KR20160095851A - Pressure sensitive adhesive compositions, method for preparing the same, pressure sensitive adhesive film comprising the same and method for preparing organic electronic device using the same - Google Patents

Abstract

The present invention relates to an adhesive composition, an adhesive film, an organic electronic device comprising the same, and a producing method of an organic electronic device, using the same and, more specifically, to an adhesive composition which can block moisture or oxygen from entering the organic electronic device from the outside and can implement reliability and excellent optical properties in harsh conditions such as the high temperature and high humidity, and to an adhesive film comprising the same.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a pressure-sensitive adhesive composition, a pressure-sensitive adhesive composition containing the same, a pressure-sensitive adhesive composition containing the pressure- }

The present invention relates to a pressure-sensitive adhesive composition, a method for producing the pressure-sensitive adhesive composition, a pressure-sensitive adhesive film containing the pressure-sensitive adhesive film, and a method for producing an organic electronic device using the pressure-

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.

Therefore, it is required to develop an encapsulant that can maintain the reliability at high temperature and high humidity conditions and has excellent optical characteristics, while securing the required lifetime in the organic electronic device and effectively blocking the penetration of moisture.

Korean Patent Publication No. 2008-0088606

The present invention provides a pressure-sensitive adhesive composition capable of effectively blocking moisture or oxygen introduced from the outside into an organic electronic device and capable of forming a sealing structure capable of realizing excellent transparency, a method for producing the pressure-sensitive adhesive composition, and a pressure-sensitive adhesive film containing the pressure-

The present invention relates to a pressure-sensitive adhesive composition. The pressure-sensitive adhesive composition can be applied to encapsulating or encapsulating organic electronic devices such as, for example, OLEDs.

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 invention, the organic electronic device may be an OLED.

Exemplary pressure-sensitive adhesive compositions may include a sealing resin, a polyfunctional active energy pre-polymerizable compound, and a radical initiator. The pressure-sensitive adhesive composition may have a C-Score _i according to the following general formula (1), which is greater than 0 or less than 5, and may be, for example, 0.1 to 4 or 0.2 to 2.

[Formula 1]

C-Score _i = 2.97 tanh (1.197 x _i ) - 0.381 log ₁₀ (0.119 y _i ) - 0.307 (0.160z _i ) ^0.463

X _i represents the mixed energy (ΔE ₁ , KJ / mol) of the active energy ray polymerizable compound and the radical initiator, and y _i represents the mixing energy (ΔE ₂ ) between the active energy ray polymerizable compound and the encapsulating resin , KJ / mol). In the above, x _i and y _i can be calculated using the COSMO-RS theory and can be evaluated using a COSMOtherm program based on the COSMO-RS theory. In addition, z _i represents the reaction energy (ΔE _rxn , KJ / mol) of the active energy ray polymerizable compound and the encapsulating resin. Z _i can be calculated using the DMol3 program.

In the present specification, the term " C-Score _i " refers to a compound having a desired physical property in terms of energy, taking into account the mixing energy and reactivity between the encapsulating resin constituting the pressure-sensitive adhesive composition, the polyfunctional active energy- Lt; RTI ID = 0.0 > tack < / RTI > That is, the present application discloses that when the pressure-sensitive adhesive composition is applied to an organic electronic device, the sealing resin, the polyfunctional active energy ray-polymerizable compound and the radical, which may affect the crosslinking structure and the crosslinking degree, The mixing energy of the initiator and the reaction energy are calculated and expressed as C-Score _i . When the C-Score _i is larger than 0, the optimum crosslinking structure and crosslinking degree desired in the present invention can be realized. The crosslinking structure and degree of crosslinking can be evaluated by gel content or a high-modulus elasticity described later, but the present invention is not limited thereto. Further, when the desired crosslinking structure and degree of crosslinking are realized, when the pressure-sensitive adhesive composition is applied by sealing an organic electronic device such as an OLED, heat resistance and durability can be maintained even at high temperature and high humidity.

The pressure-sensitive adhesive composition can be applied to encapsulating or encapsulating an organic electronic device such as an OLED or the like, as described above. The pressure-sensitive adhesive composition showing the above range of the value (C-Score _i ), when applied to the encapsulation or encapsulation process, can form an excellent durable encapsulation or encapsulation structure free from bubbles or the like under high temperature durability test conditions. In one example, the pressure sensitive adhesive composition can be used to form an encapsulation or encapsulation structure covering both the top and sides of an element of an organic electronic device, as described below.

In one example, the mixing energy (ΔE ₁ ) of the active energy ray polymerizable compound and the radical initiator calculated using the COSMO-RS theory can be 0 KJ / mol or more, specifically 0 to 5 KJ / mol, 0 To 3 KJ / mol or 0.02 to 1 KJ / mol. In the pressure-sensitive adhesive composition, the crosslinking reaction is initiated by radical generation by the radical initiator. If the compatibility of the active energy ray-polymerizable compound with the radical initiator is too high, a crosslinking reaction occurs between the polymerizable compounds having a double bond , Rather, the crosslinking efficiency between the active energy ray polymerizable compound and the encapsulating resin is reduced. Therefore, by controlling the lower limit of the mixing energy (ΔE ₁ ) to 0 KJ / mol, an optimum crosslinking structure of the pressure-sensitive adhesive composition is realized, thereby providing a sealing structure having excellent moisture barrier properties, reliability at high temperature and high humidity, can do.

The mixing energy (? E ₂ ) of the active energy ray polymerizable compound and the encapsulating resin calculated using the COSMO-RS theory may be 8 KJ / mol or less, specifically 0 to 8 KJ / mol, 2 to 8 KJ / mol, 3 to 8 KJ / mol or 4 to 7.5 KJ / mol. As described above, in the pressure-sensitive adhesive composition, the crosslinking reaction is initiated by radical generation by the radical initiator. In this case, the crosslinking reaction can be effectively performed because the compatibility of the active energy ray-polymerizable compound and the encapsulating resin is good. Thus, by controlling the upper limit of the mixing energy (? E ₂ ) to 8 KJ / mol, the active energy ray polymerizable compound and the encapsulating resin can realize the degree of crosslinking desired in the present invention.

In the present specification, in the case of mixed energy, the surface screening charge distribution of each material can be quantitatively calculated. Specifically, the chemical potential of a pure substance or mixture is thermodynamically calculated using the surface screening charge distribution. This can be used to calculate how much it can be stabilized as a mixture. That is, the chemical potential of the mixture and the chemical potential difference of the pure substance can be calculated. Among the information necessary for the calculation, the parameters affecting the result are the initial structure of the material, the exchange-correlation functional, the basis set, the program used and the version thereof in the quantum mechanical calculation. In the thermodynamic calculation, Receive. The parameters of the calculation used in the present invention are as follows. First of all, the structure of each material was calculated for the structure in which the 3D structure can spread as straight or wide as possible. The straight or widened structure can be evaluated by chemical structure model coordinates, which can be implemented by a person skilled in the art in a known manner. The surface-screening charge distribution for the calculation of the mixing energy was used in the program TURBOMOLE version 6.5 (TURBOMOLE GmbH, Karlsruhe) (DFT, Density Functional Theory calculation program) , And the basis set used def-TZVP. Thermodynamic calculations were performed using the COSMO therm version C30_1301 (COSMO logic GmbH & Co. KG, COSMO-RS theory).

On the other hand, the reaction energy (ΔE _rxn , KJ / mol) of the active energy ray polymerizable compound and the encapsulating resin calculated using DMol3 may be 10 KJ / mol or less, specifically -2 to 10 KJ / 8 KJ / mol or 0 to 5 KJ / mol. The reaction energy can be calculated quantum mechanically and can be evaluated by the DMol3 program, which is a quantum mechanical program as described above. In the case of the present invention, by controlling the upper limit of the reaction energy ([Delta] E _rxn ) to 10 KJ / mol, the pressure sensitive adhesive composition can _{exhibit an} optimum crosslinking A structure can be formed, and a sealing or encapsulating structure having excellent durability against electronic devices can be provided.

