KR20160114358A

KR20160114358A - Adhesive composition, adhesive film comprising the same, organic electronic device comprising the same and method for preparing the organic electronic device

Info

Publication number: KR20160114358A
Application number: KR1020150040739A
Authority: KR
Inventors: 김소영; 양세우; 이승민; 심정섭; 이진규
Original assignee: 주식회사 엘지화학
Priority date: 2015-03-24
Filing date: 2015-03-24
Publication date: 2016-10-05
Also published as: KR101917081B1

Abstract

The present invention relates to an adhesive composition, an adhesive film containing the adhesive composition, and an organic electronic device including the adhesive composition, and it is possible to form a structure capable of effectively blocking moisture or oxygen introduced from the outside into the organic electronic device, An adhesive composition, an adhesive film, and an organic electronic device including the adhesive composition are provided.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to an adhesive composition, an adhesive film containing the adhesive composition, an organic electronic device including the adhesive composition, and a method of manufacturing the organic electronic device.

The present application relates to an adhesive composition, an adhesive film comprising the same, an organic electronic device including the same, and a method of manufacturing the organic electronic device.

An organic electronic device (OED) refers to an apparatus that includes an organic material layer that generates holes and electrons to generate an alternating current. Examples thereof include a photovoltaic device, a rectifier, A transmitter and an organic light emitting diode (OLED).

Organic light emitting diodes (OLEDs) among the organic electronic devices have lower power consumption, faster response speed, and are advantageous for thinning display devices or illumination. In addition, OLEDs are expected to be applied in various fields covering various portable devices, monitors, notebooks, and televisions because of their excellent space utilization.

In commercialization of OLEDs and expansion of applications, the main problem is durability. Organic materials and metal electrodes contained in OLEDs are very easily oxidized by external factors such as moisture. Thus, products containing OLEDs are highly sensitive to environmental factors. Accordingly, various methods have been proposed to effectively block penetration of oxygen or moisture from the outside into organic electronic devices such as OLEDs.

Patent Document 1 is a film of an adhesive encapsulating composition and an organic electroluminescent device, which is an adhesive based on PIB (polyisobutylene) and has poor processability and poor reliability under high temperature and high humidity conditions.

Korean Patent Publication No. 2008-0088606

The present application relates to an adhesive composition which is capable of forming a structure capable of effectively blocking water or oxygen introduced from the outside into an organic electronic device, realizing a top emission organic electronic device, excellent in handleability and processability, And an organic electronic device including the same.

The present application relates to an adhesive composition. The adhesive composition can be applied to encapsulating or encapsulating organic electronic devices such as, for example, OLEDs. In one example, the adhesive composition of the present application can be applied to encapsulating or encapsulating at least one side of an organic electronic device. Thus, after the adhesive composition has been applied to the encapsulation, it may be present at the periphery of the organic electronic device.

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

Exemplary adhesive compositions may include thermosetting resins, thermosetting agents, moisture sorbents and magnetic materials. As described above, the adhesive composition can be applied to encapsulating the organic electronic device, and specifically, to sealing the side surface of the organic electronic device. Conventionally, in sealing a side surface of an organic electronic device, a liquid adhesive composition is applied. However, the fluidity of the composition at a high temperature is increased during the post-application curing process, which makes it difficult to achieve the desired encapsulation shape. For example, when an adhesive composition is formed using only a photo-curable compound, the moisture adsorbent contained in the composition hinders light from being transmitted, and the desired degree of crosslinking or curing can not be achieved. Accordingly, in order to solve the above problem, when the adhesive composition is formed using a thermosetting compound, the adhesive composition spreads at a high temperature as the curing proceeds by applying heat for a long time, It was practically impossible to form an encapsulation structure. In the present application, by applying a magnetic field to a liquid adhesive composition applied at a desired position, heat is generated by the magnetic material contained in the composition, and the heat hardening of the composition rapidly proceeds due to the heat. Accordingly, the present application can provide an encapsulating material having excellent moisture barrier properties while maintaining the encapsulation encapsulation shape. That is, the adhesive composition according to the present application not only has a good moisture barrier property including a large amount of moisture adsorbent, but also has a high degree of curing even though it contains a large amount of the moisture adsorbent, thereby providing a reliable sealing structure.

In one example, the adhesive composition of the present application may have a viscosity of at least 10,000 cPs, measured at 25 ° C temperature, with a rotational speed of 10 rpm and torque on a Brookfield viscometer at 7 spindles. Specifically, the viscosity can be measured using DV-II + Pro as a Brookfield viscometer, and may range from 10,000 cPs to 500,000 cPs, from 20,000 cPs to 400,000 cPs, or from 30,000 cPs to 300,000 cPs. In the present application, it is possible to prevent sedimentation of a magnetic substance or a moisture adsorbent or the like present in the composition by controlling the viscosity of the composition at room temperature to 10,000 cPs or more, and to provide a desired It may be possible to implement and maintain the shape. The method for controlling the viscosity is not particularly limited, but can be controlled through the kind of the constituent constituting the composition, the content between the constituents, and the like.

In one example, as described above, the adhesive composition may comprise a thermosetting resin. The thermosetting resin may include at least one thermosetting functional group. In addition, the thermosetting resin may be, for example, a cationic thermosetting compound.

