After forming the , it can be measured using an impedance/gain-phase measuring instrument HP 4194A on a specimen in which aluminum is deposited to a thickness of about 50 nm on the organic layer.

The dielectric constant of the film mass-produced in the prior art is in the range of about 3.4 or more to 4.5, which is unsuitable for use in large-sized displays due to parasitic capacitance between electrodes. In addition, in general, the thinner the thickness, the higher the dielectric constant value. In this way, since the organic layer formed from the composition of the above configuration satisfies the above dielectric constant range, even if a thin organic layer is applied to an organic electronic device described below, interference between circuits does not occur, and thus an organic electronic device capable of thinning can provide Since lowering the dielectric constant is advantageous for improving the sensitivity of the touch sensor, the lower limit of the dielectric constant is not particularly limited, but may be, for example, 0.01 or 0.1.

In an embodiment of the present application, it may be 3.6 GPa or more, 3.7 GPa or more, or 3.8 GPa or more at 25°C after curing. As the modulus is satisfied as described above, the surface hardness is excellent, and damage to the organic layer, which is a cured product of the encapsulant composition, can be prevented in a process such as CVD for forming an inorganic layer.

The modulus is measured by forming a sealing material composition into a film on a glass substrate to a predetermined thickness and curing it under UV conditions of 1000 mW/cm ² through an LED UV lamp to prepare a specimen having both width and length of 20 cm and a thickness of 3 μm. can be In particular, it is measured by loading the specimen for 5 seconds with a nano indenter HM-2000 (Fisher) for the cured specimen, holding the specimen for 2 seconds, and then unloading it for 5 seconds again. The measurement conditions may be Experimental mode: Indentation Mode (using Berkovitz), Control mode: Force control, Maximum force: 2 mN, 250 kHz, and 25 °C conditions.

In addition, in an embodiment of the present application, the sealing material composition may have a light transmittance of 90% or more, 92% or more, or 95% or more in a visible ray region after curing. Within the above range, the present application provides an organic electronic device with high resolution, low power consumption and long life by applying the sealing material 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 sealing material 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 sealing material composition is cured into an organic layer, and may be an optical characteristic measured when the thickness of the organic layer is any one of 2 to 20 μm. In an embodiment of the present application, in order to implement the optical properties, the above-described moisture absorbent or inorganic filler may not be included.

<Organic Electronic Devices>

The present application also relates to an organic electronic device. An exemplary organic electronic device 3 includes a substrate 31 , as shown in FIG. 1 ; an organic electronic device 32 formed on the substrate 31; and an organic layer 33 that seals the entire surface of the organic electronic device 32 and is formed of the above-described sealing material composition.

In the embodiment 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 the present 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 formed 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 thickness of the inorganic layer may be from 10 to 70 nm or from about 20 to about 60 nm. In one example, the inorganic layer 34 of the present application may be an inorganic material that does not include a dopant or an inorganic material that includes a dopant. The dopant that may be doped is at least one element 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 or different material from the inorganic layer 35 formed between the organic electronic device 32 and the organic layer, and the inorganic layer 34 may be formed in the same manner as the inorganic layer 35 . can be formed.

Also, the organic layer may have a thickness of 25 μm or less. In 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 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 thickness of the 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 device/inorganic layer/(organic layer/inorganic layer) n, and n may be a number within 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, and a touch sensor 37 formed on the encapsulation structure.

In one embodiment, the touch sensor 37 may be formed directly on the encapsulation structure 36 . That is, a separate layer such as an adhesive layer or an adhesive layer is not interposed between the touch sensor 37 and the encapsulation structure 36 , and the touch sensor 37 and the encapsulation structure 36 may be in direct contact with each other. Such a layered structure can be called a TOE (Touch On Encapsulation) structure. By having such a TOE structure, the thickness of the organic electronic device can be reduced compared to the existing one.

On the other hand, according to the thinning of the organic electronic device, the gap between the electrode for the touch panel 37 (ie, the conductive layer) and the electrode for the organic electronic device adjacent to the touch panel is narrowed, so that a parasitic current is generated between them. A problem in which the sensitivity of the touch sensor is lowered may occur. Therefore, since the TOE structure requires an organic layer for an encapsulant having a low dielectric constant in order to prevent the touch sensitivity from being lowered, the present application provides a sealing material composition according to this necessity.

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 in a user's body contact area (eg, hand) and a current change resulting therefrom; Alternatively, it may be a pressure-sensitive sensor that recognizes a touch based on a change in capacitance that occurs when the conductive layers of the upper and lower plates of the touch sensor come into contact with the pressure applied by the user. A configuration of a sensor for recognizing a user's contact 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 sides. 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 the uppermost surface. That is, the organic electronic device 3 according to the present invention may sequentially include the encapsulation structure 36 , the touch sensor 37 , and the cover substrate. In this case, the cover substrate and the touch sensor may be collectively referred to as the touch panel 37 . An encapsulant is positioned on the touch panel to implement the TOE structure.