Specifically, in the present specification, the reaction energy can quantitatively calculate the energy of each constituent material before and after the reaction, and calculate the difference. The quantum mechanics calculation is the same as the principle of the quantum mechanical calculation described above. The program used was the quantum mechanics program (DFT program) of DMol3 version 6.1 (BIOVIA), the exchange-correlation functional using BP functional and the basis set using DNP.

In the present invention, the pressure-sensitive adhesive composition may include an encapsulating resin, a polyfunctional active energy ray-polymerizable compound and a radical initiator, as described above. The numerical range of the above-mentioned C-Score _i , the compatibility between the respective compositions and the reaction energy can be determined by the composition, content or crosslinking conditions constituting the pressure-sensitive adhesive composition.

In embodiments of the present invention, the encapsulating resin may have a glass transition temperature of less than 0 占 폚, less than -10 占 폚, or less than -30 占 폚, less than -50 占 폚, or less than -60 占 폚. The glass transition temperature described above refers to a glass transition temperature after irradiation with ultraviolet rays of about 1 J / cm ² or more; Or the glass transition temperature after further thermosetting after ultraviolet irradiation.

In one example, the sealing resin may be a styrene resin or an elastomer, a polyolefin resin or an elastomer, other elastomers, a polyoxyalkylene resin or an elastomer, a polyester resin or an elastomer, a polyvinyl chloride resin or an elastomer, a polycarbonate A resin or an elastomer, a polyphenylene sulfide resin or an elastomer, a mixture of hydrocarbons, a polyamide resin or an elastomer, an acrylate resin or an elastomer, an epoxy resin or an elastomer, a silicone resin or an elastomer, a fluorine resin or an elastomer, And the like.

Examples of the styrene resin or elastomer include styrene-ethylene-butadiene-styrene block copolymer (SEBS), styrene-isoprene-styrene block copolymer (SIS), acrylonitrile-butadiene- (ABS), acrylonitrile-styrene-acrylate block copolymer (ASA), styrene-butadiene-styrene block copolymer (SBS), styrene homopolymer or mixtures thereof. As the olefin resin or elastomer, for example, a high density polyethylene resin or an elastomer, a low density polyethylene resin or an elastomer, a polypropylene resin or an elastomer or a mixture thereof may be exemplified. As the elastomer, for example, an ester type thermoplastic elastomer, an olefin type elastomer, a silicone type elastomer, an acrylic type elastomer, or a mixture thereof can be used. As the olefinic thermoplastic elastomer, a polybutadiene resin, an elastomer or a polyisobutylene resin or an elastomer may be used. As the polyoxyalkylene resin or elastomer, for example, a polyoxymethylene resin or an elastomer, a polyoxyethylene resin or an elastomer or a mixture thereof can be exemplified. As the polyester resin or elastomer, for example, a polyethylene terephthalate resin or an elastomer, a polybutylene terephthalate resin or an elastomer or a mixture thereof may be exemplified. As the polyvinyl chloride resin or elastomer, for example, polyvinylidene chloride and the like can be mentioned. As the mixture of the hydrocarbons, for example, hexatriacotane or paraffin can be exemplified. As the polyamide-based resin or elastomer, for example, nylon and the like can be mentioned. As the acrylate resin or elastomer, for example, polybutyl (meth) acrylate and the like can be mentioned. Examples of the epoxy resin or elastomer include bisphenol type epoxy resins such as bisphenol A type, bisphenol F type, bisphenol S type and water additives thereof; Novolak types such as phenol novolac type and cresol novolak type; Nitrogen-containing cyclic rings such as triglycidyl isocyanurate type and hydantoin type; Alicyclic type; Fat type; Aromatic types such as naphthalene type and biphenyl type; Glycidyl types such as glycidyl ether type, glycidyl amine type and glycidyl ester type; Dicyclopentane type such as dicyclopentadiene type; Ester type; Ether ester type, mixtures thereof, and the like. As the silicone resin or elastomer, for example, polydimethylsiloxane and the like can be mentioned. Examples of the fluororesin or elastomer include a polytrifluoroethylene resin or an elastomer, a polytetrafluoroethylene resin or an elastomer, a polychlorotrifluoroethylene resin or an elastomer, a polyhexafluoropropylene resin or an elastomer, a polyfluorinated Vinylidene fluoride, vinyl fluoride, vinylidene fluoride, polyfluorinated ethylene propylene, or a mixture thereof.

The above-mentioned resin or elastomer may be grafted with, for example, maleic anhydride or the like, and may be used by being copolymerized with another resin or elastomer or a monomer for producing a resin or elastomer, . Examples of the other compounds include carboxyl-terminated butadiene-acrylonitrile copolymers and the like.

In one example, the pressure-sensitive adhesive composition may include, but is not limited to, an olefin elastomer, a silicone-based elastomer, or an acrylic-based elastomer, among the above-

In one example, the encapsulating resin may be an olefinic resin, specifically, a copolymer of an olefinic compound containing a diene and one carbon-carbon double bond. Here, the olefin compound may include isobutylene, propylene, ethylene or the like, and the diene may be a monomer capable of polymerizing with the olefin-based compound, and examples thereof include 1-butene, 2-butene, isoprene, . ≪ / RTI > That is, the sealing resin of the present invention may be, for example, a homopolymer of an isobutylene monomer; A copolymer obtained by copolymerizing an isobutylene monomer with another monomer capable of polymerization; Or a mixture thereof. In one example, the copolymer of an olefinic compound and a diene containing one carbon-carbon double bond may be a butyl rubber. By using a specific resin as described above, it is possible to satisfy the water barrier property to be implemented in the present invention.

In one example, the sealing resin may be represented by a copolymer comprising a polymerization unit represented by the following formula (A) and a polymerization unit represented by the following formula (B).

(A)

[Chemical Formula B]

In the above, the copolymer may contain from 95 mol% to 99.5 mol% or 97 mol% to 99 mol% of the polymerized units of the formula (A) and from 0.5 mol% to 5 mol% or 1 mol% To 3 mol%. In the above, * represents a bonding site in which the polymerization units are connected to each other in the copolymer. In one example, the monomer of formula (A) may be isobutylene, the monomer of formula (B) may be isoprene, and the copolymer may be butyl rubber.

Since the conventional isobutylene polymer has low water permeability and low heat resistance, the present invention can realize a pressure-sensitive adhesive composition satisfying the numerical value range according to the above-mentioned general formula (1), thereby controlling the crosslinking structure and degree of crosslinking. Accordingly, a film containing the composition can be applied to the sealing structure, thereby improving the moisture resistance and heat resistance of the sealing structure.

In the pressure-sensitive adhesive composition, the resin or the elastomer component may have a weight average molecular weight (Mw) to such an extent that the pressure-sensitive adhesive composition can be formed into a film. For example, the resin or elastomer may have a weight average molecular weight of about 100,000 to 2,000,000, 100,000 to 1,500,000, or 100,000 to 1,000,000. The term "weight average molecular weight" as used herein means a value converted to a standard polystyrene measured by GPC (Gel Permeation Chromatograph). However, the above-mentioned weight average molecular weight does not necessarily have to be contained in the resin or elastomer component. For example, in the case where the molecular weight of the resin or elastomer component does not become so high as to form a film, a separate binder resin may be blended into the pressure-sensitive adhesive composition.

Further, the pressure-sensitive adhesive composition of the present invention may contain an active energy ray-polymerizable compound having high compatibility with the encapsulating resin and capable of forming a specific crosslinking structure together with the encapsulating resin.

