KR101867013B1 - Organic light emitting diode display and method for manufacturing the same - Google Patents

Abstract

Board; An organic light emitting device formed on the substrate; An encapsulation substrate formed on the organic light emitting device; And an adhesive layer formed on the substrate and covering the organic light emitting device and bonding the substrate on which the organic light emitting device is formed to the sealing substrate.

Description

TECHNICAL FIELD [0001] The present invention relates to an organic light emitting diode (OLED) display device,

To an organic light emitting display.

An organic light emitting diode (OLED) display has self-emission characteristics, and unlike a liquid crystal display, it does not require a separate light source, thereby reducing thickness and weight. In addition, organic light emitting display devices are attracting attention as next generation display devices for portable electronic devices because they exhibit high quality characteristics such as low power consumption, high luminance, and high response speed.

The organic light emitting diode display includes a plurality of organic light emitting diodes having a hole injection electrode, an organic light emitting layer, and an electron injection electrode. Light is emitted by energy generated when an exciton generated by the combination of electrons and holes in the organic light emitting layer falls from the excited state to the ground state, and the organic light emitting display forms an image using the energy.

However, the organic light emitting layer is sensitive to an external environment such as moisture or oxygen, and when the organic light emitting layer is exposed to moisture and oxygen, the quality of the organic light emitting display deteriorates. Therefore, in order to protect the organic light emitting element and to prevent moisture or oxygen from penetrating into the organic light emitting element, the sealing substrate is sealed and attached to the display substrate on which the organic light emitting element is formed through an additional sealing process, Layer.

However, in order to completely prevent water or oxygen from penetrating into the organic light emitting layer both in the case of using the sealing substrate or in the case of forming the protective layer, the manufacturing process of the organic light emitting display is complicated, There was a difficulty in forming.

In one embodiment of the present invention, an organic light emitting display device is provided which effectively inhibits penetration of moisture or oxygen, simplifies the manufacturing process, and has an improved yield.

In another embodiment of the present invention, a method of manufacturing the above-described organic light emitting display device is provided.

In one embodiment of the present invention, a substrate comprises a substrate; An organic light emitting device formed on the substrate; An encapsulation substrate formed on the organic light emitting device; And an adhesive layer formed on the substrate and covering the organic light emitting device and bonding the substrate on which the organic light emitting device is formed to the sealing substrate.

The adhesive layer is formed by laminating at least one filler adhesive layer and at least one hygroscopic adhesive layer, for example, a first filler adhesive layer, a hygroscopic adhesive layer and a second filler adhesive layer sequentially laminated.

The moisture-absorbing adhesive layer is a silica gel _{(silica gel: SiO 2 · H} 2 O), alumino-silicate beads the zeolite (zeolite as the (alumino-silicate beads), montmorillonite (montmorillonite), molecular sieves (molecular sieve): Na ₁₂ At least one moisture absorber selected from the group consisting of AlO ₃ SiO ₂ .12H ₂ O), activated carbon, alkali metal oxides, alkaline earth metal oxides, metal sulfates, metal halides and metal perchlorates have.

The first and second filler adhesion layers may each independently be formed of a material selected from the group consisting of talc, silica, magnesium oxide, mica, montmorillonite, alumina, graphite, beryllium oxide, aluminum nitride, At least one filler selected from the group consisting of silicon carbide, mullite, and silicon.

The particle size of the hygroscopic material may be 10 nm to 20 um.

The particle size of the filling material may be between 10 nm and 20 um.

The hygroscopic material or the fill material may be of a mesoporous type, a plate type, a spherical type, a rod type, a fiber type or a core-shell type type.

The adhesive layer may include a thermosetting resin or a photocurable resin.

The first filling adhesive layer, the hygroscopic adhesive layer and the second filling adhesive layer may all be formed as a single sheet including a thermosetting resin or a photo-curing resin of the same kind, so that the adhesive layer does not form an interlayer interface.

Wherein the first filler adhesive layer and the second filler adhesive layer each independently comprise 100 parts by weight of a thermosetting resin or a photocurable resin; And 5 to 50 parts by weight of a filler.