As used herein, the term " thermosetting resin " means a resin that can be cured through an appropriate heat application or aging process, and the term " photo-curable resin " means a resin that can be cured by irradiation with electromagnetic waves it means.

The specific kind of the thermosetting resin in the present application is not particularly limited as long as it has the above-mentioned characteristics. Examples of the resin include one or more thermosetting functional groups such as an epoxy group, a glycidyl group, an isocyanate group, a hydroxyl group, a carboxyl group or an amide group which can be cured to exhibit an adhesive property. Specific examples of the resin include acrylic resins, polyester resins, isocyanate resins, epoxy resins, and the like, but the present invention is not limited thereto.

As the thermosetting resin in the present application, aromatic or aliphatic; Or a linear or branched epoxy resin may be used. In one embodiment of the present invention, an epoxy resin having an epoxy equivalent of 180 g / eq to 1,000 g / eq, which contains two or more functional groups, may be used. By using an epoxy resin having an epoxy equivalent in the above range, properties such as adhesion performance and glass transition temperature of the cured product can be effectively maintained. Examples of such an epoxy resin include cresol novolak epoxy resin, bisphenol A epoxy resin, bisphenol A novolac epoxy resin, phenol novolak epoxy resin, tetrafunctional epoxy resin, biphenyl type epoxy resin, An epoxy resin, an alkyl-modified triphenolmethane epoxy resin, a naphthalene-type epoxy resin, a dicyclopentadiene-type epoxy resin, or a dicyclopentadiene-modified phenol-type epoxy resin.

In the present application, for example, an epoxy resin containing a cyclic structure in a molecular structure can be used as the thermosetting resin, and more preferably, an epoxy resin containing an aromatic group (for example, a phenyl group) can be used. When the epoxy resin contains an aromatic group, the cured product has excellent thermal and chemical stability and exhibits a low moisture absorption amount, thereby improving the reliability of the organic electronic device encapsulation structure. Specific examples of the aromatic group-containing epoxy resin that can be used in the present invention include biphenyl type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, dicyclopentadiene modified phenol type epoxy resin, cresol type epoxy resin, A phenol novolac epoxy resin, a triphenol methane type epoxy resin, and an alkyl-modified triphenol methane epoxy resin, and the like, or a mixture of two or more thereof, but is not limited thereto no.

As the epoxy resin in the present application, for example, a silane-modified epoxy resin or a silane-modified epoxy resin having an aromatic group can be used. When an epoxy resin having such a silane-modified structure and having a silane group is used, it is possible to maximize the adhesiveness with the glass substrate or the substrate inorganic material of the organic electronic device, and to improve the moisture barrier property, the durability and the reliability. The specific kind of the above-mentioned epoxy resin which can be used in the present invention is not particularly limited, and such a resin can be easily obtained from, for example, a purchase place such as Kukdo Chemical Co.,

Further, in the embodiments of the present application, the adhesive composition may include a thermosetting agent. The curing agent may be appropriately selected and used depending on the type of the functional group contained in the thermosetting resin or the thermosetting resin.

In one example, in the case where the thermosetting resin is an epoxy resin, examples of the curing agent that can be used as the curing agent of an epoxy resin well known in the art include amine curing agents, imidazole curing agents, phenol curing agents, phosphorus curing agents, and acid anhydride curing agents Or more, but the present invention is not limited thereto.

In one example, as the curing agent, an imidazole compound which is solid at room temperature and has a melting point or a decomposition temperature of 80 ° C or higher can be used. Such compounds include, for example, 2-methylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole or 1-cyanoethyl- For example, but not limited to,

The content of the thermosetting agent can be selected according to the composition of the composition, for example, the type and ratio of the thermosetting resin. For example, the thermosetting agent may be contained in an amount of 0.01 to 20 parts by weight, 0.05 to 10 parts by weight or 0.08 to 5 parts by weight based on 100 parts by weight of the resin component. However, the weight ratio can be changed depending on the kind and ratio of the functional groups of the thermosetting resin or the thermosetting resin, the crosslinking density to be implemented, and the like. In the present specification, the term " 100 parts by weight of resin component " means 100 parts by weight of the above-mentioned thermosetting resin, or may mean 100 parts by weight of an olefin resin to be described later. That is, the resin component means the resin constituting the adhesive composition, and when the adhesive composition includes the thermosetting resin and the olefin resin together, it may mean 100 parts by weight of the thermosetting resin plus the olefin resin.

Also, in embodiments of the present application, the adhesive composition may exclude cationic photoinitiators. That is, the adhesive composition of the present application may not contain a cationic photoinitiator. Considering that the cationic photo-curing agent is vulnerable to moisture, heat can be applied by the magnetic material and the thermosetting resin can be cured by the heat curing agent.

In one example, the adhesive composition of the present application may comprise a magnetic material. The type of the magnetic body is not particularly limited as long as it can generate heat by vibrating when a magnetic field is applied. In one example, the magnetic body may be at least one selected from the group consisting of Fe ₃ O ₄ , Fe ₂ O ₃ , MnFe ₂ O ₄ , CoFe ₂ O ₄ , Fe, CoPt, and FePt. The average particle size of the magnetic material may be in the range of 1 nm to 1 탆, 5 nm to 800 nm, 10 nm to 600 nm, 20 nm to 400 nm, 30 nm to 200 nm, or 40 nm to 100 nm. By controlling the size of the magnetic substance as described above, it is possible to have a suitable dispersibility in the composition and to realize a dense crosslinked structure of the composition containing a large amount of the moisture adsorbent.