For example, the pressure sensitive adhesive composition of the present invention may comprise a polyfunctional active energy ray polymerizable compound that can be polymerized by irradiation of an active energy ray with an encapsulating resin. The active energy ray polymerizable compound is a compound having a functional group capable of participating in polymerization reaction by irradiation of an active energy ray, for example, a functional group containing an ethylenically unsaturated double bond such as an acryloyl group or a methacryloyl group , An epoxy group, or an oxetane group.

As the polyfunctional active energy pre-polymerizable compound, for example, multifunctional acrylate (MFA) can be used.

Further, the polyfunctional active energy ray polymerizable compound that can be polymerized by irradiation with the active energy ray may satisfy the following formula (1). The active energy ray polymerizable compound may be added in an amount of 5 to 30 parts by weight, 5 to 25 parts by weight, 8 to 20 parts by weight, 10 to 19 parts by weight or 13 By weight to 19 parts by weight.

[Chemical Formula 1]

Wherein R ₁ is hydrogen or an alkyl group having 1 to 4 carbon atoms, n is an integer of 2 or more, and X represents an n-substituted residue derived from a linear, branched or cyclic alkyl group having 3 to 30 carbon atoms. In the above, when X is a residue derived from a cyclic alkyl group, X may be, for example, a residue derived from a cyclic alkyl group having 3 to 30 carbon atoms, 6 to 28 carbon atoms, 8 to 22 carbon atoms, or 12 to 20 carbon atoms have. Further, when X is a residue derived from a linear alkyl group, X may be a residue derived from a straight chain alkyl group having 3 to 30 carbon atoms, 6 to 25 carbon atoms, or 8 to 20 carbon atoms. Further, when X is a residue derived from a branched alkyl group, X may be a residue derived from a branched chain alkyl group having 3 to 30 carbon atoms, 5 to 25 carbon atoms, or 6 to 20 carbon atoms. On the other hand, n may be 2 or 3.

As used herein, the term " residue derived from an alkyl group " may mean that it consists of an alkyl group as a residue of a specific compound. In one example, in the above formula (1), when n is 2, X may be an alkylene group. When n is 3 or more, X may be bonded to the (meth) acroyl group of Formula 1 by desorbing two or more hydrogen atoms of the alkyl group.

The term "alkyl group" as used herein means an alkyl group having 1 to 30 carbon atoms, 1 to 25 carbon atoms, 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms or 1 to 4 carbon atoms ≪ / RTI > The alkyl group may have a linear, branched or cyclic structure and may optionally be substituted with one or more substituents.

The term "alkylene group" as used herein means an alkylene group having 2 to 30 carbon atoms, 2 to 25 carbon atoms, 2 to 20 carbon atoms, 2 to 16 carbon atoms, 2 to 12 carbon atoms, 2 to 10 carbon atoms, May mean an alkylene group of 2 to 8 carbon atoms. The alkylene group may have a linear, branched or cyclic structure and may optionally be substituted with one or more substituents.

The term "alkoxy group" as used herein may mean an alkoxy group having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms or 1 to 4 carbon atoms, unless otherwise specified. The alkoxy group may be linear, branched or cyclic. In addition, the alkoxy group may be optionally substituted with one or more substituents.

The polyfunctional active energy ray polymerizable compound which can be polymerized by irradiation with the above active energy ray can be used without limitation as long as it satisfies the above formula (1). For example, the compound may be selected from the group consisting of 1,4-butanediol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,6- Dodecanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, cyclohexanediol di Acrylate, trimethylolpropane di (meth) acrylate, hexane-1,4-dimethanol di (meth) acrylate, tricyclodecane dimethanol metha diacrylate, dimethylol dicyclopentanedi (meth) acrylate, neopentyl glycol- (Meth) acrylate, trimethylol propane tri (meth) acrylate, or a mixture thereof.

As the polyfunctional active energy pre-polymerizable compound, for example, a compound having a molecular weight of less than 1,000 and containing two or more functional groups can be used. In this case, the molecular weight may mean a weight average molecular weight or a conventional molecular weight. The ring structure included in the polyfunctional active energy ray polymerizable compound may be a carbon cyclic structure or a heterocyclic structure; Or a monocyclic or polycyclic structure.

In embodiments of the present invention, the pressure sensitive adhesive composition may further comprise a radical initiator which is capable of inducing the polymerization reaction of the above-mentioned active energy pre-polymerizable compound. The radical initiator may be a photoinitiator or an 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 radical initiator may be contained in an amount of 0.2 to 20 parts by weight, 7 to 15 parts by weight, 8 to 14 parts by weight or 10 to 13 parts by weight based on 100 parts by weight of the active energy ray polymerizable compound. In one example, for an appropriate range of crosslinking implementations, at least 7 parts by weight may be preferred. This can effectively induce the reaction of the active energy ray-polymerizable compound and prevent the deterioration of the physical properties of the pressure-sensitive adhesive composition due to the remaining components after curing.

In one example, the tackifier composition may further comprise a tackifier, which may preferably be a hydrogenated cyclic olefin-based polymer. As the tackifier, for example, a hydrogenated petroleum resin obtained by hydrogenating a petroleum resin can be used. The hydrogenated petroleum resin may be partially or fully hydrogenated and may be a mixture of such resins. Such a tackifier can be selected to have good compatibility with the pressure-sensitive adhesive composition, excellent moisture barrier property, and low organic volatile components. Specific examples of the hydrogenated petroleum resins include hydrogenated terpene resins, hydrogenated ester resins, and hydrogenated dicyclopentadiene resins. The weight average molecular weight of the tackifier may be from about 200 to about 5,000. The content of the tackifier can be appropriately adjusted as needed. For example, the content of the tackifier may be selected in consideration of the gel content and the like described below. According to one example, 5 parts by weight to 100 parts by weight, 8 to 95 parts by weight , 10 parts by weight to 93 parts by weight or 15 parts by weight to 90 parts by weight.

The pressure-sensitive adhesive composition, if necessary, may further comprise a moisture adsorbent. As used herein, the term " moisture absorbent " may mean a material capable of removing the moisture through chemical reaction with water or moisture penetrated by, for example, an adhesive film described later. When the pressure-sensitive adhesive composition of the present invention comprises a moisture adsorbent, when formed into a film, the light transmittance described later can not be satisfied, but an excellent moisture barrier property can be achieved instead. Specifically, the pressure-sensitive adhesive composition can be applied to encapsulating an organic electronic device when formed into a film. In this case, the pressure-sensitive adhesive composition does not contain a moisture adsorbent and exhibits excellent transparency, and is applied to encapsulation of a top emission type organic electronic device; Or a moisture adsorbent, exhibits excellent moisture barrier properties, and is applicable to encapsulation of a bottom emission type organic electronic device. However, the present invention is not limited thereto. That is, the pressure-sensitive adhesive composition does not contain a moisture adsorbent and exhibits excellent transparency, and may be applied to encapsulation of a bottom emission type organic electronic device.

For example, the moisture adsorbent may be present evenly dispersed in the pressure-sensitive adhesive composition or the pressure-sensitive adhesive film. Here, the uniformly dispersed state may mean a state in which the moisture adsorbent is present at the same or substantially the same density in any portion of the pressure-sensitive adhesive composition or the pressure-sensitive adhesive film. Examples of the moisture adsorbent that can be used in the above include metal oxides, sulfates, and organic metal oxides. Specifically, examples of the sulfate include magnesium sulfate, sodium sulfate, and nickel sulfate, and examples of the organic metal oxide include aluminum oxide octylate and the like. Specific examples of the metal oxide include P ₂ O ₅ , Li ₂ O, Na ₂ O, BaO, CaO, MgO, Examples of the metal salt 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 sulfate, calcium chloride (CaCl _2), magnesium chloride (MgCl _2), strontium chloride, such as (NiSO ₄₎ (SrCl ₂ ), YCl ₃ , CuCl ₂ , CsF ₅ , TaF ₅ , NbF ₅ , LiBr, CaBr ₂ , Metal halides such as cesium bromide (CeBr ₃ ), selenium bromide (SeBr ₄ ), vanadium bromide (VBr ₃ ), 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. As the moisture adsorbent which can be contained in the pressure-sensitive adhesive composition, one kind of the above-described constitution may be used, or two or more kinds may be used. In one example, calcined dolomite or the like may be used when two or more species are used as a moisture adsorbent.