The cover substrate may have light-transmitting properties, for example, when the transmittance of visible light is 80% or more. In the case of having light-transmitting properties, 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 it is necessary to impart flexible properties, the cover substrate may include a polymer resin. Although not particularly limited, for example, the cover substrate may include, 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.

<Method for manufacturing organic electronic device>

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

In one example, the manufacturing method includes the steps of forming the organic layer 33 on the substrate 31 on which the organic electronic device 32 is formed so that the above-described sealing material composition seals the entire surface of the organic electronic device 32 . may 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 vacuum deposition or sputtering, and the It may be manufactured by forming an organic material layer on the reflective electrode. The organic material layer may include a hole injection layer, a hole transport layer, a light emitting layer, an electron injection layer, and/or an electron transport layer. Next, a second electrode is further formed on the organic material layer. The second electrode may be a transparent electrode or a reflective electrode.

The manufacturing method of the present application may further include forming the inorganic layer 35 on the first electrode, the organic material layer, and the second electrode formed on the substrate 31 . Thereafter, the above-described organic layer 33 is applied on the substrate 31 to cover the entire surface of the organic electronic device 32 . In this case, the step of forming the organic layer 33 is not particularly limited, and the above-described sealing material composition is applied to the entire surface of the substrate 31 by inkjet printing, gravure coating, spin coating, screen printing, or reverse offset. 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 for encapsulating the organic electronic device, and the curing process may be performed, for example, in a heating chamber or a UV chamber, preferably in a UV chamber. In one example, the above-described sealing material composition may be applied by an inkjet printing method, and an organic layer may be formed by inducing crosslinking of the applied sealing material composition by irradiation with light, which, as described above, has a wavelength range of 250 to 450 nm and 300 to 6,000 mJ/cm ² It is possible to form an organic layer by irradiating light in a light quantity range.

The manufacturing method of the present application may further include forming the 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 above-described method of forming the inorganic layer (35 in FIG. 1).

In addition, the step of disposing the touch sensor 37 on the organic layer 33 or the inorganic layers 35 and 34 , that is, the encapsulation structure 36 may be added.

As described above, the encapsulant composition according to embodiments of the present invention may improve the touch sensitivity of an adjacent touch sensor and provide excellent protection against the external environment. However, the effects of the present invention are not limited to the above-mentioned effects, and other effects not mentioned will be clearly understood by those skilled in the art from the following description.

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

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

Experimental example

1. Shrinkage

Shrinkage refers to the volume change before and after curing of the sealing material composition, and was calculated by the following general formula (1).

[General formula 1]

Shrinkage (%) = (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 was measured under an atmosphere of 25 °C, and the volume of the "sealing material composition before curing" was obtained by measuring a certain volume of the sealing material composition before curing, and after curing the composition, "after curing" according to the Archimedes principle The volume of the sealing material composition" was obtained.

In addition, the "sealing material composition after curing" is obtained by applying the "sealing material composition before curing" or coating the inkjet printing method on an aluminum plate or a glass substrate, and UV curing with a light quantity 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. On the surface of the deposited Al plate, each of the sealing material compositions prepared according to Examples and Comparative Examples was inkjet coated, and the coated composition was cured at a light quantity of 1,000 mJ/cm ² through an LED UV lamp to 20 μm. A thickness of the organic layer was formed. A specimen was prepared by depositing an Al plate (conductive plate) with a thickness of 50 nm on the organic layer again. Thereafter, the dielectric constant of each prepared specimen 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 sealing material compositions prepared according to Examples and Comparative Examples were coated on the inorganic layer by an inkjet device and then cured to form an organic layer. Then, the SiOx inorganic layer was coated to a thickness of 550 nm to cover the entire organic layer on the formed organic layer to obtain a specimen. After exposing the specimen for 100 hours under 85 °C environment, the light emission state was checked and NB when dark spots were generated, and OK when light was uniformly emitted without dark spots.

4. Modulus

Each of the sealing material compositions prepared according to Examples and Comparative Examples was formed into a film on a glass substrate to a predetermined thickness and cured under UV conditions of 1,000 mW/cm ² through an LED UV lamp, so that both the width and length were 20 cm and the thickness was A specimen having a value of 3 μm was prepared. Measurements were carried out in Experimental mode: Indentation Mode (using Berkovitz), Control mode: Force control, Maximum force: 2 mN, 250 kHz, and 25 °C for the cured specimen with a nano-indenter HM-2000 (Fisher). The specimen was loaded for 5 seconds, held for 2 seconds, and then removed for 5 seconds again for measurement.

Example

Examples 1-3

The composition and content according to Table 1 below (including 100 parts by weight of the monofunctional alicyclic compound, the monofunctional aliphatic compound, the polyfunctional aliphatic compound, and the polyfunctional alicyclic compound are each weight based on 100 parts by weight of the monofunctional alicyclic compound represents parts, and the photoinitiator and surfactant each represent parts by weight based on 100 parts by weight of the sealing material composition) were prepared and mixed at 25° C. for 3 hours or more to prepare compositions according to Examples 1 to 3.