The magnetic material may be contained in an amount of 1 to 25 parts by weight, 2 to 23 parts by weight, 5 to 20 parts by weight, or 10 to 20 parts by weight based on 100 parts by weight of the resin component. In the present application, by controlling the content of the magnetic material in the above range, the curing of the composition can be sufficiently promoted and the curing degree in an appropriate range can be realized, thereby securing the physical properties of the sealing material of the present invention.

The adhesive composition of the present application may contain a moisture adsorbent, as described above. The term " moisture adsorbent " may be used to mean a component capable of adsorbing or removing moisture or moisture introduced from the outside through physical or chemical reaction or the like. Means a water-reactive adsorbent or a physical adsorbent, and mixtures thereof are also usable.

The water-reactive adsorbent chemically reacts with moisture, moisture or oxygen introduced into the resin composition or the cured product thereof to adsorb moisture or moisture. The physical adsorbent is capable of inhibiting the penetration of moisture or moisture penetrating into the resin composition or the cured product thereof to increase the permeability of the resin composition or the cured product. The physical adsorbent is capable of suppressing the penetration of water or moisture through the matrix structure of the resin composition or the cured product thereof, It is possible to maximize the barrier property against moisture.

Specific examples of the moisture adsorbent that can be used in the present application are not particularly limited. For example, in the case of a water-reactive adsorbent, a metal powder such as alumina, a metal oxide, a metal salt, or a phosphorus pentoxide (P ₂ O ₅ ) And mixtures of two or more species. Examples of the physical adsorbent include silica, zeolite, titania, zirconia or montmorillonite.

Specific examples of the metal oxide include lithium oxide (Li ₂ O), sodium oxide (Na ₂ O), barium oxide (BaO), calcium oxide (CaO) and magnesium oxide (MgO) Examples include lithium sulfate (Li ₂ SO _4), sodium sulfate (Na ₂ SO _4), calcium sulfate (CaSO _4), magnesium sulfate (MgSO _4), cobalt sulfate (CoSO _4), sulfate, gallium (Ga ₂ (SO ₄₎ _3), titanium sulfate (Ti (SO ₄₎ ₂₎ or nickel sulfate (a sulfate such as NiSO _4), calcium chloride (CaCl _2), magnesium chloride (MgCl _2), strontium chloride (SrCl _2), chloride, yttrium (YCl ₃₎ , Cobalt chloride (CuCl ₂ ), cesium fluoride (CsF), tantalum fluoride (TaF ₅ ), niobium fluoride (NbF ₅ ), lithium bromide (LiBr), calcium bromide (CaBr ₂ ), cesium bromide (CeBr ₃ ) (SeBr _4), vanadium bromide (VBr _3), a metal halide such as magnesium bromide (MgBr _2), barium iodide (BaI _2), or magnesium iodide (MgI _2); Or metal chlorates such as barium perchlorate (Ba (ClO ₄ ) ₂ ) or magnesium perchlorate (Mg (ClO ₄ ) ₂ ), and the like.

In the present application, the moisture adsorbent such as the metal oxide or the like can be blended into the composition in a properly processed state. For example, a grinding process of the moisture adsorbent may be necessary, and a grinding process of the moisture adsorbent may be performed using a three-roll mill, a bead mill or a ball mill.

The adhesive composition of the present application may contain a moisture adsorbent in an amount of 10 parts by weight to 100 parts by weight, 10 to 90 parts by weight, 10 parts by weight to 80 parts by weight or 15 to 50 parts by weight based on 100 parts by weight of the resin component have. The adhesive composition of the present application can preferably control the content of the moisture adsorbent to 10 parts by weight or more so that the adhesive composition or the cured product thereof exhibits excellent moisture and moisture barrier properties. In addition, when the content of the moisture adsorbent is controlled to 100 parts by weight or less to form a thin film sealing structure, excellent moisture barrier properties can be exhibited.

The adhesive composition of the present application may also contain an olefin resin having a moisture permeability of 50 g / m ² · day or less.

Considering that the adhesive composition of the present application is applied to encapsulate or encapsulate an organic electronic device, it can be applied as a sealing material having excellent moisture barrier property by including an olefin resin satisfying the above-mentioned moisture permeability range. The moisture permeability may be a water vapor transmission rate measured with respect to the thickness direction of the film in the state that the olefin resin is in the form of a film formed of a resin layer having a thickness of 100 탆. The moisture permeability is not more than 50 g / m ² · day, not more than 40 g / m ² · day, not more than 30 g / m ² · day, not more than 20 g / m ² · day, or 10 g / m ² · day or less. The composition and crosslinking conditions of the olefin resin can be adjusted to have such a moisture permeability. The lower limit of the water vapor permeability may be an excellent water barrier property. Therefore, the lower limit is not particularly limited, but may be, for example, 0 g / m ² · day or 0.1 g / m ² · day.

