Adhesive composition

Abstract

Provided are an adhesive composition and an organic electronic device (OED) including the same. The adhesive composition can form a structure that effectively blocks the inflow of moisture or oxygen from the outside into the OED, thereby ensuring the lifespan of the OED, enabling a top-emission OED, and exhibiting excellent adhesive durability and reliability. The adhesive composition shows a first peak having a glass transition temperature in the range of 20°C to 60°C and a second peak having a glass transition temperature in the range of 80°C to 120°C measured by differential scanning calorimetry after curing. The adhesive composition has a tensile modulus of 1 MPa to 300 Mpa at 25°C after curing, the adhesive composition is a liquid at 25°C, and the adhesive composition includes an olefin-based resin, a curable resin, and a free-radical photocurable compound.

Description

[0001] This application is a divisional application of a Chinese patent application with an application date of March 24, 2016, an application number of "201680027064.8", and an invention title of "Adhesive Composition".

[0002] Cross-reference to related applications

[0003] This application claims the benefit of Korean Patent Application No. 10-2015-0040741, filed with the Korean Intellectual Property Office on March 24, 2015, the disclosure of which is incorporated herein by reference in its entirety. Technical field

[0004] The present invention relates to an adhesive composition, an organic electronic device (OED) comprising the same, and a method of manufacturing an OED. Background art

[0005] An OED is a device including an organic material layer that uses holes and electrons to exchange charges, and the OED can be, for example, a photovoltaic device, a rectifier, a transmitter, or an organic light emitting diode (OLED).

[0006] Among these OEDs, the OLED has lower power consumption and higher response speed, and is more advantageous than conventional light sources in reducing the thickness of a display device or in lighting. Such an OLED also has excellent space utilization and is expected to be applied to various fields, including all types of portable devices, monitors, laptops, and TVs.

[0007] For the commercialization and extended use of OLEDs, the most critical issue is durability. The organic materials and metal electrodes included in OLEDs are very easily oxidized by external factors such as moisture. Therefore, products including OLEDs are very sensitive to environmental factors. For this reason, various methods have been proposed to effectively prevent oxygen or moisture from infiltrating from the outside into an OED, such as an OLED.

[0008] Patent Document 1 discloses an adhesive encapsulation composition film and an organic electroluminescent element, wherein the composition is a pressure-sensitive adhesive based on polyisobutylene (PIB), and does not have high processability and has low reliability under high temperature and high humidity conditions.

[0009] [Prior art documents]

[0010] [Patent documents]

[0011] (Patent Document 1) Korean Unexamined Patent Application Publication No. 2008-0088606 Summary of the invention

[0012] Technical problem

[0013] The present application provides an adhesive composition and an OED including the same, which can form a packaging structure that effectively blocks the inflow of moisture or oxygen from the outside into the OED, thereby ensuring the lifespan of the OED, realizing a top-emitting OED, and exhibiting moisture resistance, excellent adhesive durability and reliability, and excellent reliability under high temperature and high humidity.

[0014] Technical solution

[0015] The present application relates to an adhesive composition. The adhesive composition can be a packaging material applied to encapsulate or enclose an OED, such as an OLED. In one exemplary embodiment, the adhesive composition of the present application can be applied to at least one side surface of an organic electronic component for encapsulation or enclosing. Thus, after being applied for encapsulation, the adhesive composition can be present in the peripheral portion of the OED.

[0016] The term "OED" herein refers to a product or device having a structure including an organic material layer in which holes and electrons exchange charges between a pair of opposing electrodes, and examples of the OED can include but are not limited to photovoltaic devices, rectifiers, emitters, and OLEDs in the present application. In one exemplary embodiment of the present application, the OED can be an OLED.

[0017] An exemplary adhesive composition for encapsulating an organic electronic component may exhibit a first peak having a glass transition temperature of 20°C to 60°C and a second peak having a glass transition temperature of 80°C to 120°C as determined by differential scanning calorimetry after curing. That is, the cured adhesive according to the present application can have at least two peaks, which can be respectively present in the ranges of 20°C to 60°C and 80°C to 120°C. In addition, in one exemplary embodiment of the present application, the tensile modulus of the adhesive composition at 25°C after curing can be 1 MPa to 150 MPa, 5 MPa to 140 MPa, 10 MPa to 130 MPa, or 20 MPa to 120 MPa. The tensile modulus can be measured using a texture analyzer, and the sample for measuring the tensile modulus is prepared to have a size of 1 cm × 3 cm and a thickness of 200 μm. The present application can provide excellent moisture resistance and excellent durability and reliability under high temperature and high humidity by controlling the glass transition temperature and tensile modulus of the cured adhesive within the above ranges. In addition, previously, when a moisture absorbent was included in the packaging material to absorb moisture, it was difficult for the packaging material to maintain adhesive durability and reliability due to the generated expansion and contraction stresses. For this reason, the present application uses an adhesive composition having a first peak and a second peak as the packaging material to reduce the expansion and contraction stresses, and thus can maintain adhesive durability and reliability.

[0018] In an exemplary embodiment, to achieve an adhesive composition having the glass transition temperature and the tensile modulus, the content ratios of the compositions and their components used to form the adhesive composition can be controlled. As long as the above physical properties are satisfied, the materials used to form the composition are not particularly limited. For example, the present application can maintain excellent adhesive durability and reliability as follows: by controlling the composition of the adhesive composition to achieve a tensile modulus, a crosslinking degree between components, and a crosslinked structure within a desired range. Meanwhile, the term "adhesive" herein can be used with the same meaning as the adhesive composition.

[0019] In an exemplary embodiment, the adhesive composition may include an olefin-based resin having a water vapor transmission rate (WVTR) of 50 g / m 2 · day or less, and a curable resin.

[0020] The adhesive composition of the present application may include an olefin-based resin having a WVTR of 50 g / m 2 · day or less. Since the adhesive composition of the present application includes an olefin-based resin that satisfies the above WVTR range, when the adhesive composition is applied to encapsulate or enclose an OED, it can provide excellent moisture resistance. The term "resin having a WVTR of 50 g / m 2 · day or less" herein may refer to a resin having a WVTR of 50 g / m measured in the thickness direction of the film when the film is formed as a layer of the resin with a thickness of 100 μm. 2 · day or less. The WVTR measured at 100°F and 100% relative humidity may be 50 g / m 2 · day, 40 g / m 2 · day, 30 g / m 2 · day, 20 g / m 2 · day or 10 g / m 2 · day or less. When the WVTR is lower, more excellent moisture resistance can be exhibited. The lower limit can be, but is not particularly limited to, for example, 0 g / m 2 · day or 0.1 g / m 2 · day.

[0021] Specifically, the exemplary olefin-based resins of the present invention include olefin-based resins derived from monomer mixtures, and the mixture may have an isobutene monomer component or a polyolefin monomer component having at least 4 to 7 carbon atoms. Isobutene may be present in an amount of, for example, 70 wt% to 100 wt%, or 85 wt% to 99.5 wt% based on the total weight of the monomers. The polyolefin-derived component may be present in an amount of 0.5 wt% to 30 wt%, 0.5 wt% to 15 wt%, or 0.5 wt% to 8 wt%.

[0022] The isoolefin can be, for example, isobutene, 2-methyl-1-butene, 3-methyl-1-butene, 2-methyl-2-butene, 1-butene, 2-butene, methyl vinyl ether, indene, vinyltrimethylsilane, hexene, or 4-methyl-1-pentene. The polyolefin can have 4 to 14 carbon atoms and can be, for example, isoprene, butadiene, 2,3-dimethyl-1,3-butadiene, myrcene, 6,6-dimethylfulvene, hexadiene, cyclopentadiene, or piperylene. Other polymerizable monomers, such as styrene and dichlorostyrene, can also be homopolymerized or copolymerized.