Comparative Examples 1 to 2

The composition and content according to Table 1 below (including 100 parts by weight of the monofunctional alicyclic compound, the monofunctional aliphatic compound, the polyfunctional aliphatic compound, and the polyfunctional alicyclic compound are each weight based on 100 parts by weight of the monofunctional alicyclic compound represents parts, and the photoinitiator and surfactant each represent parts by weight based on 100 parts by weight of the sealing material composition) were prepared and mixed at 25° C. for 3 hours or more to prepare compositions according to Comparative Examples 1 and 2.

Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Monofunctional alicyclic compound (X1) 100 100 100 100 100 Monofunctional aliphatic compound (Y1) 140 35.5 100 140 20 Polyfunctional aliphatic compound (Y2) 25 46 7 130 50 Polyfunctional alicyclic compound (X2) 6.9 43 80 110 50 Photoinitiator (Darocure, TPO-L) 3 3 3 3 3 Surfactant (BYK-333) 0.5 0.5 0.5 0.5 0.5 X1: M1150 (Miwon, 4-Tert-Butylcyclohexyl acrylate)
Y1 : Lauryl acrylate
Y2: M600 (Miwon, dipentaerythritol hexaacrylate)
X2: 1,4-cyclohexanedimethyldimethacrylate

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

Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Shrinkage (%) 5.5 7.9 6.2 15.9 17.3 permittivity (250 kHz, 25 °C) 2.5 2.6 2.6 3.3 3.2 reliability OK OK OK NG NG modulus
(GPa) 3.6 3.8 4 3.3 3.6

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

3: organic electronic device
31: substrate
32: organic electronic device
36: bag structure
35: inorganic layer
33: organic layer
34: inorganic layer
37: touch sensor

Claims (20)

a radical curable compound having at least one radical curable functional group, wherein the radical curable compound comprises a monofunctional alicyclic compound (X1);
A sealing material composition having a shrinkage ratio of less than 10% according to the following general formula 1:
[General formula 1]
Shrinkage (%) = (volume of sealing material composition before curing - volume of sealing material composition after curing) / volume of sealing material composition before curing × 100 The method of claim 1,
The radical curable compound has a boiling point of 250 °C or higher. The method of claim 1,
A sealing material composition comprising 25 to 70% by weight of the monofunctional alicyclic compound (X1). The method of claim 1,
The radical curable compound is a sealing material composition further comprising a polyfunctional aliphatic compound (Y2) having a linear or branched alkyl group. 5. The method of claim 4,
The polyfunctional aliphatic compound (Y2) is a sealing material composition having at least a difunctional or higher radical curable functional group. 5. The method of claim 4,
A sealing material composition comprising 1 to 48 parts by weight of the polyfunctional aliphatic compound (Y2) relative to 100 parts by weight of the polyfunctional alicyclic compound (X1). The method of claim 1,
The radical curable compound is a sealing material composition further comprising a polyfunctional alicyclic compound (X2). 8. The method of claim 7,
A sealing material composition comprising 1 to 100 parts by weight of the polyfunctional alicyclic compound (X2) based on 100 parts by weight of the monofunctional alicyclic compound (X1). The method of claim 1,
The radical curable compound is a sealing material composition further comprising a monofunctional aliphatic compound (Y1) having a straight-chain or branched alkyl group. 10. The method of claim 9,
The monofunctional aliphatic compound (Y1) is a sealing material composition comprising an aliphatic compound having an alkyl group having 8 to 16 carbon atoms. 10. The method of claim 9,
A sealing material composition comprising 30 to 200 parts by weight of the monofunctional aliphatic compound (Y1) based on 100 parts by weight of the monofunctional alicyclic compound (X1). The method of claim 1,
A sealing material composition further comprising a photoinitiator. The method of claim 1,
A sealing material composition further comprising a surfactant. The method of claim 1,
A sealing material composition having a viscosity of 50 cP or less and a surface energy in the range of 10 to 50 mN/m, measured at 25°C, 90% torque, and a shear rate of 20 rpm. The method of claim 1,
A sealing material composition which is a solvent-free type ink composition. The method of claim 1,
A sealing material composition having a dielectric constant of 2.7 or less at a frequency of 1 to 250 kHz and a temperature of 25°C after curing. The method of claim 1,
Encapsulant composition having a modulus of 3.5 GPa or higher at 25°C after curing. Board; an organic electronic device formed on a substrate; and an organic layer that seals the entire surface of the organic electronic device and is formed of the sealing material composition according to any one of claims 1 to 17. 19. The method of claim 18,
and an inorganic layer formed between the organic electronic device and the organic layer or on the organic layer. 18. A method of manufacturing an organic electronic device, comprising: forming an organic layer on a substrate on which an organic electronic device is formed so that the sealing material composition according to any one of claims 1 to 17 seals the entire surface of the organic electronic device .

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