Specifically, the exemplary olefin-based resin of the present application comprises an olefin-based resin derived from a mixture of monomers, and the mixture may have an isoolefin monomer component or a multi-olefin monomer component having at least 4 to 7 carbon atoms. The isoolefin may be present, for example, in the range of from 70 to 99.5 wt%, or from 85 to 99.5 wt%, based on the total monomer weight. The multi-olefin-derived component may be present in the range of 0.5 to 30 wt%, 0.5 to 15 wt%, or 0.5 to 8 wt%.

Examples of the isoolefin include isobutylene, 2-methyl-1-butene, 3-methyl-1-butene, Vinyltrimethylsilane, hexene, or 4-methyl-1-pentene. The multi-olefins may have from 4 to 14 carbon atoms and include, for example, isoprene, butadiene, 2,3-dimethyl-1,3-butadiene, myrcene, 6,6-dimethyl-fulvene, hexadiene, cyclopentadiene, or Piperylene may be exemplified. Other polymerizable monomers such as styrene and dichlorostyrene can also be homopolymerized or copolymerized in the butyl rubber.

In the present application, the olefin-based resin may include an isobutylene-based copolymer. As mentioned above, the isobutylene-based olefin-based resin or polymer may refer to an olefin-based resin or polymer containing 70 mol% or more of repeating units from isobutylene and at least one other polymerizable unit.

In the present application, the olefin-based resin may be a butyl rubber or a branched butyl rubber. Exemplary olefinic resins are unsaturated butyl rubbers such as olefins or copolymers of isoolefins and multi olefins. As the olefin-based resin to be contained in the adhesive composition of the present invention, poly (isobutylene-co-isoprene), polyisoprene, polybutadiene, polyisobutylene, poly (styrene-co-butadiene), natural rubber, Mixtures of these can be exemplified. The olefinic resins useful in the present invention can be prepared by any suitable means known in the art, and the present invention is not limited by the method of preparing the olefinic resins here.

In one example, the olefin resin may be a low molecular weight polyisobutylene resin. For example, the olefin resin may have a weight average molecular weight of 100,000 or less and 10,000 or more. In this application, the liquid adhesive composition can be realized by controlling the weight average molecular weight of the olefin resin within the above range. The liquid adhesive composition can be suitably applied to side encapsulation of the organic electronic device described later.

In one example, the olefin resin may be a resin containing a functional group having reactivity with the above-mentioned thermosetting resin. Examples of the reactive functional group include, but are not limited to, an acid anhydride group, carboxyl group, epoxy group, amino group, hydroxyl group, isocyanate group, oxazoline group, oxetane group, cyanate group, phenol group, hydrazide group, Or an amide group. Examples of the olefin resin having a reactive functional group include succinic anhydride modified polyisobutylene, maleic anhydride modified liquid polyisobutylene, maleic anhydride modified liquid polyisoprene, epoxy modified polyisoprene, hydroxyl group modified liquid phase Polyisoprene, or allyl-modified liquid polyisoprene. The olefin resin as described above forms a crosslinked structure with a thermosetting resin to be described later, so that an adhesive composition having physical properties such as moisture barrier properties and handling property desired in the present application can be realized.

In embodiments of the present application, the adhesive composition may comprise 60 to 90 parts by weight of an olefinic resin and 10 to 40 parts by weight of a thermosetting resin. The present application can provide an adhesive composition excellent in moisture barrier property, durability and reliability by controlling the content within the above range.

The present application may further comprise, if desired, a radical curable compound. The radical curable compound may be a photo-radical curable compound. That is, the adhesive composition according to the present application may further comprise a photo-radical curable compound together with the thermosetting resin as described above. In this case, the adhesive composition can form a crosslinked structure by light irradiation before the aforementioned thermosetting resin is thermoset. The present application can ensure a high-temperature fluidity by which the adhesive composition applied at a desired position can effectively maintain a desired shape by the crosslinking structure by light irradiation.

The radical-curable compound may include, for example, a polyfunctional polymerizable compound which is highly compatible with the above-mentioned olefin resin or thermosetting resin and can form a specific crosslinked structure. In one embodiment, the crosslinked structure may be a crosslinked structure formed by application of heat, a crosslinked structure formed by irradiation of an active energy ray, or a crosslinked structure formed by aging at room temperature. The term " active energy ray " as used herein includes alpha-particle beams, proton beams, as well as microwaves, infrared (IR), ultraviolet A particle beam such as a neutron beam or an electron beam, and the like, and may be typically an ultraviolet ray or an electron beam.

In one embodiment, the radically curable compound may be a polyfunctional active energy ray polymerizable compound, and the polyfunctional active energy ray polymerizable compound may be, for example, a compound capable of participating in a polymerization reaction by irradiation of an active energy ray A functional group such as an acryloyl group, a methacryloyl group, an acryloyloxy group, or a methacryloyloxy group, or a functional group containing an ethylenically unsaturated double bond such as an epoxy group or an oxetane group &Lt; / RTI > In one example, the polyfunctional active energy pre-polymerizable compound may comprise at least bifunctional epoxy acrylate or polybutadiene dimethacrylate.

In the embodiments of the present application, for example, multifunctional acrylate (MFA) can be used as the polyfunctional active energy ray polymerizable compound.