[0023] In the present application, the olefin-based resin can include a homopolymer or copolymer based on isobutene. As described above, the olefin-based resin or polymer based on isobutene can refer to an olefin-based resin or polymer containing 70 mol% or more of repeating units derived from isobutene and one or more different polymerizable units.

[0024] In the present application, the olefin-based resin can be butyl rubber or a branched butyl-like rubber. An exemplary olefin-based resin is an unsaturated butyl rubber, such as a copolymer of an olefin or isoolefin and a polyolefin. As the olefin-based resin included in the adhesive composition of the present application, poly(isobutene-co-isoprene), polyisoprene, polybutadiene, polyisobutene, poly(styrene-co-butadiene), natural rubber, butyl rubber, and mixtures thereof can be used. The olefin-based resin usable in the present application can be prepared by any suitable method known in the art, and the present application is not limited to the method for preparing the olefin-based resin.

[0025] In one exemplary embodiment, the olefin-based resin can be a low molecular weight polyisobutene resin. For example, the weight average molecular weight of the olefin-based resin can be 100,000 or less, and 500 or more or 55,000 or more. The present application can achieve a suitable adhesive composition for coating and encapsulation processes by controlling the weight average molecular weight of the olefin-based resin within the above range. The adhesive composition can have a liquid phase and can be suitably applied to encapsulate the side surface of the following OED.

[0026] Furthermore, in one exemplary embodiment, the olefin-based resin can be a resin having one or more reactive functional groups having reactivity with the above thermosettable resin. The reactive functional groups included in the olefin-based resin can be polar functional groups. The type of the reactive functional group is not particularly limited and can be, for example, an acid anhydride group, a carboxyl group, an epoxy group, an amino group, a hydroxyl group, an isocyanate group, Oxazolinyl, oxetanyl, cyanate ester group, phenol group, hydrazide group or amide group. Examples of the olefin-based resin having a reactive functional group may include succinic anhydride-modified polyisobutylene, maleic anhydride-modified liquid polyisobutylene, maleic anhydride-modified liquid polyisoprene, epoxy-modified polyisoprene, hydroxy-modified liquid polyisoprene, and allyl-modified liquid polyisoprene. The present application can provide an adhesive having the following characteristics: for example, desired moisture resistance, and durability and reliability after curing by forming a crosslinked structure between the olefin-based resin and the thermosettable resin, which will be described below.

[0027] In one exemplary embodiment, as described above, the adhesive composition may include a curable resin. The thermosettable resin may be a resin containing one or more thermosettable functional groups. The curable resin may be a thermosettable resin or a photocurable resin. The curable resin may be a resin containing one or more curable functional groups. The specific type of curable resin that can be used in the present application is not particularly limited, and for example, various curable resins known in the art can be used.

[0028] In this specification, the term "thermosettable resin" refers to a resin that can be cured by an appropriate heating or aging process, and the term "photocurable resin" herein refers to a resin that can be cured by the radiation of electromagnetic waves. For example, the photocurable resin may be a photocationic curable resin.

[0029] In the present application, the specific type of the thermosettable resin is not particularly limited as long as the resin has the above properties. For example, a thermosettable resin that can have adhesiveness after curing may be a resin containing one or more thermosettable functional groups, such as epoxy group, glycidyl group, isocyanate group, hydroxy group, carboxyl group or amide group, or a resin containing one or more functional groups that can be cured by the radiation of electromagnetic waves, such as epoxy group, cyclic ether group, thioether group, acetal group or lactone group. In addition, the specific types of such resins may include, but are not limited to, acrylic resins, polyester resins, isocyanate resins and epoxy resins, and epoxy acrylate or urethane acrylate is preferred.

[0030] In an exemplary embodiment, in the present application, as the thermosetting resin, aromatic or aliphatic, or linear or branched epoxy resins can be used. In an exemplary embodiment of the present application, the epoxy resin may contain at least two or more functional groups and the epoxy equivalent weight may be from 180 g / eq to 1,000 g / eq. The epoxy resin having an epoxy equivalent weight within the above range can effectively maintain the properties of the cured product, such as adhesive properties and glass transition temperature. Such epoxy resins may be one or a mixture of two or more of the following: cresol novolac epoxy resin, bisphenol A epoxy resin, bisphenol A novolac epoxy resin, phenol novolac epoxy resin, tetrafunctional epoxy resin, biphenyl type epoxy resin, triphenol methane type epoxy resin, alkyl-modified triphenol methane epoxy resin, naphthalene type epoxy resin, dicyclopentadiene type epoxy resin, and dicyclopentadiene-modified phenol type epoxy resin.

[0031] In the present application, as the thermosetting resin, epoxy resins having a cyclic structure in the molecular structure can be used, and for example, alicyclic epoxy resins can be used. Since the alicyclic epoxy resin has excellent compatibility with olefin-based resins, it cures without phase separation and thus uniform crosslinking in the adhesive can be achieved.

[0032] In an exemplary embodiment, the curable resin may be included in an amount of 10 parts by weight to 80 parts by weight based on 100 parts by weight of the olefin-based resin. Specifically, the curable compound may be included in an amount of 10 parts by weight to 80 parts by weight, 20 parts by weight to 75 parts by weight, or 40 parts by weight to 75 parts by weight based on 100 parts by weight of the olefin-based resin. The present application can provide such an adhesive composition by controlling the content of the curable resin within the above range, which can ensure heat resistance after curing and at the same time has excellent moisture resistance, durability, and reliability.

[0033] In addition, in an exemplary embodiment of the present application, the adhesive composition may contain a curing agent. The curing agent can be a thermal curing agent or a photo-curing agent. For example, one or more suitable types of curing agents can be selected and used according to the type of the curable resin or the functional groups contained in the curable resin. For example, the adhesive composition of the present application may contain both a cationic photo-curing agent and a thermal curing agent, and the present application can be achieved by using pre-curing and main-curing methods and two or more types of curing agents, which will be described below.

[0034] In an exemplary embodiment, when the curable resin is an epoxy resin, as curing agents for epoxy resins known in the art, for example, one or both or more of the following can be used: amine curing agents, imidazole curing agents, phenol curing agents, phosphorus curing agents, and anhydride curing agents, but the present application is not limited thereto.

[0035] In an exemplary embodiment, as a curing agent, an imidazole compound that is in a solid phase at room temperature and has a melting point or decomposition temperature of 80 °C or higher can be used. Such compounds can be, for example, 2-methylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, or 1-cyanoethyl-2-phenylimidazole, but the present application is not limited thereto.

[0036] In an exemplary embodiment of the present application, the thermal curing agent can be a latent curing agent, such as an imidazole-isocyanuric acid addition product, an amine-epoxy addition product, a boron trifluoride-amine complex, or a blocked imidazole. That is, in the present application, light radiation can be first carried out during the curing process of the adhesive composition to control the initial fluidity, and the curing agent as a latent curing agent can be used to cure the curable resin in the main curing after the light radiation.

[0037] The content of the curing agent can be selected according to the composition of the composition, such as the type or ratio of the curable resin. For example, the curing agent can be included in an amount of 1 part by weight to 100 parts by weight, 1 part by weight to 90 parts by weight, or 1 part by weight to 80 parts by weight relative to 100 parts by weight of the curable resin. The weight ratio can be adjusted according to the type and ratio of the curable resin or its functional groups, or the crosslinking density to be achieved.

[0038] When the curable resin is a resin that can be cured by irradiating active energy rays, as an initiator, for example, a cationic photoinitiator or a free radical photoinitiator can be used.