Such a moisture adsorbent can be controlled to an appropriate size depending on the application. In one example, the average particle size of the moisture adsorbent can be controlled to about 10 to 15,000 nm. The moisture adsorbent having a size within the above range is not too fast to react with moisture, so that it is easy to store, and water can be effectively removed without damaging the device to be sealed.

The content of the moisture adsorbent is not particularly limited and may be suitably selected in consideration of the desired blocking characteristics.

The pressure-sensitive adhesive composition may further include a moisture barrier agent, if necessary. As used herein, the term " moisture blocker " may refer to a material that is free or low in reactivity with moisture, but can block or interfere with movement of moisture or moisture within the film. As the moisture barrier agent, for example, clay, talc, needle-like silica, plate-like silica, porous silica, zeolite, titania or zirconia may be used. In addition, the moisture barrier agent can be surface-treated with an organic modifier or the like to facilitate penetration of organic substances. Such organic modifiers include, for example, dimethylbenzyl hydrogenated tallow quaternary ammonium, dimethyl dihydrogenated tallow quaternary ammonium, methyl tallow bis-2-hydroxyethyl The present invention relates to a method for producing a hydrogenated tallow quaternary ammonium salt, comprising the steps of: (a) mixing a first aqueous solution of tetraethylammonium hydroxide with a first aqueous solution of tetraethylammonium hydroxide; ) Or an organic modifier such as a mixture thereof.

The content of the moisture barrier agent is not particularly limited and may be suitably selected in consideration of the desired blocking characteristics.

In one example, the pressure-sensitive adhesive composition of the present invention may have a gel content of 40% or more represented by the following general formula (2).

[Formula 2]

Gel content (% by weight) = B / A x 100

In the general formula (2), A represents the mass of the pressure-sensitive adhesive composition, and B represents the mass of the pressure-sensitive adhesive composition obtained by immersing the pressure-sensitive adhesive composition in toluene at 60 ° C for 24 hours and then filtering it through a mesh of 200 mesh. Indicates dry mass.

The gel content represented by the general formula 2 may be 40% or more, 45% to 99%, 50% to 99%, 50% to 90%, 50 to 80% or 50 to 70%. That is, the present invention can realize a pressure-sensitive adhesive film having excellent moisture barrier properties, reliability, and optical characteristics by judging the crosslinking structure and degree of crosslinking in an appropriate range of the pressure-sensitive adhesive composition through the gel content.

In addition, the pressure-sensitive adhesive composition of the present invention can satisfy the following general formula (3).

[Formula 3]

2.4 x 10 ⁵ Pa? G _N ⁰ ? 5.0 x 10 ⁵ Pa

In the above general formula (3), G _N ⁰ was determined by using a DHR (Discovery Hybrid Rheometer) for a circular sample (diameter: 8 mm, thickness: 500 탆) made of a pressure- (X-axis: complex modulus of elasticity, Y-axis: phase angle) in the graph of the phase angle and the complex modulus measured while increasing the frequency range from 0.01 to 100 Hz at a strain of 1% Is the complex elastic modulus value when

Specifically, after loading the sample, the storage elastic modulus and the loss elastic modulus can be measured according to changes in frequency while increasing the frequency from 0.01 Hz to 100 Hz. From the storage elastic modulus and the loss elastic modulus, the phase angle and the complex elastic modulus can be calculated by the following general formulas 4 and 5 (the phase angles and complex elastic moduli at 0.1 Hz are calculated in the following general formulas 4 and 5, Phase angle and complex elastic modulus in the range of Hz to 100 Hz) were calculated. The phase angle and the complex elastic modulus value calculated according to the measurement result were plotted as a graph of the phase angle with respect to the complex elastic modulus. In the plotted graph, the complex modulus at the minimum of the phase angles can be G _N ⁰ , and G _N ⁰ means the plateau modulus.

The term " DHR (Discovery Hybrid Rheometer) " as used herein is a rheological property measuring device for evaluating viscoelastic properties such as viscosity, shear modulus, loss coefficient, phase angle and elastic modulus of a material. In the present invention, a DHR-2 stress control type rheometer manufactured by TA Corporation can be used as the apparatus.

Exemplary pressure-sensitive adhesive compositions may have a high modulus of elasticity according to the general formula 3 of from 2.4 10 ⁵ to 5.0 10 ⁵ Pa, 2.5 10 ⁵ to 4.5 10 ⁵ Pa, or 2.6 10 ⁵ to 4.0 10 ⁵ Pa have. By controlling the composition and crosslinking conditions of the pressure-sensitive adhesive composition to have a high plateau elastic modulus in this numerical range, a pressure-sensitive adhesive film capable of realizing a sealing or encapsulating structure having excellent durability against electronic devices can be provided. That is, as described above, the pressure-sensitive adhesive composition according to the general formula (1) may be crosslinked by crosslinking conditions or the like to be described later to form a pressure-sensitive adhesive or a pressure-sensitive adhesive layer. Such a pressure-sensitive adhesive or pressure-sensitive adhesive layer can satisfy the desired range of the high- have.

In one example, the pressure-sensitive adhesive layer comprising the pressure-sensitive adhesive composition of the present invention may have a phase angle? According to the following general formula (4) within a range of 10 to 18 degrees.

[Formula 4]

? = tan ^-1 (G? / G?)

In the above general formula 4, G 'and G' 'were measured by using a DHR (Discovery Hybrid Rheometer) on a circular sample (diameter: 8 mm, thickness: 500 탆) made of the pressure-sensitive adhesive layer containing the pressure- (G`) and loss modulus (G``) measured under the conditions of the temperature, the strain of 1% and the frequency of 0.1 Hz.

Specifically, the sample was loaded on a DHR2 stress control type rheometer of TA, and then the viscoelasticity (storage elastic modulus and loss elastic modulus) according to the change in frequency was measured while the frequency was increased from 0.01 Hz to 100 Hz. The phase angle calculated by the general formula 4 at 0.1 Hz can be calculated. On the other hand, in order to plot the graph of the phase angle and the complex elastic modulus in the above-mentioned general formula 3, a value in the range of 0.1 Hz to 100 Hz can be measured and then plotted. In one example, the phase angle may be 10 ° to 18 °, 11 ° to 17 °, 12 ° to 16 °, or 13 ° to 16 °. In one example, the complex modulus (| G * |, Complex Modulus) according to the following general formula (5) is 1.5 × 10 ⁴ Pa to 4.0 × 10 ⁴ Pa, 1.6 × 10 ⁴ Pa to 3.5 × 10 ⁴ Pa, 1.7 10 ⁴ Pa to 3.0 10 ⁴ Pa or 1.8 10 ⁴ Pa to 2.8 10 ⁴ Pa.

[Formula 5]

In one example, by controlling the plateau modulus, phase angle, and complex modulus of elasticity to the specific range, the pressure-sensitive adhesive film composed of the above-mentioned pressure-sensitive adhesive composition can have excellent moisture barrier properties, reliability at high temperature and high humidity, and optical characteristics.

The pressure-sensitive adhesive composition may contain various additives in addition to the above-described composition according to the application and the manufacturing process of the pressure-sensitive adhesive film described later. For example, the pressure-sensitive adhesive composition may contain a curable material, a cross-linking agent, a filler or the like in an appropriate range depending on the desired properties.