Wherein the hygroscopic adhesive layer comprises 100 parts by weight of a thermosetting resin or a photocurable resin; And 5 to 50 parts by weight of a hygroscopic material.

The thickness of the adhesive layer may be from 5 [mu] m to 30 [mu] m.

In the adhesive layer, the thickness ratio of the first filling adhesive layer, the moisture absorption bonding layer and the second filling adhesive layer may be 0.1 to 1.2: 0.1 to 1.2: 0.1 to 1.2.

In another embodiment of the present invention, there is provided a method of manufacturing a light emitting device, comprising: forming an organic light emitting element on a substrate; Forming an adhesive layer by sequentially laminating a first filling adhesive layer, a moisture absorbing adhesive layer, and a second filling adhesive layer on the substrate; and bonding the organic EL panel to the sealing substrate through the adhesive layer, A device manufacturing method is provided.

The organic light emitting display device may be manufactured by a roll-to-roll process, a roll-to-glass process, a press-fit process, or a diaphragm process. The first filling adhesive layer, And sequentially forming a laminated adhesive layer.

In the method of manufacturing an organic light emitting diode display device, the step of forming the adhesive layer on the sealing substrate, followed by laminating the substrate with the substrate on which the organic light emitting diode is formed by a lamination process, a pressing process, or a diaphragm process is performed .

The organic light emitting display has excellent lifetime characteristics.

1 is a schematic cross-sectional view of an OLED display according to an embodiment of the present invention.
2 is a schematic view illustrating a method of manufacturing an adhesive layer that can be included in an OLED display according to another embodiment of the present invention.
3 is a schematic cross-sectional view of an OLED display according to another embodiment of the present invention.

Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings, which will be readily apparent to those skilled in the art to which the present invention pertains. The present invention may be embodied in many different forms and is not limited to the embodiments described herein.

In order to clearly illustrate the present invention, parts not related to the description are omitted, and the same or similar components are denoted by the same reference numerals throughout the specification.

In addition, since the sizes and thicknesses of the respective components shown in the drawings are arbitrarily shown for convenience of explanation, the present invention is not necessarily limited to those shown in the drawings.

In addition, the size and thickness of each component shown in the drawings are arbitrarily exaggerated for convenience of explanation, and thus the present invention is not necessarily limited to those shown in the drawings.

In the drawings, the thickness is enlarged to clearly represent the layers and regions. In the drawings, for the convenience of explanation, the thicknesses of some layers and regions are exaggerated. Whenever a portion such as a layer, film, region, plate, or the like is referred to as being "on" or "on" another portion, it includes not only the case where it is "directly on" another portion but also the case where there is another portion in between. Conversely, when a part is "directly over" another part, it means that there is no other part in the middle.

Hereinafter, an embodiment of the present invention will be described with reference to FIGS. 1 to 3. FIG.

1 is a cross-sectional view of an OLED display 100 according to an embodiment of the present invention.

1, the OLED display 100 includes a substrate 10, an organic light emitting diode 20 formed on the substrate 10, an encapsulation substrate 40 formed on the organic light emitting diode 20, And an adhesive layer 30 interposed between the substrate 10 and the encapsulation substrate 40.

The organic light emitting device 20 displays an image with an organic light emitting layer (not shown) that emits light, and the driving circuit unit DC (shown in FIG. 3) drives the organic light emitting device 20. The organic light emitting diode 70 and the driving circuit DC are not limited to the structure shown in FIG. 3, and the organic light emitting diode 70 may emit light to easily display an image, And may be formed into various structures within a range that can be modified.

The upper portion of the organic light emitting element 20 is sealed with the sealing substrate 40 through the adhesive layer 30 in order to inhibit moisture or oxygen from penetrating into the organic light emitting layer. That is, the adhesive layer 30 is formed on the substrate 10 on which the organic light emitting device 20 is formed to cover the organic light emitting device 20, and the sealing substrate 40 is formed thereon.