[0039] As a cationic photopolymerization initiator, a salt or an organometallic salt ionizing cation initiator, or an organosilane- or latent sulfonic acid non-ionizing cationic photopolymerization initiator can be used. The salt initiator can be a diaryliodonium salt, a triarylsulfonium salt, or an aryldiazonium salt. The organometallic salt initiator can be an iron arene. The organosilane initiator can be o-nitrobenzyl triarylsilyl ether, triarylsilyl peroxide, or acylsilane. The latent sulfonic acid initiator can be α-sulfonyloxy ketone or α-hydroxymethyl benzoin sulfonate, but the present application is not limited thereto.

[0040] In an exemplary embodiment of the present application, the adhesive composition may further contain a free radical photocurable compound. The free radical photocurable compound can be different from the above-mentioned curable resin.

[0041] To seal the side surface of an organic electronic component, a process of coating the surface with a liquid adhesive composition is performed. However, generally, after coating, it is difficult to maintain the desired encapsulation shape due to the high fluidity of the composition. In the present application, the fluidity can be controlled by pre-curing the adhesive composition applied to the desired position by light irradiation and then subjecting it to main curing. Thus, in the present application, the applied adhesive composition can maintain the desired encapsulation shape before main curing. That is, in the present application, since the adhesive composition contains both a curable resin and / or a free-radical photo-curable compound, a dual-curing method can be introduced, and thus the fluidity of the adhesive composition can be controlled at a high temperature after coating.

[0042] The free-radical photo-curable compound may include a polyfunctional polymerizable compound having high compatibility with the above-described olefin-based resin and curable resin and capable of forming a specific crosslinked structure. In addition, in one exemplary embodiment, the crosslinked structure may be a crosslinked structure formed by heating, a crosslinked structure formed by irradiating active energy rays, or a crosslinked structure formed by aging at room temperature. Here, among the types of "active energy rays", microwaves, infrared (IR) rays, ultraviolet (UV) rays, X-rays, γ-rays, and particle beams including α-particle beams, proton beams, neutron beams, and electron beams can be used, and generally UV rays or electron beams can be used.

[0043] In one exemplary embodiment, the free-radical photo-curable compound may be a polyfunctional active energy ray polymerizable compound, which may be a compound, for example, containing two or more functional groups capable of participating in polymerization by irradiating active energy rays, such as functional groups containing ethylenically unsaturated double bonds, such as acryloyl, methacryloyl, acryloyloxy, or methacryloyloxy; or functional groups such as epoxy groups or oxetanyl groups. In one exemplary embodiment, the polyfunctional active energy ray polymerizable compound may be a bifunctional or higher-functional compound.

[0044] In one exemplary embodiment of the present application, as the polyfunctional active energy ray polymerizable compound, for example, multifunctional acrylate (MFA) can be used.

[0045] In one exemplary embodiment of the present application, the free-radical photo-curable compound may satisfy Formula 1.

[0046] [Formula 1]

[0047]

[0048] In Formula 1, R1 is hydrogen or an alkyl group having 1 to 4 carbon atoms, n is an integer of 2 or greater, and X is a residue derived from a linear, branched, or cyclic alkyl or alkenyl group having 3 to 30 carbon atoms. Here, when X is a residue derived from a cyclic alkyl or alkenyl group, X can be a residue derived from a cyclic alkyl or alkenyl group having 3 to 30, 4 to 28, 6 to 28, 8 to 22, or 12 to 20 carbon atoms. In addition, when X is a residue derived from a linear alkyl or alkenyl group, X can be a residue derived from a linear alkyl or alkenyl group having 3 to 30, 4 to 28, 6 to 25, or 8 to 20 carbon atoms. In addition, when X is a residue derived from a branched alkyl or alkenyl group, X can be a residue derived from a branched alkyl or alkenyl group having 3 to 30, 4 to 28, 5 to 25, or 6 to 20 carbon atoms.

[0049] The term "residue derived from an alkyl or alkenyl group" herein may refer to a residue of a specific compound, such as an alkyl or alkenyl group. In one exemplary embodiment, in Formula 1, when n is 2, X can be an alkylene or a sub-alkylene group. In addition, when n is 3 or greater, X can be an alkyl or alkenyl group in which two or more hydrogen atoms are released and then linked to the (meth)acryloyl group of Formula 1. n can be one within the range of 2 to 20.

[0050] Unless otherwise specifically stated, the term "alkyl" or "alkenyl" herein can be an alkyl or alkenyl group having 1 to 30, 1 to 25, 1 to 20, 1 to 16, 1 to 12, 1 to 8, or 1 to 4 carbon atoms. The alkyl or alkenyl group can have a linear, branched, or cyclic structure and can be optionally substituted with one or more substituents.

[0051] Unless otherwise specifically defined, the term "alkylene" or "sub-alkylene" herein can be an alkylene or sub-alkylene group having 2 to 30, 2 to 25, 2 to 20, 2 to 16, 2 to 12, 2 to 10, or 2 to 8 carbon atoms. The alkylene or sub-alkylene group can have a linear, branched, or cyclic structure and can be optionally substituted with one or more substituents.

[0052] Unless otherwise specifically defined, the term "alkoxy" herein can be an alkoxy group having 1 to 20, 1 to 16, 1 to 12, 1 to 8, or 1 to 4 carbon atoms. The alkoxy group can have a linear, branched, or cyclic structure. In addition, the alkoxy group can be optionally substituted with one or more substituents.

[0053] In an exemplary embodiment, the polyfunctional energy ray-polymerizable compound that can be polymerized by irradiating active energy rays may be polybutadiene dimethacrylate, 1,4-butanediol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,12-dodecanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, dicyclopentanyl di(meth)acrylate, cyclohexane-1,4-dimethanol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, dimethylol dicyclopentane di(meth)acrylate, neopentyl glycol-modified trimethylolpropane di(meth)acrylate, adamantane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, or a mixture thereof.

[0054] The free-radical photocurable compound may be included in an amount of 10 to 100 parts by weight, 10 to 90 parts by weight, 13 to 80 parts by weight, 14 to 70 parts by weight, or 14 to 65 parts by weight based on 100 parts by weight of the olefin-based resin. This application can provide a cured product of an adhesive that maintains the encapsulation structure during pre-curing by adjusting the content of the free-radical photocurable compound within the above range.

[0055] In an exemplary embodiment, the adhesive composition may include a radical initiator and a free-radical photocurable compound. The radical initiator may be a photo radical initiator. A specific type of photoinitiator can be appropriately selected by considering the curing rate and the probability of yellowing. For example, benzoin-based, hydroxyketone-based, aminoketone-based, or phosphine oxide-based photoinitiators can be used, and specifically, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether, acetophenone, dimethylaminoacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 4-(2-hydroxyethoxy)phenyl-2-(hydroxy-2-propyl)ketone, benzophenone, p-phenylbenzophenone, 4,4'-diethylaminobenzophenone, dichlorobenzophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-aminoanthraquinone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, benzyl dimethyl ketal, acetophenone dimethyl ketal, p-dimethylaminobenzoate, oligo[2-hydroxy-2-methyl-1-[4-(1-methylethenyl)phenyl]acetone], or 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide can be used.

[0056] The content of the photo-radical initiator can be varied depending on the type and ratio of the functional groups of the free-radical photocurable compound, or the crosslinking density to be achieved. For example, the photo-radical initiator can be mixed in an amount of 0.1 to 120 parts by weight, or 0.1 to 110 parts by weight, relative to 100 parts by weight of the free-radical photocurable compound. By controlling the content of the photo-radical initiator within the above range, the present application can introduce a suitable crosslinked structure into the adhesive composition, and thus can control the fluidity at high temperatures.