The present invention also relates to a method for producing a pressure-sensitive adhesive composition. The process comprises the steps of: selecting the encapsulating resin, the polyfunctional active energy pre-polymerizing compound and the radical initiator so that C-Score _i according to general formula 1 is greater than 0 and the encapsulating resin, polyfunctional active energy ray polymerization Lt; RTI ID = 0.0 > and / or < / RTI > radical initiator.

[Formula 1]

C-Score _i = 2.97 tanh (1.197 x _i ) - 0.381 log ₁₀ (0.119 y _i ) - 0.307 (0.160z _i ) ^0.463

X _i represents the mixed energy (ΔE ₁ , KJ / mol) of the active energy ray polymerizable compound and the radical initiator, and y _i represents the mixing energy (ΔE ₂ ) between the active energy ray polymerizable compound and the encapsulating resin , KJ / mol), and z _i represents the reaction energy (ΔE _rxn , KJ / mol) of the active energy ray polymerizable compound and the encapsulating resin.

The present invention also relates to an adhesive film comprising the above-mentioned pressure-sensitive adhesive composition. In one example, the pressure-sensitive adhesive film according to the present invention has a water vapor transmission rate measured with respect to the thickness direction of the pressure-sensitive adhesive layer in a state of being manufactured to a thickness of 100 탆 at a relative humidity of 100 ℉ and 100% m ² · day or less, 40 g / m ² · day or less, 30 g / m ² · day or less, 20 g / m ² · day or less, or 10 g / m ² · day or less. By controlling the composition and crosslinking conditions of the pressure-sensitive adhesive so as to have such a moisture permeability, the sealing or encapsulating structure capable of stably protecting the device by effectively blocking water or oxygen penetrating from the outside when the sealing or encapsulating structure is applied to an electronic device Structure can be implemented. The lower the moisture permeability is, the better the water barrier property can be exhibited. Therefore, the lower limit is not particularly limited, but may be, for example, 0 g / m ² · day.

In the present invention, the adhesive film may include a pressure sensitive adhesive, and the pressure sensitive adhesive may be composed of a layer. Thus, the term pressure-sensitive adhesive layer as used herein may be used in the same sense as the pressure-sensitive adhesive or pressure-sensitive adhesive film. The material of the pressure-sensitive adhesive composition constituting the pressure-sensitive adhesive layer is not particularly limited as long as it satisfies the general formula 1, and ordinary technicians can be appropriately configured according to the object of the invention within the range satisfying the general formula 1. [

In the embodiment of the present invention, the adhesive film may be formed as a single layer structure including a pressure sensitive adhesive as described above, and may be formed of two or more layers as described later. For example, the adhesive film may comprise a first layer comprising the above-described pressure-sensitive adhesive and a second layer comprising a tacky resin or an adhesive resin. The adhesive resin or the adhesive resin contained in the second layer may be the same as or different from the above-mentioned encapsulating resin, and may be appropriately selected according to the purpose of the ordinary artisan. Further, the first layer and the second layer may or may not include a moisture adsorbent, respectively.

In one example, the adhesive resin contained in the second layer is, for example, one that can be cured to exhibit adhesive properties, and may be a thermosetting functional group such as a glycidyl group, an isocyanate group, a hydroxyl group, a carboxyl group or an amide group Or a functional group capable of being cured by irradiation of electromagnetic waves such as an epoxide group, a cyclic ether group, a sulfide group, an acetal group or a lactone group Or more of the curable resin. 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.

In the present invention, as the curable resin, 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 embodiment of the present invention, the first layer or the second layer may have a structure other than the above-mentioned resin, for example, the above-mentioned active energy ray polymerizable compound, radical initiator, tackifier, moisture absorber, Or a silane compound, and the configurations of the first layer and the second layer may be the same or different from each other. The second layer may contain a curable material, a curing agent, a filler or the like in an appropriate range depending on the intended physical properties.

The stacking order of the first layer and the second layer which is additionally stacked is not particularly limited, and the second layer may be formed on the first layer, and conversely, the first layer may be formed on the second layer. Further, the adhesive film may be composed of three or more layers, for example, the first layer may be included as two or more layers, or the second layer may be included as two or more layers.

In one example, the pressure sensitive adhesive film may include a barrier film on one side of the pressure sensitive adhesive. The barrier film can be used without limitation as long as it is a material commonly used in the art. For example, the barrier film may include a base substrate layer, an organic undercoat layer, an inorganic vapor deposition film, and an organic top coating layer, and the organic top coating layer may contact the pressure sensitive adhesive.

In addition, the pressure-sensitive adhesive film may have excellent light transmittance with respect to the visible light region. In one example, the adhesive film of the present invention can exhibit a light transmittance of 85% or more with respect to the visible light region. For example, the adhesive film may have a light transmittance of 85% or more, 87% or more, or 90% or more with respect to the visible light region. Further, the adhesive film of the present invention can exhibit low haze with excellent light transmittance. In one example, the adhesive film may exhibit a haze of 3% or less, 2% or less, 1% or less, 0.8% or less, 0.5% or less, or 0.3% or less.

In one example, the adhesive film is formed by irradiating light having a wavelength ranging from 250 nm to 400 nm, wherein light having a wavelength ranging from 250 nm to 300 nm is emitted from 5% to 50%, 5% to 45%, or 10% to 40% Sensitive adhesive layer crosslinked by a radiation source, which is a ratio of the pressure-sensitive adhesive layer to the pressure-sensitive adhesive layer. The source can be, for example, D-bulb (metal halide lamp) or V-bulb (gallium lamp). Accordingly, the pressure-sensitive adhesive layer may be a pressure-sensitive adhesive layer crosslinked by D-bulb or V-bulb. In the embodiment of the present invention, the pressure-sensitive adhesive layer may be affected by crosslinking conditions and the like in the process of realizing the heat resistance required in the sealing structure at high temperature and high humidity. Therefore, in order to realize the desired physical properties of the pressure-sensitive adhesive layer in the present invention, it is preferable that the irradiation source having a high ratio of short wavelength is excluded.

The adhesive film may further have a structure in which the adhesive film is formed on the base material or the release film, further comprising a base film or a release film (hereinafter may be referred to as " first film " The structure may further include a substrate or a release film (hereinafter also referred to as " second film ") formed on the pressure-sensitive adhesive.

1 and 2 are sectional views of an exemplary adhesive film.

The adhesive film 1 may include a pressure-sensitive adhesive 11 formed on the base material or the release film 12 as shown in Fig. Another exemplary adhesive film 2 may additionally include a substrate or a release film 21 formed on the pressure-sensitive adhesive 11, as shown in Fig. Although not shown in the drawings, the pressure-sensitive adhesive film may have a structure containing only the pressure-sensitive adhesive composition without a supporting substrate such as a substrate or a release film and containing only a film or sheet- Or may have a structure in which an adhesive is formed on both sides of one base material or release film.

The specific kind of the first film is not particularly limited. As the first film, for example, a plastic film can be used. Examples of the first film include a polyethylene terephthalate film, a polytetrafluoroethylene film, a polyethylene film, a polypropylene film, a polybutene film, a polybutadiene film, a vinyl chloride copolymer film, a polyurethane film, an ethylene- -Propylene copolymer film, an ethylene-ethyl acrylate copolymer film, an ethylene-methyl acrylate copolymer film, or a polyimide film.

When the first film is a release film, one or both sides of the plastic film may be subjected to appropriate mold release treatment. Examples of the releasing agent used in the releasing treatment include an alkyd releasing agent, a silicone releasing agent, a fluorine releasing agent, an unsaturated ester releasing agent, a polyolefin releasing agent and a wax releasing agent. An alkyd-based releasing agent, a silicone-based releasing agent, a fluorine-containing releasing agent, and the like may be commonly used in view of heat resistance and the like, but the present invention is not limited thereto.

As the first film, for example, a plastic film in which a gas barrier layer is formed on the surface or side surface of the substrate can be used. Such a film may be used, for example, in the fabrication of a flexible device by constituting a substrate of a direct organic electronic device.