The sealing substrate 40 may be a glass substrate, a transparent plastic substrate, or the like, which is an insulator, and may be used for a front emission type when the sealing substrate is made of a transparent material.

The adhesive layer 30 is formed by sequentially laminating the first filling adhesive layer 31, the moisture absorption bonding layer 32 and the second filling adhesive layer 33 in this order. The first filling adhesive layer 31 and the second filling adhesive layer 33 include a filling material, and the moisture absorption bonding layer 32 includes a moisture absorbing material.

The adhesive layer 30 is formed by bonding the substrate 10 on which the organic light emitting diode 20 is formed and the sealing substrate 40 to each other while simultaneously bonding moisture absorbing materials having moisture absorption / adsorption characteristics and moisture to external moisture, And can protect the organic light emitting diode 20 from moisture and improve lifetime.

The first filling adhesive layer 31, the moisture absorption bonding layer 32 or the second filling adhesive layer 33 can be manufactured from a composition obtained by mixing a thermosetting resin or a photocurable resin with a filling material or a hygroscopic material. The composition will be described later.

When the first filling adhesive layer 31, the hygroscopic adhesive layer 32 and the second filling adhesive layer 33 are all formed from a composition containing the same kind of thermosetting resin or photo-curable resin, the adhesive layer 30 is bonded to the first filling adhesive layer 31 ), The moisture-absorbing adhesive layer (32), and the second filling adhesive layer (33).

The hygroscopic material that may be contained in the hygroscopic adhesive layer 32 may be any getter material that easily reacts with an active gas such as moisture and oxygen to prevent the active gas from harming the organic light emitting device 20. [ For example, a desiccant which is a kind of getter material that removes moisture can be used. Such a hygroscopic material may be a particle or a medium having a characteristic capable of absorbing and adsorbing moisture and oxygen, and any kind of material capable of absorbing and adsorbing moisture and oxygen may be used, It does not.

The hygroscopic material may be, for example, Clay such as silica gel (SiO ₂ .H ₂ O), alumino-silicate beads, montmorillonite, zeolite as a molecular sieve, Na ₁₂ AlO ₃ SiO ₂ .12H ₂ O), activated carbon, alkali metal oxides, alkaline earth metal oxides, metal sulfates, metal halides and metal perchlorates, or a combination of at least one of these.

More specifically, the alkali metal oxide may be lithium oxide (Li ₂ O), sodium oxide (Na ₂ O) or potassium oxide (K ₂ O), and the alkaline earth metal oxide may be barium oxide (BaO), calcium oxide CaO and MgO and the metal sulfate may be selected from the group consisting of lithium sulfate (Li ₂ SO ₄ ), sodium sulfate (Na ₂ SO ₄ ), calcium sulfate (CaSO ₄ ), magnesium sulfate (MgSO ₄ ) (CoSO _4), sulfate, gallium _{(Ga 2 (SO 4) 3} ), titanium sulfate _{(Ti (SO 4) 2)} , nickel sulfate (NiSO _4), and the like, the metal halide salt (CaCl _2), chloride magnesium (MgCl _2), chloride, strontium (SrCl _2), chloride, yttrium (YCl _3), copper chloride (CuCl _2), cesium fluoride (CsF), fluoride tantalum (TaF _5), fluoride, niobium (NbF _5), bromide (LiBr), CaBr ₂ , CeBr ₃ , SeBr ₄ , VBr ₃ , MgBr ₂ , BaI ₂ , and magnesium iodide MgI ₂₎ etc. And the metal perchlorate is barium perchlorate _{(Ba (ClO 4) 2)} , magnesium perchlorate (Mg (ClO _{4) 2)} Although the like, and the like.

Silica gel is an amorphous silica prepared from sodium silicate and sulfuric acid and exhibits an excellent adsorption amount of about 40 wt% based on the weight of water. When the temperature is increased, the adsorption capacity is lowered to about the same as that of clay, Corrosive, non-corrosive, non-aqueous, easy to handle, inexpensive and does not cause contamination problems.