[0057] In one exemplary embodiment, the adhesive composition of the present application may comprise 40 to 90 parts by weight of an olefin-based resin having a WVTR of 50 g / m 2 · day or less, 5 to 50 parts by weight of a curable resin, and 1 to 40 parts by weight of a free-radical photocurable compound. In another exemplary embodiment, the adhesive composition may comprise 50 to 80 parts by weight of an olefin-based resin having a WVTR of 50 g / m 2 · day or less, 10 to 40 parts by weight of a curable resin, and 5 to 30 parts by weight of a free-radical photocurable compound. By adjusting the content ranges of the respective components of the above adhesive composition, the present application can provide such an encapsulating material that can exhibit excellent moisture resistance and excellent durability and reliability at high temperatures and high humidities, and promote the realization of an encapsulation structure of a desired shape.

[0058] The adhesive composition of the present application may comprise a moisture absorbent. The term "moisture absorbent" herein may be a general term for components capable of adsorbing or removing moisture or vapor introduced from the outside through physical or chemical reactions. That is, the moisture absorbent may refer to a moisture-reactive absorbent, a physical absorbent, or a mixture thereof.

[0059] The moisture-reactive absorbent chemically reacts with the vapor, moisture, or oxygen flowing into the resin composition or its cured product to adsorb moisture or vapor. The physical absorbent can extend the migration path of the moisture or vapor permeating through the resin composition or its cured product, and thus can inhibit the penetration of moisture or vapor, and maximize the barrier properties against moisture and vapor through the matrix structure of the resin composition or its cured product and the interaction with the moisture-reactive absorbent.

[0060] Specific types of moisture absorbents that can be used in the present application may be, but are not particularly limited to, for example, one or a mixture of two or more of metal oxides, metal salts, and phosphorus pentoxide (P2O5) as the moisture-reactive absorbent, and zeolite, zirconia, or montmorillonite as the physical absorbent.

[0061] In the present text, specifically, the metal oxide may be lithium oxide (Li2O), sodium oxide (Na2O), barium oxide (BaO), calcium oxide (CaO), or magnesium oxide (MgO), and the metal salt may be, but is not limited to, sulfates such as lithium sulfate (Li2SO4), sodium sulfate (Na2SO4), calcium sulfate (CaSO4), magnesium sulfate (MgSO4), cobalt sulfate (CoSO4), gallium sulfate (Ga2(SO4)3), titanium sulfate (Ti(SO4)2), or nickel sulfate (NiSO4); metal halides such as calcium chloride (CaCl2), magnesium chloride (MgCl2), strontium chloride (SrCl2), yttrium chloride (YCl3), copper chloride (CuCl2), cesium fluoride (CsF), tantalum fluoride (TaF5), niobium fluoride (NbF5), lithium bromide (LiBr), calcium bromide (CaBr2), cerium bromide (CeBr3), selenium bromide (SeBr4), vanadium bromide (VBr3), magnesium bromide (MgBr2), barium iodide (BaI2), or magnesium iodide (MgI2); or metal chlorates such as barium perchlorate (Ba(ClO4)2) or magnesium perchlorate (Mg(ClO4)2), etc.

[0062] In the present application, a properly processed moisture absorbent, such as a metal oxide, can be mixed with the composition. For example, grinding processing may be required for the moisture absorbent, and for this purpose, a three-roll mill, bead mill, or ball mill can be used.

[0063] The adhesive composition of the present application may contain 5 to 100 parts by weight, 5 to 90 parts by weight, 5 to 80 parts by weight, or 10 to 50 parts by weight of a moisture absorbent based on 100 parts by weight of an olefin-based resin. In the adhesive composition of the present application, the content of the moisture absorbent can be controlled to be 5 parts by weight or more so that the adhesive composition or its cured product can exhibit excellent moisture and vapor barrier properties. In addition, since the content of the moisture absorbent is controlled to be 100 parts by weight or less, excellent moisture resistance can be exhibited when forming a film-type encapsulation structure. In addition, in an exemplary embodiment, the adhesive composition of the present application may have a thixotropic index (TI) calculated by Formula 1 of 1.35 to 5.

[0064] [Formula 1]

[0065] T = V 0.5 / V5

[0066] In Formula 1, V 0.5The viscosity of the adhesive composition was measured using a Brookfield viscometer with an RV-7 spindle at a temperature of 25 °C and a rotational speed of 0.5 rpm. V5 is the viscosity of the adhesive composition measured using a Brookfield viscometer with an RV-7 spindle at a temperature of 25 °C and a rotational speed of 5 rpm. Specifically, the thixotropic index (TI) can be 1.35 to 5, or 1.39 to 3.3. As used herein, the term "thixotropy" can refer to the property of a composition that does not flow in a stationary state but flows when oscillated.

[0067] In the present application, when controlling the thixotropic index (TI) of the adhesive composition as described above, an encapsulation structure having excellent moisture resistance can be provided via an olefin-based resin, and problems such as air bubbles flowing into the encapsulating material during the encapsulation of organic electronic components or clogging of the nozzle during the coating of the composition can be prevented, and thus processability and productivity can be improved.

[0068] In one exemplary embodiment, the viscosity of the adhesive composition measured using a Brookfield viscometer with an RV-7 spindle at a temperature of 25 °C and a rotational speed of 0.5 rpm with respect to torque can be 100,000 cP to 1,000,000 cPs. Specifically, in the present application, unless otherwise specifically defined, the viscosity can be measured using a DV-II+Pro as a Brookfield viscometer with an RV-7 spindle under the conditions of a temperature of 25 °C and a rotational speed of 0.5 rpm, and the viscosity range can be 100,000 cPs to 1,000,000 cPs, 200,000 cPs to 900,000 cPs, or 300,000 cPs to 800,000 cPs. When controlling the viscosity of the composition at room temperature to be 100,000 cP or greater, precipitation of substances such as moisture absorbents or inorganic fillers present in the composition can be prevented, and a desired shape of the encapsulation structure can be formed and maintained by coating a desired position with the composition.

[0069] In one exemplary embodiment, the adhesive composition may further contain an inorganic filler. Fillers other than the above-mentioned moisture absorbent can be included to control the thixotropic index (TI) of the adhesive composition. As described above, the thixotropic index (TI) of the adhesive composition needs to be controlled within a specific range. The method of controlling the thixotropic index (TI) within the above range is not particularly limited, but a sufficient amount of inorganic filler can be used. Specific types of fillers that can be used in the present application can be, but are not particularly limited to, for example, one or a mixture of two or more of clay, talc, alumina, calcium carbonate, and silica.

[0070] In addition, in order to improve the coupling efficiency between the filler and the organic adhesive, the present application can use a product in which the filler is surface-treated with an organic material or further contains a coupling agent.

[0071] The adhesive composition of the present application may contain 0 to 50 parts by weight, 1 to 40 parts by weight, or 1 to 20 parts by weight of an inorganic filler based on 100 parts by weight of an olefin-based resin. The present application can provide a packaging structure having excellent moisture or vapor barrier properties and mechanical properties by controlling the content of the inorganic filler to preferably 1 part by weight or more. In addition, the present application can provide a cured product having excellent moisture resistance even when formed into a thin film by controlling the content of the inorganic filler to 50 parts by weight or less.