The type of the second film is also not particularly limited. For example, as the second film, the same or different kinds as the first film may be used within the scope exemplified in the first film described above.

The thickness of the first or second film is not particularly limited. In one example, the thickness of the first film may be about 50 탆 to 500 탆 or about 100 탆 to 200 탆. In this range, it is possible to effectively automate the production process of the pressure-sensitive adhesive or the organic electronic device, and is also advantageous from the viewpoint of economy.

The thickness of the second film is also not particularly limited. For example, the thickness of the second film may be the same as that of the first film, or may be adjusted to a relatively thin or thick thickness as compared with the first film.

The pressure-sensitive adhesive of the pressure-sensitive adhesive film includes the above pressure-sensitive adhesive composition, and has a film or sheet form. In the pressure-sensitive adhesive, the pressure-sensitive adhesive composition may be crosslinked or uncrosslinked. The pressure-sensitive adhesive may be solid or semi-solid at room temperature. Such a pressure-sensitive adhesive resin can form a crosslinked structure in an encapsulating structure of an organic electronic device to be described later.

The thickness of the pressure-sensitive adhesive is not particularly limited and may be suitably selected in consideration of the application. For example, the pressure-sensitive adhesive may have a thickness of about 5 to 200 mu m. The thickness of the pressure-sensitive adhesive can be adjusted, for example, in consideration of the filling property, the processability and the economical efficiency when the sealing material is used as an encapsulating material for an organic electronic device.

The present application also relates to a method for producing an adhesive film. Exemplary methods for producing an adhesive film include the steps of selecting the encapsulating resin, the polyfunctional active energy pre-polymerizing compound and the radical initiator so that C-Score _i according to general formula 1 is larger than 0, The active energy ray-polymerizable compound and radical initiator may be mixed to prepare a pressure-sensitive adhesive composition, and the pressure-sensitive adhesive composition may be formed into a film or sheet.

In one example, the step of forming the film or sheet may include applying the coating liquid containing the pressure-sensitive adhesive composition in the form of a sheet or a film on a substrate or release film, and drying the applied coating liquid. The method of manufacture may also include adhering an additional substrate or release film onto the dried coating solution.

The coating liquid containing the pressure-sensitive adhesive composition can be prepared, for example, by dissolving or dispersing the components of the pressure-sensitive adhesive composition described above in an appropriate solvent. In one example, the pressure-sensitive adhesive composition may be prepared by dissolving or dispersing the moisture adsorbent, blocking agent or filler in a solvent if necessary, and then mixing the pulverized moisture adsorbent, blocking agent or filler with the encapsulating resin can do.

The kind of the solvent used for preparing the coating liquid is not particularly limited. However, when the drying time of the solvent is excessively long or when drying at a high temperature is required, a problem may arise in terms of workability or durability of the pressure-sensitive adhesive film, and therefore a solvent having a volatilization temperature of 150 ° C or lower may be used. In view of film formability and the like, a small amount of a solvent having a volatilization temperature higher than the above range may be mixed and used. Examples of the solvent include methyl ethyl ketone (MEK), acetone, toluene, dimethylformamide (DMF), methylcellosolve (MCS), tetrahydrofuran (THF), xylene or N-methylpyrrolidone , But is not limited thereto.

The method of applying the coating solution to the base material or the release film is not particularly limited and a known coating method such as knife coat, roll coat, spray coat, gravure coat, curtain coat, comma coat or lip coat can be applied .

The applied coating liquid may be dried to volatilize the solvent and form a pressure-sensitive adhesive. The drying is carried out at a temperature of, for example, 70 캜 to 150 캜, more than 100 캜, less than 150 캜, 105 캜 to 150 캜, 110 캜 to 150 캜 or 120 캜 to 140 캜 for 1 minute to 100 minutes . The conditions of the drying may be changed in consideration of the kind of the solvent used. Through the above drying conditions, crosslinking degree and the like desired for the purpose of the present invention can be realized. Drying may be followed by formation of an additional substrate or release film on the pressure sensitive adhesive, and then crosslinking the pressure sensitive adhesive. The crosslinking may be carried out in an amount of 0.2 J / cm ² to 5 J / cm ² , 0.2 J / cm ² to 3 J / cm ² , UV cross-linking may be performed at 0.5 J / cm ² to 1.8 J / cm ² or at 0.8 J / cm ² to 1.5 J / cm ² . The UV crosslinking can be conducted by using D-bulb (metal halide lamp) or V-bulb (gallium lamp). By irradiating the lamp with light, the crosslinking structure and degree of crosslinking to be realized in the present invention can be satisfied. For example, in the case of H-bulb (mercury lamp), the ratio of short wavelength is high, so that it may be difficult to realize the desired degree of crosslinking in the present invention.

In order to realize the desired effect in the present invention, the compatibility and the reaction energy between the compositions in which the crosslinking reaction takes place influence the pressure sensitive adhesive composition constituting the pressure sensitive adhesive film of the present invention satisfies the numerical range in the general formula 1 One, in addition, the crosslinking conditions as well as the abovementioned composition can also be influenced. Accordingly, by controlling the drying conditions or the crosslinking conditions of the pressure-sensitive adhesive film as described above, it is possible to provide a reliable pressure-sensitive adhesive film in severe conditions such as high humidity and high humidity by realizing the above-mentioned degree of crosslinking.

The present invention also relates to organic electronic devices. The organic electronic device comprising: a substrate; An organic electronic device formed on the substrate; And an adhesive film which encapsulates the front surface of the organic electronic device, for example, both the top surface and the side surface. The pressure-sensitive adhesive film may include a pressure-sensitive adhesive containing the pressure-sensitive adhesive composition in a crosslinked state. The organic electronic device encapsulation product may further include a cover substrate formed on the adhesive.

The organic electronic device may be, for example, an organic light emitting device.

The present invention also relates to a method of manufacturing an organic electronic device. The organic electronic device encapsulation product can be produced, for example, by using the adhesive film.

The pressure sensitive adhesive can be formed as a structural sealant layer that efficiently fixes and supports the substrate and the cover substrate while exhibiting excellent moisture barrier properties and optical characteristics in an organic electronic device.

In addition, the pressure-sensitive adhesive exhibits excellent transparency and can be formed of a stable pressure-sensitive adhesive regardless of the form of organic electronic devices such as top emission or bottom emission.

The term sealing layer in this specification may mean a pressure sensitive adhesive covering both the top and side surfaces of the organic electronic device.

3 is a schematic diagram showing an example of an organic electronic device in which the organic electronic device is an organic light emitting device.

In order to manufacture the organic electronic device, for example, the above-described adhesive film is applied to the substrate on which the organic electronic device is formed to cover the organic electronic device. And curing the adhesive film.

As used herein, the term " curing " means that the pressure-sensitive adhesive composition of the present invention forms a cross-linking structure through heating or UV irradiation process and is produced in the form of a pressure-sensitive adhesive.

Specifically, a transparent electrode is formed on a glass or polymer film 31 used as a substrate by a method such as vacuum deposition or sputtering, and a transparent electrode is formed on the transparent electrode, for example, a hole transport layer, a light emitting layer and an electron transport layer After forming a layer of the luminescent organic material, an electrode layer may be further formed on the layer to form the organic electronic device 32. Then, the adhesive of the adhesive film is placed so as to cover the entire surface of the organic electronic device 32 of the substrate 31 that has undergone the above process.

And then the pressure-sensitive adhesive is heated using a laminate or the like to pressurize the organic electronic element in a fluidized state, and the resin in the pressure-sensitive adhesive is crosslinked to form the sealing layer.