Montmorillonite or montmorillonite is a natural acid, which is a subbentonite magnesium aluminosilicate, which is usually dried in the form of beads through a drying process or is easily pulverized, It has the disadvantage of being inferior to silica gel but also has the advantage of being the cheapest

Since the zeolite has a micro-sphere structure with a crystalline network structure and has a very large specific surface area of about 700 to about 800 m ² per gram, the temperature of the silica gel or clay increases the moisture content However, it has a disadvantage of relatively high cost.

The activated carbon has a very large specific surface area of about 200 to about 1200 m ² per gram, which is excellent in adsorbability, but is contaminated with the product and is rarely used as a desiccant for ordinary use.

The calcium oxide in the alkaline earth metal oxide is a calcined or recalcinated type lime having a moisture adsorption capacity of about 28.5 wt% or less and has moisture adsorption ability even at a very low relative humidity, and therefore, Is mainly used for dehumidifying food packaging.

Calcium sulfate in metal sulfates is known commercially as Drierite and is produced by dewatering gypsum, chemically stable, non-pyrogenic, non-toxic, and non-corrosive, and releases moisture that once adsorbed However, it has a disadvantage of low water absorption capacity of about 10 wt% and is mainly used in a limited range.

The filling material which can be used for the first filling adhesive layer 31 and the second filling adhesive layer 33 is to realize a barrier property against moisture. Any kind of filler that can act as a filler having a barrier property in the adhesive layer 30 of the filler material can be used. Specific examples of the filler include talc, silica, magnesium oxide, mica, montmorillonite, alumina, But are not limited to, graphite, beryllium oxide, aluminum nitride, silicon carbide, mullite, silicon or combinations thereof. Such a filler may be a particle prepared by synthesis or a particle processed from a raw material.

The filling material contained in the resin composition for the filling adhesive layer of the first filling adhesive layer 31 and the second filling adhesive layer 33 is dispersed evenly inside the composition after curing to disperse the stress acting on the composition, In addition, it has the effect of effectively preventing water penetrating and diffusing into the composition and preventing moisture from diffusing toward the organic light emitting diode 20 through the first filling adhesive layer 31 or the second filling adhesive layer 33.

The particle size of the hygroscopic material may be about 10 nm to about 20 um. For example, the average particle diameter of the hygroscopic material may be about 10 nm to 100 nm.

The particle size of the fill material may be between about 10 nm and about 20 um. For example, the average particle size of the fill material may be between about 10 nm and 100 nm. In another example, the filler material may have an average particle size of from about 2 um to about 5 um.

The hygroscopic material or the filling material may be of a mesoporous type, a plate type, a spherical type, a rod type, a fiber type, a core-shell type type, and the like.

The first filling adhesive layer 31 or the second filling adhesive layer 33 may comprise 5 to 50 parts by weight of a moisture absorbing material with respect to 100 parts by weight of a thermosetting resin or a photocurable resin. It is preferable that the barrier property against moisture permeation can be improved when the filling material is contained in an amount ranging from about 5 to about 50 parts by weight based on 100 parts by weight of the thermosetting resin or the photocurable resin.

The hygroscopic adhesive layer 32 may include about 5 to about 50 parts by weight of hygroscopic material with respect to 100 parts by weight of the thermosetting resin or the photocurable resin.

The thickness of the adhesive layer 30 may be between about 5 um and about 50 um. For example, the thickness of the adhesive layer 30 may be 10 [mu] m, 20 [mu] m or 30 [mu] m. When the thickness of the adhesive layer 30 is in the above range, it can be advantageous to secure the adhesive property without being influenced by the surface step difference.

The first fill adhesive layer 31, the moisture absorbent adhesive layer 32 and the second fill adhesive layer 33 may have a thickness ratio of about 0.1 to about 1.2: about 0.1 to about 1.2: about 0.1 to about 1.2. For example, each layer may be fabricated in a ratio of 1: 1: 1. When the thickness ratio is within the above range, it is advantageous to secure the adhesive property without being influenced by the surface step difference.