[0072] In addition, the BET surface area of the inorganic filler may be 35 m 2 / g to 500 m 2 / g, 40 m 2 / g to 400 m 2 / g, 50 m 2 / g to 300 m 2 / g, or 60 m 2 / g to 200 m 2 / g. The specific surface area is measured by the BET method. Specifically, a sample of 1 g of the inorganic filler is added to a tube, and then the specific surface area is measured at -195 °C using ASAP2020 (Micromeritics, US) without pretreatment. The same sample can be subjected to such measurements 3 times to obtain an average value. The present application can provide a packaging material for promoting the desired shape of the packaging structure achieved in the present application by adjusting the specific surface area of the inorganic filler within the above range.

[0073] In the adhesive composition of the present application, in addition to the above components, various additives may be included without affecting the above effects of the present application. For example, the resin composition may contain an appropriate range of defoamers, coupling agents, tackifiers, UV stabilizers, or antioxidants according to the desired physical properties. In an exemplary embodiment, the adhesive composition may further contain a defoamer. When the present application contains a defoamer, defoaming properties are achieved during the above coating process of the adhesive composition, and thus a reliable packaging structure can be provided. In addition, as long as the physical properties of the adhesive composition required in the present application are satisfied, the type of the defoamer is not particularly limited.

[0074] In an exemplary embodiment, the adhesive composition may be a liquid at room temperature, for example, about 25 °C. In an exemplary embodiment of the present application, the adhesive composition may be a solvent-free liquid. Here, a free-radical photocurable compound may be applied as a reactive diluent to the solvent-free liquid composition. The adhesive composition can be applied to encapsulate an organic electronic component, and specifically, the side surface of the organic electronic component. In the present application, since the adhesive composition is a liquid at room temperature, the component can be encapsulated by a method of coating the side surface of the organic electronic component with the composition.

[0075] The viscosity of the exemplary adhesive composition after light irradiation may be from 700 Pa·s to 5,000 Pa·s. Within the above viscosity range, the adhesive composition can maintain the desired shape of the encapsulation structure. In one exemplary embodiment, the viscosity of the adhesive composition can be measured after irradiating the adhesive composition with light in the UV-A wavelength range at a dose of 3 J / cm 2 Furthermore, the viscosity of the adhesive composition can be the viscosity measured with respect to shear stress under the conditions of a temperature of 25 °C, a strain of 10%, and a frequency of 1 Hz. In one exemplary embodiment, the viscosity of the composition may be from 700 Pa·s to 4,000 Pa·s, from 800 Pa·s to 3,000 Pa·s, or from 900 Pa·s to 2,000 Pa·s.

[0076] The term "UV-A wavelength range" herein may refer to a wavelength range of 315 nm to 400 nm. Specifically, in the present specification, light having a UV-A wavelength range may refer to light having any wavelength within the range of 315 nm to 400 nm, or light having two or more wavelengths within the range of 315 nm to 400 nm.

[0077] In one exemplary embodiment of the present application, the adhesive composition can be irradiated with light for primary curing, resulting in the formation of an encapsulation structure of the OED. The primary curing can be carried out by heating or light irradiation. In order to form the encapsulation structure, the adhesive composition requires physical properties such that primary curing can be carried out even at a high primary curing temperature without changing the shape of the UV pre-cured composition. That is, it is necessary to prevent the phenomenon of the adhesive composition spreading at high temperatures. In one exemplary embodiment, the adhesive composition can be pre-cured by irradiating light in the UV-A wavelength range at a dose of 3 J / cm 2 as described above, and the viscosity of the pre-cured resin composition measured with respect to shear stress under the conditions of a temperature of 80 °C, a strain of 10%, and a frequency of 1 Hz may be from 500 Pa·s to 2,000 Pa·s. The viscosity may be, for example, from 500 Pa·s to 1,800 Pa·s, from 500 Pa·s to 1,600 Pa·s, or from 600 Pa·s to 1,500 Pa·s. The adhesive composition of the present application can satisfy the viscosity within the above range and can therefore be effectively applied to encapsulate the side surface of the OED.

[0078] The present application also relates to an OED. As Figure 1 shown, an exemplary OED may include a substrate 21; an organic electronic element 23 formed on the substrate 21; and a side encapsulation layer 10 formed on the peripheral portion of the substrate 21 to surround the side surface of the organic electronic element 23 and containing the above adhesive composition. Furthermore, the exemplary OED may also include a full encapsulation layer 11 covering the entire surface of the organic electronic element 23.

[0079] The full encapsulation layer and the side encapsulation layer can be formed in the same plane. Here, the term "same" in this text can mean substantially the same. For example, "substantially the same" in the same plane means that there may be an error of ±5 μm or ±1 μm in the thickness direction. The full encapsulation layer can encapsulate the top surface of the component, or encapsulate the side surface and the top surface of the component. The side encapsulation layer can be formed on the side surface of the component, but may not be in direct contact with the side surface of the organic electronic component. For example, the organic electronic component can be encapsulated such that the full encapsulation layer can be in direct contact with the top surface and the side surface of the component. That is, the side encapsulation layer may not be in contact with the component, but can be arranged on the peripheral portion of the substrate in the plan view of the OED.

[0080] The term "peripheral portion" in this text refers to the edge. That is, the peripheral portion of the substrate can refer to the edge of the substrate.

[0081] The material for forming the side encapsulation layer can include but is not particularly limited to the above-mentioned adhesive composition.

[0082] At the same time, the full encapsulation layer can include an encapsulation resin, and the encapsulation resin can be an acrylic resin, an epoxy resin, a silicone resin, a fluororesin, a styrene resin, a polyolefin resin, a thermoplastic elastomer, a polyoxyalkylene resin, a polyester resin, a polyvinyl chloride resin, a polycarbonate resin, a polyphenylene sulfide resin, a polyamide resin, or a mixture thereof. The components for forming the full encapsulation layer can be the same as or different from the above-mentioned adhesive composition. However, since the full encapsulation layer is in direct contact with the component, the full encapsulation layer may not contain or contain a small amount of the above-mentioned moisture absorbent. For example, the full encapsulation layer can be included in an amount of 0 parts by weight to 20 parts by weight relative to 100 parts by weight of the encapsulation resin.

[0083] In one exemplary embodiment, the organic electronic component can include a reflective electrode layer formed on a substrate; an organic layer formed on the reflective electrode layer and at least including an emission layer; and a transparent electrode layer formed on the organic layer.

[0084] In this application, the organic electronic component 23 can be an OLED.

[0085] In one exemplary embodiment, the OED according to this application can be but is not limited to a top-emission OED or a bottom-emission type OED.

[0086] The OED can also include a protective film for protecting the organic electronic component between the above-mentioned full encapsulation layer or side encapsulation layer and the organic electronic component.

[0087] In addition, this application relates to a method for manufacturing an OED.

[0088] In an exemplary embodiment, the manufacturing method may include applying the above-described adhesive composition to a peripheral portion of a substrate 21 on which an organic electronic element 23 is formed to surround a side surface of the organic electronic element 23. The application of the adhesive composition may be a step for forming the above-described side encapsulation layer 10.

[0089] Specifically, the formation of the side encapsulation layer may include applying the above-described adhesive composition to the organic electronic element 23 to surround the side surface of the organic electronic element 23, pre-curing the adhesive composition, and performing main curing thereon. The pre-curing may include light radiation, and the main curing may include light radiation or heating.