10 to 90 parts by weight, 13 to 80 parts by weight, 15 to 70 parts by weight or 17 to 60 parts by weight, based on 100 parts by weight of the thermosetting resin, &Lt; / RTI >

In one example, the adhesive composition of the present application may comprise 50 to 90 parts by weight of an olefinic resin, 5 to 50 parts by weight of a thermosetting resin and 1 to 40 parts by weight of a radical curable compound.

In one example, the polyfunctional active energy ray polymerizable compound that can be polymerized by irradiation of the active energy ray is 1,4-butanediol di (meth) acrylate, 1,3-butylene glycol 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 (Meth) acrylate, neopentyl glycol-modified trimethylpropane di (meth) acrylate, adamantane di (meth) acrylate, trimethylol propane tri .

In one example, the adhesive composition may comprise a radical initiator together with a radical curable compound. The radical initiator may be a photo radical initiator. The specific kind of the photoinitiator can be appropriately selected in consideration of the curing rate and the possibility of yellowing. For example, benzoin, hydroxy ketone, amino ketone or phosphine oxide photoinitiators can be used. Specific examples thereof include 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- Methyl-1 - [4- (methylthio) phenyl] -2-morpholino-propane-1-one, 1-hydroxycyclohexyl phenyl ketone, (2-hydroxyethoxy) phenyl-2- (hydroxy-2-propyl) ketone, benzophenone, p-phenylbenzophenone, 4,4'-diethylaminobenzophenone, dichlorobenzophenone, 2-methylanthraquinone, 2-ethyl anthraquinone, 2-t-butyl anthraquinone, 2-aminoanthraquinone, thioxanthone, 2-ethylthioxanthone, 2- - dimethylthio Diethyl thioxanthone, benzyldimethyl ketal, acetophenone dimethyl ketal, p-dimethylamino benzoic acid ester, oligo [2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl ] Propanone] and 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide can be used.

The content of the initiator may be varied depending on the kind and ratio of the functional group of the radical-curable compound, the crosslinking density to be achieved, and the like. For example, the radical initiator may be formulated in an amount of 0.1 to 20 parts by weight or 0.1 to 15 parts by weight based on 100 parts by weight of the radical-curable compound. By controlling the radical initiator in the above content range, the present invention can realize a flow control at a high temperature by introducing an appropriate cross-linking structure into the adhesive composition.

In one example, when the adhesive composition comprises a photo-radical curable compound, a specific range of viscosity after light irradiation can be satisfied as follows. Exemplary, the adhesive composition may have a viscosity of 700 Pa-s to 50,000 Pa-s after irradiation. Within the above range of viscosity, the adhesive composition can maintain the encapsulation structure of the desired organic electronic device. In one example, the viscosity of the adhesive composition may be measured after the light having a wavelength range of the UV-A region is irradiated with a light quantity of 3 J / cm ² . Further, the viscosity of the adhesive composition may be a viscosity measured according to a shear stress at a temperature of 25 캜, a 5% strain and a frequency of 1 Hz. In one example, the viscosity of the resin composition may be from 700 Pa · s to 40,000 Pa · s, from 800 Pa · s to 30,000 Pa · s, or from 900 Pa · s to 20,000 Pa · s.

As used herein, the term " UV-A region " may mean a wavelength range of 315 nm to 400 nm. Specifically, in the present specification, light having a wavelength range of the UV-A region refers to light including any one of the wavelengths in the range of 315 nm to 400 nm, or includes light in the wavelength range of 315 nm to 400 nm It can mean light.

In the embodiment of the present application, the adhesive composition can form an encapsulation structure of the organic electronic device by irradiating the light and proceeding the final curing by applying heat. The thermosetting can proceed by applying a magnetic field as described above. Therefore, when the magnetic field is applied, the UV curable adhesive composition is required to have physical properties capable of realizing the final curing without changing the shape. That is, it is necessary to prevent the spreading of the adhesive composition at a high temperature. In one example, the adhesive composition can be cured by irradiating light having a wavelength range of the UV-A region to a light quantity of 3 J / cm ² as described above, and the resin composition vulcanized is 80 Lt; 0 > C, a 5% strain and a frequency of 1 Hz, the viscosity according to shear stress may be 500 Pa · s to 50,000 Pa · s. The viscosity may be, for example, 500 Pa · s to 40,000 Pa · s, 500 Pa · s to 30,000 Pa · s, or 600 Pa · s to 20,000 Pa · s.

By satisfying the viscosity range as described above, the adhesive composition of the present application can be effectively applied to the side encapsulation of an organic electronic device. The method of controlling the viscosity range is not particularly limited, and can be controlled by controlling the kinds of components constituting the adhesive composition, the content of the components, and the like. For example, the present application can realize the physical properties of a desired composition by controlling the radical scavenging compound and the radical initiator in the proper amount range together with the above-mentioned thermosetting resin, thermosetting agent, magnetic substance and moisture adsorbent.