In one example, the adhesive 33 positioned to cover the front surface of the organic electronic device 32 may be previously transferred to a cover substrate 34 such as a glass or a polymer film. The transfer of the pressure sensitive adhesive onto the cover substrate 34 can be carried out by, for example, peeling off the first or second film from the pressure sensitive adhesive film, and then pressing the pressure sensitive adhesive on the cover substrate 34 in a vacuum press or vacuum laminate And so on. If the pressure-sensitive adhesive contains a thermosetting curable pressure-sensitive adhesive resin, if the curing reaction is excessively performed in the above process, the adhesion or adhesion of the pressure-sensitive adhesive layer may be decreased, so that the process temperature is controlled to be about 100 캜 or less, can do.

The cover substrate 34 onto which the pressure-sensitive adhesive is transferred may be placed on the organic electronic device 32, and the sealing layer may be formed by performing the heat-pressing process.

The pressure sensitive adhesive 33 may be cured to form an encapsulating layer. In this specification, the sealing layer can be used in the same sense as the pressure-sensitive adhesive layer. The curing process can be carried out in an appropriate heating chamber or ultraviolet chamber, for example, depending on the curing method of the curable pressure-sensitive adhesive resin. The heating condition or the irradiation condition of the active energy ray can be appropriately selected in consideration of the stability of the organic electronic device and the curing property of the adhesive resin, and an autoclave for simultaneously applying heat and pressure may be executed to increase the compression efficiency.

Although one example of the manufacturing method of organic electronic devices has been mentioned above, the organic electronic devices may be manufactured in other ways as well. For example, the fabrication of the device is performed in the same manner as described above, but the order or conditions of the process may be changed. For example, the pressure sensitive adhesive is not transferred to the cover substrate 34 in advance, but is first transferred to the organic electronic device on the substrate 31 first, and the cover substrate 34 is laminated and the curing process is performed to form an encapsulating layer You may.

The pressure-sensitive adhesive composition of the present application can be applied to encapsulation or encapsulation of an organic electronic device such as an OLED or the like. In particular, the pressure-sensitive adhesive composition of the present application can be applied to encapsulation or encapsulation as described above to form an encapsulation or encapsulation structure having excellent durability reliability, such as not generating bubbles even under high-temperature and high-humidity conditions. The pressure-sensitive adhesive composition is also capable of forming a structure capable of effectively blocking water or oxygen introduced into the organic electronic device from the outside, and is excellent in mechanical properties and transparency such as handleability and processability. The pressure-sensitive adhesive composition may be applied, for example, to encapsulation or encapsulation of an OLED having a top emission structure.

1 and 2 are sectional views showing an adhesive film according to one example of the present invention.
3 is a cross-sectional view showing an encapsulation product of 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

20 g (SU-90, Kolon) of a hydrogenated DCPD tackifier resin as a tackifier, 80 g of a butyl rubber as a sealing resin (BR268_alkane: BR268_olefin = 19: 1 (molar ratio)) and tricyclodecane dimethanol 15 g (M262, Miwon) of diacrylate and 1 g (Irgacure 651, Ciba) of 2,2-dimethoxy-1,2-diphenylethane-1-one as a radical initiator were added, To prepare a coating pressure sensitive adhesive composition solution.

The prepared solution was applied to the releasing surface of the releasing PET and dried to produce a pressure-sensitive adhesive film comprising a pressure-sensitive adhesive layer having a thickness of 20 탆. The prepared film was irradiated with ultraviolet light at a rate of 1 J / cm ² through D-bulb to measure physical properties.

Example  2

An adhesive film was prepared in the same manner as in Example 1, except that 10 g of trimethylolpropane tri (meth) acrylate was used as the active energy ray polymerizable compound.

Comparative Example  One

Except that 10 g of ethylene glycol dimethacrylate was used as the active energy ray polymerizable compound and the produced film was irradiated with ultraviolet rays at 0.1 J / cm ² through H-bulb, A film was prepared.

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

1. Reliability Evaluation

The films prepared in Examples and Comparative Examples were laminated on a barrier film (serving as a cover substrate), laminated on a glass substrate, and pressed under heating at 50 ° C under a pressure of 5 atm under an autoclave to prepare specimens. Thereafter, the specimen was kept in a constant temperature and humidity chamber at 85 ° C and 85% relative humidity for about 500 hours to observe the occurrence of lifting, bubbling or haze at the interface between the glass substrate and the pressure-sensitive adhesive layer. When viewed from the naked eye, X is indicated when any lifting, bubble or haze occurs at the interface between the glass substrate and the pressure-sensitive adhesive layer, and 0 when no bubbles or haze occurs.

2. Gel content  Measure

Gel content (% by weight) = B / A x 100

In the above, A represents the mass of the pressure-sensitive adhesive composition of Examples and Comparative Examples, and B represents the mass of the pressure-sensitive adhesive composition obtained by immersing the pressure-sensitive adhesive composition at 60 DEG C in toluene for 24 hours, filtering it with a mesh of 200 mesh (pore size 200 mu m) The dry mass of the insoluble component of the pressure-sensitive adhesive composition.

3. Δ E _One , Δ E ₂ , Δ E _rxn  And C- Score _i Measure

? E _{1 ,?} E _{2 ,?} E _rxn and C-Score _i of the sealing resin, the active energy ray polymerizable compound and the radical initiator used in Examples and Comparative Examples were measured by the following methods. In the case of mixed energy, the surface charge distribution of each material is quantitatively computed. In addition, the chemical potential of pure materials and mixtures is calculated thermodynamically using the surface screening charge distribution. Use this to calculate how much it can stabilize when it becomes a mixture. With respect to the mixed energy measurement, the surface screening charge distribution was programmed using the program TURBOMOLE version 6.5 (TURBOMOLE GmbH, Karlsruhe) (DFT, Density Functional Theory calculation program) functional, and the basis set used def-TZVP. Thermodynamic calculations were performed using the COSMO therm version C30_1301 (COSMO logic GmbH & Co. KG, COSMO-RS theory).

The energy of the reaction is quantitatively calculated before and after the reaction, and the difference is calculated. Regarding the reaction energy measurement, the program used was the quantum dynamics program (DFT program) of DMol3 version 6.1 (BIOVIA), exchange-correlation functional using BP functional and basis set using DNP.

The inputs to DMol3 are as follows.

# Task parameters

Calculate optimize

Opt_energy_convergence 1.0000e-005

Opt_gradient_convergence 2.0000e-003a

Opt_displacement_convergence 5.0000e-003e

Opt_iterations 128

Opt_max_displacement 0.3000 A

Symmetry off

# Electronic parameters

Spin_Polarization unrestricted

Spin 0

Charge 0

Basis dnp

Atom_rcut 5.5000 angstrom

Pseudopotential none

Functional bp

Aux_density octupole

Integration_grid fine

Scf_density_convergence 1.0000e-006

Scf_charge_mixing 0.2000

Scf_spin_mixing 0.5000

Scf_iterations 128

Scf_diis 6 pulay

Occupation Fermi

# Print options

Print eigval_last_it

# Calculated properties

Plot homo

Plot lumo

Electrostatic_moments on

Mulliken_analysis charge

Hirshfeld_analysis charge

Esp_fit on

bond_order on

Grid msbox 3 0.2500 0.2500 0.2500 3.0000

As described above _,? E _{1 ,?} E ₂ and? E _rxn of the sealing resin, the active energy ray polymerizable compound and the radical initiator used in Examples and Comparative Examples were measured and C-Score _i was calculated according to the following general formula (1).

[Formula 1]

C-Score _i = 2.97 tanh (1.197 x _i ) - 0.381 log ₁₀ (0.119 y _i ) - 0.307 (0.160z _i ) ^0.463

X _i represents the mixed energy (ΔE ₁ , KJ / mol) of the active energy ray polymerizable compound and the radical initiator, and y _i represents the mixing energy (ΔE ₂ ) between the active energy ray polymerizable compound and the encapsulating resin , KJ / mol), and z _i represents the reaction energy (ΔE _rxn , KJ / mol) of the active energy ray polymerizable compound and the encapsulating resin.