[0090] Herein, the substrate 21 on which the organic electronic element 23 is formed may be manufactured as follows: a reflective electrode or a transparent electrode is formed on the substrate 21 (such as glass or a film) by vacuum deposition or sputtering, and an organic material layer is formed on the reflective electrode. The organic material layer may include a hole injection layer, a hole transport layer, an emission layer, an electron injection layer, and / or an electron transport layer. Subsequently, a second electrode may be further formed on the organic material layer. The second electrode may be a transparent electrode or a reflective electrode. Thereafter, the above-described side encapsulation layer 10 is applied to a peripheral portion of the substrate 21 to cover the side surface of the organic electronic element 23. Here, the method for forming the side encapsulation layer 10 is not particularly limited, and techniques such as screen printing or dispenser coating may be used to coat the side surface of the substrate 21 with the above-described adhesive composition. In addition, a full encapsulation layer 11 for encapsulating the entire surface of the organic electronic element 23 may be applied. The method for forming the full encapsulation layer 11 may use techniques known in the art, such as drop filling.

[0091] In addition, in the present application, a curing process may be performed on the full encapsulation layer or the side encapsulation layer for encapsulating the OED, and such a curing process (main curing) may be performed in, for example, a heating chamber or a UV chamber, and preferably in both chambers. The main curing conditions may be appropriately selected according to the stability of the OED.

[0092] In an exemplary embodiment, the side encapsulation layer may be formed by coating the above-described adhesive composition, and then the composition may be irradiated with light to initiate crosslinking. The light radiation may include irradiating the composition with light in the UV-A wavelength range at a dose of 0.3 J / cm 2 to 6 J / cm 2 or 0.5 J / cm 2 to 4 J / cm 2 . As described above, the basic shape of the encapsulation structure may be achieved by pre-curing via light irradiation.

[0093] In an exemplary embodiment, the manufacturing method may include subjecting a pre-cured adhesive composition by light irradiation to main curing. The main curing may also include thermally curing at a temperature of 40 °C to 100 °C for 1 hour to 24 hours, 1 hour to 20 hours, 1 hour to 10 hours, or 1 hour to 5 hours. In addition, the main curing may include irradiating light in the UV-A wavelength range at a dose of 0.3 J / cm 2 to 6 J / cm 2 、or 0.5 J / cm 2 to 4 J / cm 2 . The adhesive composition may be subjected to main curing by heating or light irradiation.

[0094] Effect

[0095] The present application provides an adhesive composition and an OED including the same, which can form a structure for effectively blocking moisture or oxygen flowing into the OED from the outside, thereby ensuring the lifespan of the OED, achieving top-emitting OED, and exhibiting excellent adhesive durability and reliability, as well as excellent reliability under high temperature and high humidity. Brief Description of the Drawings

[0096] Figure 1 is a cross-sectional view of an OED according to an exemplary embodiment of the present application.

[0097] [List of Reference Numerals]

[0098] 1: Adhesive

[0099] 10: Side encapsulation layer

[0100] 11: Full encapsulation layer

[0101] 21: Substrate

[0102] 22: Cover substrate

[0103] 23: Organic electronic element Detailed Description of the Embodiments

[0104] Hereinafter, the present application will be further described in detail with reference to examples according to the present application and comparative examples not according to the present application, and the scope of the present application is not limited to the following examples.

[0105] Example 1

[0106] The polyisobutene resin (BASF, B14, Mw = 60,000) as an olefin-based resin, the alicyclic epoxy resin (Kukdo Chemical, ST-3000) and epoxy acrylate (Sartomer, CN110) as curable resins, and 1,6-hexanediol diacrylate (HDDA) as a free-radical photocurable compound were placed in a mixing container at room temperature in a weight ratio of 70:15:15:5 (B14:ST-3000:CN110:HDDA). 5 parts by weight of 2,2-dimethoxy-1,2-diphenylethane-1-one (Irgacure 651, Ciba) as a radical initiator was placed in the container relative to 100 parts by weight of the resin components (olefin-based resin and curable resin), and 33 parts by weight of an imidazole curing agent (Shikoku, 2P4MHZ) as a curing agent was placed in the container relative to 100 parts by weight of the curable resin. In addition, 3 parts by weight of pyrogenic silica (Aerosil, Evonik, R805, particle size: 10 nm to 20 nm) as an inorganic filler was placed in the container relative to 100 parts by weight of the resin components (olefin-based resin and curable resin). At the same time, 40 parts by weight of calcium oxide (CaO, Aldrich) as a moisture absorbent was further placed in the container relative to 100 parts by weight of the resin components (olefin-based resin and curable resin).

[0107] A homogeneous composition solution was prepared in the mixing container using a planetary mixer (Kurabo Industries, KK-250s).

[0108] Example 2

[0109] The polyisobutene resin (BASF, B14, Mw = 60,000) as an olefin-based resin, the alicyclic epoxy resin (Kukdo Chemical, ST-3000) and another alicyclic epoxy resin (Daicel, Celloxide 2021P) as curable resins were placed in a mixing container at room temperature in a weight ratio of 60:25:15 (B14:ST-3000:2021P). Then, 25 parts by weight of a photo cationic initiator (San-apro, CPI-101A) was placed in the container relative to 100 parts by weight of the curable resin, and 12.5 parts by weight of an imidazole curing agent (Shikoku, 2P4MHZ) as a thermal curing agent was placed in the container relative to 100 parts by weight of the curable resin. In addition, 3 parts by weight of pyrogenic silica (Aerosil, Evonik, R805, particle size: 10 nm to 20 nm) as an inorganic filler was placed in the container relative to 100 parts by weight of the resin components (olefin-based resin and curable resin). At the same time, 40 parts by weight of calcium oxide (CaO, Aldrich) as a moisture absorbent was further placed in the container relative to 100 parts by weight of the resin components (olefin-based resin and curable resin).

[0110] A homogeneous composition solution was prepared in the mixing container using a planetary mixer (Kurabo Industries, KK-250s).

[0111] Example 3

[0112] The polyisobutene resin (BASF, B14, Mw = 60,000) as an olefin-based resin, the alicyclic epoxy resin (Kukdo Chemical, ST-3000) and epoxy acrylate (Sartomer, CN110) as curable resins, and the polybutadiene dimethacrylate (Sartomer, CN301) and 1,6-hexanediol diacrylate (HDDA) as free-radical photocurable compounds were placed in a mixing container at room temperature in a weight ratio of 50:15:20:15:10 (B14:ST-3000:CN110:CN301:HDDA). 20 parts by weight of 2,2-dimethoxy-1,2-diphenylethane-1-one (Irgacure 651, Ciba) as a radical initiator was placed in the container with respect to 100 parts by weight of the free-radical photocurable compounds, and 28.5 parts by weight of an imidazole-based curing agent (Shikoku, 2P4MHZ) as a curing agent was placed in the container with respect to 100 parts by weight of the curable resin. In addition, 3.5 parts by weight of pyrogenic silica (Aerosil, Evonik, R805, particle size: 10 nm to 20 nm) as an inorganic filler was placed in the container with respect to 100 parts by weight of the resin components (olefin-based resin and curable resin). Meanwhile, 47 parts by weight of calcium oxide (CaO, Aldrich) as a moisture absorbent was further placed in the container with respect to 100 parts by weight of the resin components (olefin-based resin and curable resin).

[0113] A homogeneous composition solution was prepared in the mixing container using a planetary mixer (Kurabo Industries, KK-250s).

[0114] Comparative Example 1

[0115] The alicyclic epoxy resins (Kukdo Chemical, ST-3000) and another alicyclic epoxy resin (Daicel, Celloxide 2021P) as curable resins were placed in a mixing container at room temperature in a weight ratio of 70:30 (ST-3000:2021P). Then, 10 parts by weight of a photo cationic initiator (San-apro, CPI-101A) was placed in the container with respect to 100 parts by weight of the curable resin, and 10 parts by weight of an imidazole curing agent (Shikoku, 2P4MHZ) as a thermal curing agent was placed in the container with respect to 100 parts by weight of the curable resin. In addition, 3 parts by weight of pyrogenic silica (Aerosil, Evonik, R805, particle size: 10 nm to 20 nm) was placed in the container as an inorganic filler with respect to 100 parts by weight of the curable resin. At the same time, 40 parts by weight of calcium oxide (CaO, Aldrich) was further placed in the container as a moisture absorbent with respect to 100 parts by weight of the curable resin.