The organic light emitting diode display 100 includes the adhesive layer 30 to improve the reliability of the organic light emitting diode 20. If the sealing substrate is not made of glass, water or the like is mixed through the defective portion of the pores formed by the pin-hole and the particles. The moisture absorbing adhesive layer in the adhesive layer 30 absorbs or adsorbs such moisture, So that the organic light emitting diode 20 can be protected.

Generally, a getter may be applied to the outer frame to protect the organic light emitting diode 20 from moisture adhering from the outside. The organic light emitting diode display 100 may be omitted, . In addition, if the getter forming process is omitted, a getter line is not formed in the outer frame portion, thereby ensuring a margin and reducing the size of the bezel.

When the adhesive layer 30 is formed of the sandwich structure of the first filling adhesive layer 31, the moisture absorbing adhesive layer 32 and the second filling adhesive layer 33, the moisture absorbing adhesive layer 32 is formed from the sealing substrate 40 to the organic light emitting element The filling adhesive layers 31 and 33 can be adhered to the substrate 10, the organic light emitting element 20, the sealing substrate 40 and the like while effectively retaining moisture adhering to the substrate 10, 20. That is, the adhesive layer 30 efficiently blocks moisture contained in the organic light emitting device 20 without decreasing the adhesive property, thereby improving the reliability of the organic light emitting device 20 and improving the lifetime.

The first filler adhesive layer 31, the moisture absorbent adhesive layer 32 and the second filler adhesive layer 33 may be made from a composition comprising a filler material or a composition comprising a hygroscopic material as described above, The composition for preparing the first adhesive layer 31, the hygroscopic adhesive layer 32 and the second adhesive layer 33 may include a thermosetting resin or a photocurable resin. The composition may further contain additives such as a heat curing agent, a curing accelerator, a coupling agent, a spacer, a photoacid generator, a radical initiator, etc., or a combination thereof, if necessary.

When the composition for the production of the first filler adhesive layer 31, the hygroscopic adhesive layer 32 and the second filler adhesive layer 33 is made of a thermosetting resin composition, a thermosetting resin, a thermosetting agent, a curing accelerator, a coupling agent, And further includes a hygroscopic material or a filler material.

As the thermosetting resin, for example, an epoxy resin can be mentioned. Examples of the epoxy resin include bisphenol type, ortho-Cresol novolac type, polyfunctional epoxy, amine type epoxy, heterocyclic ring containing epoxy, substituted epoxy and naphthol type epoxy. Specific examples thereof include bisphenol A Type epoxy resin, a hydrogenated bisphenol type epoxy resin, an alicyclic epoxy resin, an aromatic epoxy resin, a novolac type, and a dicyclopentadiene type epoxy resin. These epoxy group-containing compounds may be used alone or in combination of two or more. Can be mixed and used. Examples of bisphenol-based epoxy resins include Epiclon 830-S, Epiclon EXA-830CRP, Epiclon EXA 850-S, Epiclon EXA-850CRP, Epiclon EXA-835LV, Epicote 807, Epicote 815, Epicote 825, Epicote 827, Epicote 828, Epicote 834, Epicote 1001, Epicote 1004, Epicote 1007, Epicote 1009 from Shell Epoxy Co., YDCN-500-5P, YDCN-500-4P, YDCN-500-5P, and YDCN-500-5P of Orthocresol novolak are available as DER-301, DER-361, YD- EOCN-102S, EOCN-104S, EOCN-1012, EOCN-1025 and EOCN-1027 of YDCN-500-80P and YDCN- As the polyfunctional epoxy resin, Epon 1031S of Yucca Shell Epoxy Co., Araldite 0163 of Ciba Specialty Chemicals Co., Ltd., Detakol EX Data Cole EX-411, Data Cole EX-621, Data Cole EX-521, Data Cole EX-421, Data Cole EX-411, Examples of the amine-based epoxy resin include Epikote 604 manufactured by Yucca Shell Epoxy Co., Ltd., YH-434 manufactured by Dokdo Chemical Co., Ltd., TETRAD-X and TETRAD-C manufactured by Mitsubishi Gas Chemical Co., Ltd., and ELM-120 manufactured by Sumitomo Chemical Co., ERL-4234, ERL-4221, and ERL-4206 of UCC Co., Ltd. were used as the recycled epoxy resin, PT-810 of Ciba Specialty Chemicals KK, Clon HP-4032, Epiclon HP-4032D, Epiclon HP-4700, Epiclon 4701, etc. These may be used singly or in combination of two or more. Phenoxy resins can be applied to obtain excellent film properties, and high molecular weight resins such as Epikoto 1256 from JER, PKHH from INCEM and YP-70 from TOKO KASEI can be applied.