The adhesive composition according to the present application may contain various additives in accordance with the use, the kind of the olefin resin or the thermosetting resin, and the sealing process described below, within the range not affecting the effects of the above-described invention, in addition to the above- For example, the resin composition may contain an antifoaming agent, a coupling agent, a tackifier, a UV stabilizer, or an antioxidant in an appropriate range depending on the desired physical properties. In one example, the adhesive composition may further comprise a defoamer. This realizes the defoaming property in the application process of the above-mentioned adhesive composition, thereby providing a reliable sealing structure. In addition, as long as the physical properties of the adhesive composition required in the present application are satisfied, the kind of the defoaming agent is not particularly limited.

The present application also relates to an adhesive film comprising the above-mentioned adhesive composition. In one example, the adhesive film may comprise an adhesive layer or an encapsulating layer comprising the above-described adhesive composition. In another embodiment of the present application, the adhesive film may include a front sealing layer and a side sealing layer. The front encapsulation layer and the side encapsulation layer may be present on the same plane. The adhesive film may be applied to an organic electronic device encapsulation, and the front encapsulation layer may be applied to encapsulate the front surface of the organic electronic device. That is, the front encapsulation layer can encapsulate the upper surface of the device, and the upper surface as well as the side surface can be sealed together. The side sealing layer can be formed on the side surface of the element. The side sealing layer may or may not directly contact the side surface of the organic electronic device. For example, the front seal layer can be sealed to make direct contact with the top and sides of the device. That is, the side encapsulation layer may be located at least on one or more peripheral edges in plan view of the organic electronic device, without contacting the device.

The material constituting the side sealing layer is not particularly limited, but may include the above-mentioned adhesive composition.

On the other hand, the front encapsulation layer may include a sealing resin, and the sealing resin may be an acrylic resin, an epoxy resin, a silicone resin, a fluororesin, a styrene resin, a polyolefin resin, a thermoplastic elastomer, a polyoxyalkylene resin, Vinyl chloride resin, polycarbonate resin, polyphenylene sulfide resin, polyamide resin, or a mixture thereof.

The component constituting the front seal layer may be the same as or different from the above-mentioned adhesive composition, and may be the same as or different from the component constituting the side seal layer. However, the front seal layer may not contain the above-mentioned moisture adsorbent or may contain a small amount in that the front seal layer is in direct contact with the device. For example, the total amount of the front sealing layer may be 0 to 20 parts by weight based on 100 parts by weight of the sealing resin.

The present application also relates to organic electronic devices. Exemplary organic electronic devices include, as shown in Fig. 1, a substrate 21; An organic electronic device 23 formed on the substrate 21; And a side sealing layer 10 surrounding the side surface of the organic electronic device 23 and including the above-described adhesive composition. In addition, the exemplary organic electronic device may further include a front encapsulant layer 11 covering the front surface of the organic electronic device 23.

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

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

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

The organic electronic device may further include a protective film for protecting the organic electronic device between the front sealing layer or the side sealing layer and the 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: applying the adhesive composition described above to the substrate 21 on which the organic electronic device 23 is formed to surround the side surface of the organic electronic device 23; And applying a magnetic field to the adhesive composition.

The substrate 21 on which the organic electronic device 23 is formed may be formed by forming a reflective electrode or a transparent electrode on a substrate 21 such as a glass or a film by a method such as vacuum deposition or sputtering, And then forming an organic material layer on the reflective electrode. The organic material layer may include a hole injecting layer, a hole transporting layer, a light emitting layer, an electron injecting layer, and / or an electron transporting layer. Then, a second electrode is further formed on the organic material layer. Then, the above-described side encapsulation layer 10 is applied to cover the organic electronic device 23 on the organic electronic device 23 on the substrate 21. At this time, the method of forming the side sealing layer 10 is not particularly limited, and the adhesive composition may be applied to the side surface of the substrate 21 by screen printing, dispenser application, or the like. Also, a front encapsulation layer 11 for encapsulating the front surface of the organic electronic device 23 can be applied. As a method of forming the front encapsulation layer 11, a well-known method in the art can be applied. For example, a liquid drop injection (One Drop Fill) process can be used.

Further, in the present invention, a curing process may be performed on the front or side sealing layer that encapsulates the organic electronic device. This curing process (final curing) may be performed, for example, in a heating chamber or a UV chamber, Can be done in both. The conditions for the final curing can be appropriately selected in consideration of the stability of the organic electronic device and the like.

In one example, the adhesive composition may be applied to form a side-seal layer, and then a magnetic field may be applied to the magnetic body to generate heat, thereby thermally curing the adhesive. The step of applying the magnetic field is not particularly limited and can be performed by a known method by a person skilled in the art. For example, the step of applying a magnetic field may apply a magnetic field for 1 to 10 minutes at a current of 50 A to 250 A at a frequency of 100 kHz to 1 GHz. On the other hand, the thermosetting can proceed with the application of a magnetic field as described above, and may include applying a magnetic field followed by further heating at 40 ° C to 100 ° C for 1 hour to 24 hours. Further, the present invention is not limited to the above, and it is possible to apply heat with magnetic field application.

In one example, after the above-described adhesive composition is applied to form a side seal layer, the composition may be irradiated with light to induce crosslinking, and then a magnetic field may be applied. The irradiation of the light may include irradiating light having a wavelength range of the UV-A region band with a light quantity of 0.3 to 5 J / cm ² . As described above, it is possible to realize an encapsulation structure shape that can become a basis by making it harder through irradiation of light. The manufacturing method may further include thermally curing the adhesive composition after irradiation with light by applying a magnetic field as described above. Through the thermosetting step, the adhesive composition can undergo the final curing.