[0116] A planetary mixer (Kurabo Industries, KK-250s) was used to prepare a homogeneous composition solution in the mixing container.

[0117] Comparative Example 2

[0118] Polyisobutene resin (BASF, B14, Mw = 60,000) as an olefin-based resin, polybutadiene dimethacrylate (Sartomer, CN301) and 1,6-hexanediol diacrylate (HDDA) as free-radical photocurable compounds were placed in a mixing container at room temperature in a weight ratio of 80:20:10 (B14:CN301:HDDA). 16.66 parts by weight of 2,2-dimethoxy-1,2-diphenylethane-1-one (Irgacure651, Ciba) was placed in the container as a radical initiator with respect to 100 parts by weight of the free-radical photocurable compound. In addition, 3.75 parts by weight of pyrogenic silica (Aerosil, Evonik, R805, particle size: 10 nm to 20 nm) was placed in the container as an inorganic filler with respect to 100 parts by weight of the olefin-based resin. At the same time, 50 parts by weight of calcium oxide (CaO, Aldrich) was further placed in the container as a moisture absorbent with respect to 100 parts by weight of the olefin-based resin.

[0119] A planetary mixer (Kurabo Industries, KK-250s) was used to prepare a homogeneous composition solution in the mixing container.

[0120] Comparative Example 3

[0121] Polyisobutene resin (BASF, B14, Mw = 60,000) as an olefin-based resin, alicyclic epoxy resin (Kukdo Chemical, ST-3000) and epoxy acrylate (Sartomer, CN110) as curable resins, and 1,6-hexanediol diacrylate (HDDA) as a free-radical photocurable compound were placed in a mixing container at room temperature in a weight ratio of 40:30:30:10 (B14:ST-3000:CN110:HDDA). 5 parts by weight of 2,2-dimethoxy-1,2-diphenylethane-1-one (Irgacure 651, Ciba) as a radical initiator was placed in the container with respect to 100 parts by weight of the resin components (olefin-based resin and curable resin), and 16.66 parts by weight of an imidazole curing agent (Shikoku, 2P4MHZ) as a curing agent was placed in the container with respect to 100 parts by weight of the curable resin. In addition, 3 parts by weight of pyrogenic silica (Aerosil, Evonik, R805, particle size: 10 nm to 20 nm) as an inorganic filler was placed in the container with respect to 100 parts by weight of the resin components (olefin-based resin and curable resin). Meanwhile, 40 parts by weight of calcium oxide (CaO, Aldrich) as a moisture absorbent was further placed in the container with respect to 100 parts by weight of the resin components (olefin-based resin and curable resin).

[0122] A homogeneous composition solution was prepared in the mixing container using a planetary mixer (Kurabo Industries, KK-250s).

[0123] Comparative Example 4

[0124] The polyisobutene resin (BASF, B14, Mw = 60,000) as an olefin-based resin, the alicyclic epoxy resin (Kukdo Chemical, ST-3000) and another alicyclic epoxy resin (Daicel, Celloxide 2021P) as curable resins were placed in a mixing container at room temperature in a weight ratio of 85:10:5 (B14:ST-3000:2021P). Then, 10 parts by weight of a photo cationic initiator (San-apro, CPI-101A) was placed in the container with respect to 100 parts by weight of the resin components (olefin-based resin and curable resin), and 5 parts by weight of an imidazole curing agent (Shikoku, 2P4MHZ) as a thermal curing agent was placed in the container with respect to 100 parts by weight of the resin components (olefin-based resin and curable resin). In addition, 3 parts by weight of pyrogenic silica (Aerosil, Evonik, R805, particle size: 10 nm to 20 nm) as an inorganic filler was placed in the container with respect to 100 parts by weight of the resin components (olefin-based resin and curable resin). At the same time, 40 parts by weight of calcium oxide (CaO, Aldrich) as a moisture absorbent was further placed in the container with respect to 100 parts by weight of the resin components (olefin-based resin and curable resin).

[0125] A planetary mixer (Kurabo Industries, KK-250s) was used to prepare a homogeneous composition solution in the mixing container.

[0126] Hereinafter, the physical properties in the examples and comparative examples were evaluated by the following methods.

[0127] 1. Measurement of glass transition temperature

[0128] The adhesive compositions prepared in each of the examples and comparative examples were applied to 0.7T soda-lime glass, and the same type of glass was laminated thereon. The adhesive composition was irradiated with light in the UV-A wavelength range at a dose of 3 J / cm 2 and heated in an oven at 100 °C for 3 hours. The adhesives according to each of the examples and comparative examples cured by the above steps were collected in an amount of 3 mg to 8 mg, placed in an aluminum pan for differential scanning calorimetry (DSC), and DSC was performed in the temperature range of -50 °C to 300 °C (measurement device: TA, Q2000 type) to measure the glass transition temperature (scanning rate: 10 °C / min).

[0129] 2. Tensile modulus

[0130] The adhesive composition solutions prepared in each of the examples and comparative examples were applied to the release surface of a release PET film, and the adhesive composition was irradiated with light in the UV-A wavelength range at a dose of 3 J / cm 2Irradiate with a dose of, and heat in an oven at 100 °C for 3 hours to produce a coating film with a thickness of 200 μm. Cut the produced coating film in the longitudinal direction along the coating direction into a size of 30 mm × 10 mm (length × width) to prepare a sample, and tape both ends of the sample along the longitudinal direction, leaving the non-taped part of the 10 mm sample. Subsequently, stretch the taped part at 18 mm / min and 25 °C (measured using a texture analyzer) to measure the tensile modulus.

[0131] 3. Heat resistance

[0132] Apply the adhesive compositions prepared in each of the examples and comparative examples to 0.7T soda-lime glass, and laminate the same type of glass on it. Irradiate the adhesive composition with light in the UV-A wavelength range at a dose of 3 J / cm 2 and heat it in an oven at 100 °C for 3 hours to prepare a sample. Then, observe the specimen to determine whether bubbles are generated between the glass substrate and the adhesive layer when kept in an oven at 85 °C for about 500 hours. By visual observation, when a large number of bubbles are generated between the glass substrate and the adhesive layer, it is denoted as X; when a relatively small number of bubbles are generated, it is denoted as △; when no bubbles are generated, it is denoted as O.

[0133] 4. Adhesion reliability at high temperature and high humidity

[0134] Apply the adhesive compositions prepared in each of the examples and comparative examples to 0.7T soda-lime glass, and laminate the same type of glass on it. Irradiate the adhesive composition with light in the UV-A wavelength range at a dose of 3 J / cm 2 and heat it in an oven at 100 °C for 3 hours to prepare a sample. Then, keep the sample in a thermo-hygrostat chamber at 85 °C and 85% relative humidity for about 500 hours, and observe to determine whether lifting occurs at the interface between the glass substrate and the adhesive layer. By visual observation, when lifting occurs at the interface between the glass substrate and the adhesive layer, it is denoted as X; when no lifting occurs, it is denoted as O.

[0135] [Table 1]

[0136]

[0137] The present invention also relates to the following technical solutions:

[0138] 1. An adhesive composition for encapsulating an organic electronic component, which shows a first peak having a glass transition temperature in the range of 20°C to 60°C and a second peak having a glass transition temperature in the range of 80°C to 120°C measured by differential scanning calorimetry after curing, and has a tensile modulus of 1 MPa to 300 MPa at 25°C after curing.