The thermosetting agent is not particularly limited as long as it can be used to thermoset an epoxy resin. Specific examples include polyamine-based curing agents such as diethylenetriamine, triethylenetetramine, N-aminoethylpiperazine, diaminodiphenylmethane and adipic acid dihydrazide; Acid anhydride curing agents such as phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride and methylnadic anhydride; Phenol novolak type curing agents; Polymercaptan curing agents such as trioxane tritylene mercaptan; Tertiary amine compounds such as benzyldimethylamine and 2,4,6-tris (dimethylaminomethyl) phenol; Imidazole compounds such as 2-methylimidazole, 2-ethyl-4-methylimidazole and 1-benzyl-2-methylimidazole can be used. It is also possible to use a latent curing agent of other solid dispersion type or a latent curing agent encapsulated in microcapsules.

When an amine-based curing agent is used, the amine-based curing agent is preferably an aliphatic amine, a modified aliphatic amine, an aromatic amine, a secondary amine or a tertiary amine, and examples thereof include benzyldimethylamine, triethanolamine , triethylene tetramine, diethylene triamine, triethylene amine, dimethyl amino ethanol, tri (dimethylaminomethyl) phenol and the like may be used, the end group _{-OH, -COOH, -SO 3 H,} -CONH 2, -CONHR (R is an alkyl _{group), -CN (CN) NH 2} , -SO 3 NH 2, -SO 3 NHR may be used a curing agent having the (R represents an alkyl group) or -SH. The R represents a C1-C10 alkyl group, a straight or branched chain saturated hydrocarbon group having 1-10 carbon atoms, preferably a C1-C4 linear or branched alkyl group, specifically methyl, ethyl, n-propyl, Isobutyl, n-butyl, t-butyl, and the like.

When an imidazole-based curing agent is used, it is possible to use imidazole, isoimidizole, 2-methyl imidazole, 2-ethyl-4-methyl imidizole, 2,4-dimethyl imidizole, butyl imidizole, 2-methyldimidazole, 2-undecylidimidizole, 1-vinyl-2-methylimidizole, 2-n-heptadecylimidizole, 2- 2-methylimidizole, 1-propyl-2-methylimidizole, 1-cyanoethyl-2-methyl 1-cyanoethyl-2-ethyl-4-methylimidizole, 1-cyanoethyl-2-undecylimidizole, 1-cyanoethyl- 2-methylimidizole, an adduct of imidazole and methylimidizole, an adduct of imidazole and trimellitic acid, 2-n-heptadecyl-4-methylimidizole, phenylimidazole , Benzylimidizole, 2-methyl-4,5-diphenylimidizole, 2,3,5-triphenylimidizole, 2-styrylimidizole, 1- (dodecylbenzyl) -2- Me (2-hydroxy-4-t-butylphenyl) -4,5-diphenylimidazole, 2- (2-methoxyphenyl) -4,5-diphenylimidazole , 2- (3-hydroxyphenyl) -4,5-diphenylimidazole, 2- (p-dimethyl-aminophenyl) ) -4,5-diphenylimidazole, di (4,5-diphenyl-2-imidazole) -benzene-1,4,2-naphthyl- Benzyl-2-methylimidizole and 2-p-methoxystyrylimidazole.