4. Plate elasticity

Using a DHR2 (Discovery Hybrid Rheometer) stress control type rheometer manufactured by TA Corporation, a circular sample (diameter: 8 mm, thickness: 500 탆, removal of release PET from the pressure-sensitive adhesive film) The storage elastic modulus (G ') and the loss elastic modulus (G``) were measured while increasing the frequency from 0.01 Hz to 100 Hz at a temperature of 80 ° C. and a strain of 1% strain (linear region section strain). The phase angle at a specific frequency can be measured through the following equation (4).

[Formula 4]

? = tan ^-1 (G? / G?)

The storage elastic modulus and the loss elastic modulus can be measured in the same manner as the phase angle measurement, and the complex elastic modulus at a specific frequency can be calculated according to the following equation (5).

[Formula 5]

As in the phase angle measurement described above, the storage elastic modulus and the loss elastic modulus were measured in accordance with the change of frequency while the frequency was increased from 0.01 Hz to 100 Hz. From the storage elastic modulus and the loss elastic modulus, And complex elastic modulus were calculated.

The phase angle and complex elastic modulus values in the range of 0.01 Hz to 100 Hz are plotted as a graph of the phase angle (Y axis) with respect to the complex elastic modulus (X axis). In the plotted graph, G _N ⁰ (plateau modulus) was measured as the complex elastic modulus at the minimum value of the phase angle.

High temperature and high reliability Gel content Plateau modulus ΔE ₁ ΔE ₂ ΔE _rxn C-Score _i 85 ° C, 85% RH % Pa KJ / mol KJ / mol KJ / mol - Example 1 O 66.1 287,483 0.09 4.23 0.01 0.43 Example 2 O 44 258,277 0.05 7.48 0.01 0.18 Comparative Example 1 X 0.5 236,854 -0.21 3.94 39.78 -1.34

1, 2: Adhesive film
11: Pressure-sensitive adhesive layer
12: First film
21: Second film
3: Organic electronic device
31: substrate
32: organic electronic device
33: pressure-sensitive adhesive layer or sealing layer
34: Cover substrate

Claims (21)

A pressure-sensitive adhesive composition comprising an encapsulating resin, a polyfunctional active energy pre-polymerizable compound and a radical initiator, wherein the C-Score _i according to general formula (1)
[Formula 1]
C-Score _i = 2.97 tanh (1.197 x _i ) - 0.381 log ₁₀ (0.119 y _i ) - 0.307 (0.160z _i ) ^0.463
X _i represents the mixed energy (ΔE ₁ , KJ / mol) of the active energy ray polymerizable compound and the radical initiator, and y _i represents the mixing energy (ΔE ₂ ) between the active energy ray polymerizable compound and the encapsulating resin , KJ / mol), and z _i represents the reaction energy (ΔE _rxn , KJ / mol) of the active energy ray polymerizable compound and the encapsulating resin. The pressure-sensitive adhesive composition according to claim 1, wherein a mixing energy (ΔE ₁ ) of the active energy ray-polymerizable compound and the radical initiator is 0 KJ / mol or more. The pressure-sensitive adhesive composition according to claim 1, wherein a mixing energy (? E ₂ ) of the active energy ray-polymerizable compound and the encapsulating resin is 8 KJ / mol or less. The pressure-sensitive adhesive composition according to claim 1, wherein the reactive energy (ΔE _rxn , KJ / mol) of the active energy ray-polymerizable compound and the encapsulating resin is 10 KJ / mol or less. The pressure-sensitive adhesive composition according to claim 1, wherein C-Score _i is greater than 0 and less than 5. The pressure-sensitive adhesive composition according to claim 1, wherein the sealing resin comprises a copolymer comprising a polymerization unit represented by the following formula (A) and a polymerization unit represented by the following formula (B):
(A)

[Chemical Formula B]

The pressure-sensitive adhesive composition according to claim 6, wherein the copolymer comprises 95 mol% to 99.5 mol% of the polymerization unit of the formula (A) and 0.5 mol% to 5 mol% of the polymerization unit of the formula (B). The pressure-sensitive adhesive composition according to claim 1, wherein the polyfunctional active energy ray polymerizable compound satisfies the following formula (1):
[Chemical Formula 1]

Wherein R ₁ is hydrogen or an alkyl group having 1 to 4 carbon atoms, n is an integer of 2 or more, and X represents an n-substituted residue derived from a linear, branched or cyclic alkyl group having 3 to 30 carbon atoms. The pressure-sensitive adhesive composition according to claim 8, wherein n is 2 or 3. The pressure-sensitive adhesive composition according to claim 1, wherein the active energy ray-polymerizable compound is contained in an amount of 5 to 30 parts by weight based on 100 parts by weight of the encapsulating resin. The pressure-sensitive adhesive composition according to claim 1, wherein the radical initiator is contained in an amount of 0.2 to 20 parts by weight based on 100 parts by weight of the active energy ray-polymerizable compound. The pressure-sensitive adhesive composition according to claim 1, further comprising a moisture adsorbent. The pressure-sensitive adhesive composition according to claim 1, wherein the gel content represented by the following general formula (2) is 40% or more:
[Formula 2]
Gel content (% by weight) = B / A x 100
In the general formula 2, A represents the mass of the pressure-sensitive adhesive composition, and B represents the mass of the pressure-sensitive adhesive composition obtained by immersing the pressure-sensitive adhesive composition in toluene at 60 DEG C for 24 hours, filtering the resultant through a 200 mesh screen, Lt; / RTI > The pressure-sensitive adhesive composition according to claim 1, which satisfies the following general formula (3):
[Formula 3]
2.4 x 10 ⁵ Pa? G _N ⁰ ? 5.0 x 10 ⁵ Pa
In the above general formula (3), G _N ⁰ was determined by using a DHR (Discovery Hybrid Rheometer) for a circular sample (diameter: 8 mm, thickness: 500 탆) made of a pressure- (X-axis: complex modulus of elasticity, Y-axis: phase angle) in the graph of the phase angle and the complex modulus measured while increasing the frequency range from 0.01 to 100 Hz at a strain of 1% Is the complex elastic modulus value when Selecting an encapsulating resin, a polyfunctional active energy pre-polymerizable compound and a radical initiator such that C-Score _i according to general formula 1 is greater than zero; And mixing the encapsulating resin, the polyfunctional active energy ray polymerizable compound and the radical initiator.
[Formula 1]
C-Score _i = 2.97 tanh (1.197 x _i ) - 0.381 log ₁₀ (0.119 y _i ) - 0.307 (0.160z _i ) ^0.463
X _i represents the mixed energy (ΔE ₁ , KJ / mol) of the active energy ray polymerizable compound and the radical initiator, and y _i represents the mixing energy (ΔE ₂ ) between the active energy ray polymerizable compound and the encapsulating resin , KJ / mol), and z _i represents the reaction energy (ΔE _rxn , KJ / mol) of the active energy ray polymerizable compound and the encapsulating resin. A pressure-sensitive adhesive film comprising a pressure-sensitive adhesive layer containing the pressure-sensitive adhesive composition according to claim 1. The pressure-sensitive adhesive film according to claim 16, wherein the pressure-sensitive adhesive layer has a water vapor permeability of 50 g / m ² · day or less in a thickness direction in a state of being manufactured to a thickness of 100 μm. The adhesive film according to claim 16, wherein the adhesive film exhibits a light transmittance of 85% or more with respect to the visible light region. The adhesive film according to claim 16, wherein the adhesive film exhibits a haze of 3% or less. Board; An organic electronic device formed on a substrate; And an adhesive film according to claim 16 for sealing the organic electronic device. Applying the adhesive film of claim 16 to the substrate on which the organic electronic device is formed to cover the organic electronic device; And crosslinking the adhesive film.

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