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

Hereinafter, the present invention will be described in more detail with reference to the following examples and comparative examples, but the scope of the present invention is not limited by the following examples.

Example One

A polyisobutylene resin (BASF B10, Mw = 40,000 to 50,000) as an olefin resin and a hydrogenated BPA type epoxy resin (ST-3000, Kukdo Chemical, equivalent: 230) as a thermosetting resin were mixed at 70: ST-3000). An imidazole-based curing agent (2P4MHZ) as a heat curing agent was added in an amount of 0.1 part by weight based on 100 parts by weight of the olefin resin and the thermosetting resin. On the other hand, calcium oxide (CaO, Aldrich) as a moisture adsorbent was added to the container in an amount of 20 parts by weight per 100 parts by weight of the olefin resin and the thermosetting resin. Further, Fe ₃ O ₄ (50 nm, Sigma-Aldrich) was added as a magnetic substance to the container in an amount of 10 parts by weight per 100 parts by weight of the olefin resin and the thermosetting resin.

A uniform composition solution was prepared using the planetary mixer (Kurabo, KK-250s).

Example 2

An adhesive composition was prepared in the same manner as in Example 1, except that the olefin resin and the thermosetting resin were charged into a mixing container at a weight ratio of 80:20 and the magnetic material was added in an amount of 20 parts by weight.

Example 3

An adhesive composition was prepared in the same manner as in Example 2, except that 30 parts by weight of the moisture adsorbent was added.

Comparative Example One

An adhesive composition was prepared in the same manner as in Example 1, except that the magnetic material was added in an amount of 0.5 part by weight.

Comparative Example 2

An adhesive composition was prepared in the same manner as in Example 1, except that 30 parts by weight of the magnetic material was added.

Comparative Example 3

An adhesive composition was prepared in the same manner as in Example 1, except that the olefin resin and the thermosetting resin were charged in a mixing vessel at a weight ratio of 20:80 and the magnetic material was added in an amount of 30 parts by weight.

Comparative Example 4

An adhesive composition was prepared in the same manner as in Example 1, except that the magnetic material was not included.

The physical properties in the following examples and comparative examples were evaluated in the following manner.

1. Viscosity measurement

Viscosities of the adhesive compositions prepared in Examples and Comparative Examples were measured using a Brook field viscometer (DV-II + Pro). Specifically, the measurement conditions were set at a spindle No. 7, a temperature of 25 ° C and a rotation speed of 10 rpm, and a viscosity according to a torque was measured. The unit is cPs.

2. When curing Flow control

The adhesive compositions prepared in Examples and Comparative Examples were applied to a 0.7T Soda-Lime glass and compressed in the same glass to prepare samples. Then, the outermost portion of the sample was marked with a pen, and then a magnetic field was applied for 4 minutes at a current of 240 A at a frequency of 291 kHz to cure the sample. In the case of Comparative Example 4, it was cured at 100 DEG C for 3 hours in a high-temperature drier. When the outermost shape was observed with the naked eye, O, when the outermost shape exceeded the boundary indicated by the pen, but when the outermost shape was almost maintained, when the outermost shape was not maintained, Respectively.

On the other hand, in the adhesive composition prepared in Comparative Example 3, after the sample as described above was prepared, the outermost portion of the sample was marked with a pen, and after curing in an oven at 100 ° C for 2 hours, Respectively.

3. Moisture Barrier property

In order to investigate the moisture barrier properties of the adhesive compositions of Examples and Comparative Examples, a calcium test was conducted. Specifically, calcium (Ca) was deposited on a glass substrate having a size of 100 mm x 100 mm by depositing 7 spots in a size of 5 mm x 5 mm and a thickness of 100 nm, and the adhesive compositions of Examples and Comparative Examples were formed into a film The cover glass onto which the film was transferred was heat-pressed at 80 DEG C for 1 minute by using a vacuum press on each calcium deposition site. Thereafter, a magnetic field was applied for 4 minutes at a current of 240 A at a frequency of 291 kHz to be cured. In the case of Comparative Example 4, it was cured at 100 DEG C for 3 hours in a high-temperature drier. Thereafter, each of the Ca (Ca) specimens sealed in a size of 11 mm x 11 mm was cut. The obtained samples were allowed to stand at 85 ° C and 85% RH in a thermo-hygrostat chamber, and the time point at which calcium began to become transparent due to the oxidation reaction due to moisture penetration was evaluated and shown in Table 1 below.

4. Solution stability

The solution stability of the adhesive compositions of Examples and Comparative Examples was evaluated as follows. When the magnetic composition is mixed with the resin composition, mixing is easy and the glass coating is possible. In the case where no particle aggregation is observed in the applied composition, O can be mixed, but if the coating is poor or if the coating composition shows particle aggregation, If the particles are clumped to such a degree that they are not enough, they are indicated by X.