The acid anhydride curing agent is suitable as an epoxy resin when a hybrid epoxy resin containing a siloxane is used.

Preferably, the acid anhydrides as the curing agent are selected from the group consisting of phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methylnadic anhydride, nadic anhydride, glutaric anhydride, Methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride or 5- (2,5-dioxotetrahydro) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride.

As the curing accelerator, quaternary ammonium salts, quaternary sulfonium salts, various metal salts, imidazoles, tertiary amines and the like can be used. Specific examples thereof include tetramethylammonium bromide and tetrabutylammonium bromide as quaternary ammonium salts, tetraphenylphosphonium bromide and tetrabutylphosphonium bromide as quaternary sulfonium salts, and zinc octylate and tin octylate as metal salts. 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole and 2-ethyl-4-methylimidazole. Examples of tertiary amines include benzyldimethylamine.

Examples of the boron-based hardening accelerator include phenylboronic acid, 4-methylphenylboronic acid, 4-methoxyphenyl boronic acid, 4-trifluoromethylphenylboronic acid, 4-trifluoromethoxyphenyl boronic acid, 4-tert-butoxyphenyl boronic acid, 3-fluoro-4-methoxyphenyl boronic acid, -4-methoxyphenyl boronic acid, pyridinetriphenylborane, 2-ethyl-4-methylimidazoliumtetraphenylborate, 1,8-diazabicyclo [ 5.4.0] undecene-7-tetraphenylborate, 1,1-diazabicyclo [4.3.0] undecene-7-tetraphenylborate (1,5-diazabicyclo [4.3.0] nonene-5-tetraphenylborate) and lithium triphenyl (n-butyl) borate. Examples of the imidazole-based curing accelerator include 2- Methyl imide 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-ethyl- methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 2-phenylimidazole, 1,2-dimethylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl- 1-cyanoethyl-2-ethyl-4-methylimid azole, 1-cyanoethyl-2-undecylimidazole, 1- 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium-trimellitate, 1-cyanoethyl- 2-phenylimidazolium-trimellitate, 2,4-diamino-6 [2'-methylimidazoyl- (1 ') - ethyl- Triazine (2,4- diamino-6- [2'-methylimidazoly- (1 ')] - ethyl-s-triazine), 2,4- (2,4-diamino-6- [2'-undecylimidazoly- (1 ')] - ethyl-s-triazine), 2,4-diamino- Methylimidazoyl- (1 ')] - ethyl-s-triazine, 2,4-diamino-6- [2'- 4-diamino-6- [2'-methylimidazolyl- (1 ')] -ethyl-s-triazine isocyanuric acid derivative dihydrate (2,4- (1 ')] - ethyl-s-triazine isocyanuric acid adduct dihydrate, 2-phenylimidazole isocyanuric acid adduct, 2-methylimidazole isocyanuric acid derivative dihydrate 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethyl (2-methylimidazole isocyanuric acid adduct dihydrate) 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo [ 2-a] benzimidazole, 4,4'-methylenebis (2-ethyl-5-methylimidazole (4,4 ' 2-ethyl-5-methylimidazole, 2-methylimidazoline, 2-phenylimidazoline, 2,4-diamino- 2,4-diamino-6-vinyl-1,3,5-triazine, 2,4-diamino-6-vinyl-1,3,5-triazine, isocyanuric acid derivatives 2,4-diamino-6-vinyl-1,3,5-triazine isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-1,3,5- 2,4-diamino-6-methacryloyloxylethyl-1,3,5-triazineisocyanuric acid adduct, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-methylimidazole and 1- (2-cyanoethyl) Di (cyanoethoxymethyl) imidazole), 1-acetyl-2-phenylhydrazine (1-ace tyl-2-phenylhydrazine, 2-ethyl-4-methyl imidazoline, 2-benzyl-4-methyl dimidazoline, 2-ethyl imidazoline, 2-phenyl imidazole, 2-phenyl-4,5-dihydroxymethylimidazole, and the like. ), Melamine, dicyandiamide, etc. These may be used alone or in combination of two or more.