[0139] 2. The adhesive composition according to item 1, comprising:

[0140] An olefin-based resin having a water vapor transmission rate of 50 g / m 2 · day or less, and a curable resin.

[0141] 3. The adhesive composition according to item 2, wherein the curable resin contains one or more curable functional groups.

[0142] 4. The adhesive composition according to item 2, wherein the curable resin is included in an amount of 10 parts by weight to 70 parts by weight relative to 100 parts by weight of the olefin-based resin.

[0143] 5. The adhesive composition according to item 2, wherein the olefin-based resin has a weight average molecular weight of 100,000 or less.

[0144] 6. The adhesive composition according to item 2, wherein the olefin-based resin has one or more reactive functional groups, and the reactive functional groups have reactivity with the curable resin.

[0145] 7. The adhesive composition according to item 6, wherein the reactive functional groups are acid anhydride groups, carboxyl groups, epoxy groups, amino groups, hydroxyl groups, isocyanate groups, oxazoline groups, oxetanyl groups, cyanate ester groups, phenolic groups, hydrazide groups or amide groups.

[0146] 8. The adhesive composition according to item 2, further comprising:

[0147] 1 part by weight to 100 parts by weight of a curing agent relative to 100 parts by weight of the curable resin.

[0148] 9. The adhesive composition according to item 2, further comprising:

[0149] A free-radical photocurable compound.

[0150] 10. The adhesive composition according to item 9, wherein the free-radical photocurable compound contains a polyfunctional energy ray-polymerizable compound.

[0151] 11. The adhesive composition according to item 9, wherein the free-radical photocurable compound satisfies Formula 1:

[0152] [Formula 1]

[0153]

[0154] In Formula 1, R1 is hydrogen or an alkyl group having 1 to 4 carbon atoms, n is an integer of 2 or greater, and X is a residue derived from a linear, branched, or cyclic alkyl or alkenyl group having 3 to 30 carbon atoms.

[0155] 12. The adhesive composition according to item 9, wherein the free-radical photocurable compound is included in an amount of 10 parts by weight to 100 parts by weight relative to 100 parts by weight of the olefin-based resin.

[0156] 13. The adhesive composition according to item 9, further comprising:

[0157] A photoinitiator in an amount of 0.1 part by weight to 20 parts by weight relative to 100 parts by weight of the free-radical photocurable compound.

[0158] 14. The adhesive composition according to item 2, further comprising:

[0159] A moisture absorbent.

[0160] 15. The adhesive composition according to item 14, wherein the moisture absorbent is included in an amount of 5 parts by weight to 100 parts by weight relative to 100 parts by weight of the olefin-based resin.

[0161] 16. The adhesive composition according to item 2, further comprising:

[0162] Inorganic filler.

[0163] 17. The adhesive composition according to item 9, wherein the olefin-based resin, the curable resin, and the free-radical photocurable compound are included in amounts of 40 parts by weight to 90 parts by weight, 5 parts by weight to 50 parts by weight, and 1 part by weight to 40 parts by weight, respectively.

[0164] 18. An organic electronic device, comprising:

[0165] A substrate;

[0166] An organic electronic component formed on the substrate; and

[0167] A side encapsulation layer formed on a peripheral portion of the substrate to surround a side surface of the organic electronic component and comprising the adhesive composition according to item 1.

[0168] 19. The organic electronic device according to item 18 further comprises:

[0169] A full encapsulation layer for covering the entire surface of the organic electronic component,

[0170] wherein the full encapsulation layer is in the same plane as the side encapsulation layer.

[0171] 20. A method of manufacturing an organic electronic device, comprising:

[0172] Applying the adhesive composition according to item 1 to a peripheral portion of a substrate on which an organic electronic component is formed to surround a side surface of the organic electronic component;

[0173] Irradiating the adhesive composition with light; and

[0174] Heating the adhesive composition.

Claims

1. An adhesive composition for encapsulating an organic electronic component, wherein the adhesive composition exhibits a first peak having a glass transition temperature in the range of 20°C to 60°C and a second peak having a glass transition temperature in the range of 80°C to 120°C, measured by differential scanning calorimetry after curing, wherein the adhesive composition has a tensile modulus of 1 MPa to 300 MPa at 25°C after curing, wherein the adhesive composition is a solvent-free liquid at 25°C, wherein the adhesive composition comprises an olefin-based resin, a curable resin, and a free-radical photocurable compound, wherein the curable resin is included in an amount of 40 parts by weight to 75 parts by weight relative to 100 parts by weight of the olefin-based resin, and wherein the weight-average molecular weight of the olefin-based resin is less than 100,000.

2. The adhesive composition according to claim 1, wherein the olefin-based resin has a water vapor transmission rate of 50 g / m 2 ·day or less.

3. The adhesive composition according to claim 1, wherein the curable resin comprises one or more curable functional groups.

4. The adhesive composition according to claim 1, wherein the olefin-based resin has one or more reactive functional groups having reactivity with the curable resin.

5. The adhesive composition according to claim 4, wherein the reactive functional group is an acid anhydride group, a carboxyl group, an epoxy group, an amino group, a hydroxyl group, an isocyanate group, an oxazoline group, an oxetanyl group, a cyanate group, a phenolic group, a hydrazide group or an amide group.

6. The adhesive composition according to claim 1, further comprising: a curing agent in an amount of 1 part by weight to 100 parts by weight relative to 100 parts by weight of the curable resin.

7. The adhesive composition according to claim 1, wherein the free-radical photocurable compound comprises a polyfunctional energy-ray polymerizable compound.

8. The adhesive composition according to claim 1, wherein the free-radical photocurable compound satisfies Formula 1: [Formula 1] In Formula 1, R1 is hydrogen or an alkyl group having 1 to 4 carbon atoms, n is an integer of 2 or greater, and X is a residue derived from a linear, branched, or cyclic alkyl or alkenyl group having 3 to 30 carbon atoms.

9. The adhesive composition according to claim 1, wherein the free-radical photocurable compound is included in an amount of 10 parts by weight to 100 parts by weight relative to 100 parts by weight of the olefin-based resin.

10. The adhesive composition according to claim 1, further comprising: a photoinitiator in an amount of 0.1 part by weight to 20 parts by weight relative to 100 parts by weight of the free-radical photocurable compound.

11. The adhesive composition according to claim 1, further comprising: a moisture absorbent.

12. The adhesive composition according to claim 11, wherein the moisture absorbent is included in an amount of 5 parts by weight to 100 parts by weight relative to 100 parts by weight of the olefin-based resin.

13. The adhesive composition according to claim 1, further comprising: an inorganic filler.

14. The adhesive composition according to claim 1, wherein the olefin-based resin, the curable resin, and the free-radical photocurable compound are included in amounts of 40 parts by weight to 90 parts by weight, 5 parts by weight to 50 parts by weight, and 1 part by weight to 40 parts by weight, respectively.

15. An organic electronic device, comprising: a substrate; An organic electronic component formed on the substrate; and A side encapsulation layer formed on a peripheral portion of the substrate to surround a side surface of the organic electronic component and including the adhesive composition according to claim 1.

16. The organic electronic device according to claim 15, further comprising: A full encapsulation layer for covering an entire surface of the organic electronic component, wherein the full encapsulation layer is present in the same plane as the side encapsulation layer.

17. A method of manufacturing an organic electronic device, comprising: Applying the adhesive composition according to claim 1 to a peripheral portion of a substrate on which an organic electronic component is formed to surround a side surface of the organic electronic component; Irradiating the adhesive composition with light; and Heating the adhesive composition.

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