Viscosity Flow control during curing Moisture barrier property Solution stability cPs hr Example 1 150,000 O 650 O Example 2 180,000 O 660 O Example 3 200,000 O 700 O Comparative Example 1 150,000 △ Not measurable ¹ ⁾ O Comparative Example 2 220,000 △ 400 X Comparative Example 3 5,000 X (NG) 500 △ Comparative Example 4 140,000 X (NG) 550 O 1) It is impossible to measure moisture barrier property because hardening does not proceed.

1: Adhesive
10: side sealing layer
11: front seal layer
21: substrate
22: Cover substrate
23: Organic electronic device

Claims

A thermosetting resin, a thermosetting agent, a moisture adsorbent, and a magnetic substance, wherein the magnetic substance is contained in an amount of 1 to 25 parts by weight based on 100 parts by weight of the resin component.

The adhesive composition of claim 1, wherein the adhesive composition has a viscosity of 10,000 cPs or greater as determined by a Brookfield viscometer at a temperature of 25 캜, a rotational speed of 10 rpm, and a spindle no. 7.

The adhesive composition according to claim 1, wherein the thermosetting resin is a thermosetting resin containing at least one thermosetting functional group.

The adhesive composition according to claim 3, wherein the thermosetting functional group comprises an epoxy group, a glycidyl group, an isocyanate group, a hydroxyl group, a carboxyl group or an amide group.

The adhesive composition of claim 1, wherein the thermosetting agent comprises an amine curing agent, an imidazole curing agent, a phenol curing agent, a phosphorus curing agent, or an acid anhydride curing agent.

The adhesive composition according to claim 1, wherein the thermosetting agent is contained in an amount of 1 to 20 parts by weight based on 100 parts by weight of the resin component.

The adhesive composition according to claim 1, wherein the average particle diameter of the magnetic material is in the range of 1 nm to 1 占 퐉.

The adhesive composition according to claim 1, wherein the magnetic material is at least one selected from the group consisting of Fe ₃ O ₄ , Fe ₂ O ₃ , MnFe ₂ O ₄ , CoFe ₂ O ₄ , Fe, CoPt, and FePt.

The method of claim 1, wherein the water-absorbent _{P 2 O 5, Li 2 O} , Na 2 O, BaO, CaO, MgO, Li 2 SO 4, Na 2 SO 4, CaSO 4, MgSO 4, CoSO 4, Ga 2 ( _{SO 4) 3, Ti (SO} 4) 2, NiSO 4, CaCl 2, MgCl 2, SrCl 2, YCl 3, CuCl 2, CsF, TaF 5, NbF 5, LiBr, CaBr 2, CeBr 3, SeBr 4, VBr ₃ , MgBr ₂ , BaI ₂ , MgI ₂ , Ba (ClO ₄ ) ₂ and Mg (ClO ₄ ) ₂ .

The adhesive composition according to claim 1, wherein the moisture adsorbent is contained in an amount of 10 to 100 parts by weight based on 100 parts by weight of the resin component.

The adhesive composition according to claim 1, wherein the adhesive composition comprises an olefin resin having a moisture permeability of 50 g / m ² · day or less.

The adhesive composition according to claim 11, wherein the olefin resin is contained in an amount of 60 to 90 parts by weight and the thermosetting resin is contained in an amount of 10 to 40 parts by weight.

The adhesive composition according to claim 11, wherein the olefin resin has a weight average molecular weight of 100,000 or less.

12. The adhesive composition according to claim 11, wherein the olefin resin comprises a functional group having reactivity with the thermosetting resin.

The thermosetting resin composition according to claim 14, wherein the functional group having reactivity with the thermosetting resin is selected from the group consisting of an acid anhydride group, carboxyl group, epoxy group, amino group, hydroxyl group, isocyanate group, oxazoline group, oxetane group, cyanate group, phenol group, Or an amide group.

The adhesive composition according to claim 11, wherein the olefin resin comprises a polyisobutylene resin.

The adhesive composition of claim 1, further comprising a radically curable compound.

19. The method according to claim 17, wherein the light having a wavelength range of the UV-A region is irradiated at a light quantity of 3 J / cm ² , and then the viscosity measured according to the shear stress at a temperature of 25 캜, 5% 700 Pa · s to 50,000 Pa · s.

An adhesive film comprising the adhesive composition of claim 1.

The adhesive sheet according to claim 19, further comprising a side sealing layer formed on the front sealing layer and at least one peripheral portion, the side sealing layer comprising the adhesive composition of claim 1, wherein the side sealing layer and the front sealing layer are provided on the same plane .

Board; An organic electronic device formed on a substrate; And a side sealing layer surrounding the side surface of the organic electronic device, wherein the side sealing layer comprises the adhesive composition according to claim 1.

The organic electronic device according to claim 21, further comprising a front seal layer covering a front surface of the organic electronic device.

The organic electronic device according to claim 21, wherein the organic electronic device comprises a reflective electrode layer formed on a substrate, an organic layer formed on the reflective electrode layer and including at least a light emitting layer, and a transparent electrode layer formed on the organic layer.

Applying the adhesive composition of claim 1 to the substrate on which the organic electronic device is formed to surround the side surface of the organic electronic device; And applying a magnetic field to the adhesive composition.

25. The method of claim 24, wherein applying the magnetic field comprises applying a magnetic field at a current of 50 A to 250 A at a frequency of 100 kHz to 1 GHz for 1 to 60 minutes.