Examples of the coupling agent include a silane coupling agent, a titanate coupling agent, an aluminate coupling agent, and a silicone compound. These coupling agents can be used alone or in combination. When a coupling agent is included, it has an effect of improving the adhesiveness of the resin composition and decreasing the viscosity. It is preferable that the thermosetting resin composition contains about 0.001 to about 5 parts by weight, preferably about 0.01 to about 3 parts by weight, It should be included as part of weight.

The silane coupling agent functions as an adhesion promoter for enhancing the adhesion between the surfaces of inorganic materials such as silica in the composition and the resins. The silane coupling agent may be an epoxy-containing silane or a mercaptan-containing silane. Examples of the epoxy-containing silane coupling agent include 2- (3,4-epoxycyclohexyl) -ethyltrimethoxysilane, 3- Glycidoxypropyltriethoxysilane, 3-glycidoxypropyltriethoxysilane, and N-2 (aminoethyl) 3-aminopropylmethyldimethoxysilane, N Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, N-2 (aminoethyl) -Triethoxysilyl-N- (1, 3-dimethylbutylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, and those containing maltitol include 3-mercaptopropylmethyldimethoxy Silane, 3-mercaptopropyltriethoxysilane, isocyanate-containing 3-iso And cyanate propyltriethoxysilane, which may be used alone or in combination of two or more thereof

The antioxidant is intended to improve the thermal stability of the cured product by preventing oxidation deterioration during thermal curing of the thermosetting resin composition. As the antioxidant, phenol-based, sulfur-based, phosphorus-based antioxidant and the like can be used. Specific examples include phenolic antioxidants such as dibutylhydroxytoluene and 2,6-di-tetra-butyl-p-cresol (hereinafter referred to as BHT), sulfur-based antioxidants such as mercaptopropionic acid derivatives, , Phosphorus-based antioxidants such as 9,10-dihydro-9-oxa-10-phosphapenanthrene-10-oxide (hereinafter referred to as HCA), and the like. And may be used in an amount of about 0.001 to about 5 parts by weight, preferably about 0.01 to about 0.5 parts by weight, based on 100 parts by weight of the thermosetting resin in the thermosetting resin composition.

When the composition for the production of the first filling adhesive layer 31, the moisture absorption bonding layer 32 and the second filling adhesive layer 33 is made of a photo-curable resin composition, the photo-curable epoxy resin, photoinitiator, coupling agent, spacer, photo- A developer, and a solvent, and further includes a filler or a hygroscopic material.

As the photocurable epoxy resin applicable to the photocurable resin composition, an aromatic epoxy resin, an alicyclic epoxy resin, or a mixture thereof can be used. As the aromatic epoxy resin, biphenyl type, bisphenol A type, bisphenol F type, phenol novolac type, dicyclopentadiene type, epoxy resin and the like can be used, and mixtures thereof can also be used.

The photoinitiator is not particularly limited as long as it can cure the epoxy resin by light. Specific examples of the photoinitiator include aromatic diazonium salts, aromatic sulfonium salts, aromatic iodo aluminum salts, aromatic sulfonium aluminum salts, metallocene compounds and iron arylene-based compounds. Preferably, an aromatic sulfonium salt can be used, and specific examples thereof include an aromatic sulfonium hexafluorophosphate compound and an aromatic sulfonium hexafluoroantimonate compound.

As the coupling agent, a silane-based coupling agent or a titanium-based coupling agent or a silicone compound may be used alone or in combination. Preferably, a silane coupling agent containing alkoxysilane and diglycidyl ether in one molecule is preferable.

The spacer is not particularly limited as long as it can keep the thickness of the panel after curing at a constant level, and it is preferable that the thickness of the panel can be maintained at about 5 to 50 μm, preferably about 5 to 25 μm. The shape of the spacer is spherical, log-shaped, etc., and the shape of the spacer is not particularly limited as long as the thickness of the panel can be kept constant.

The photoacid generator is not particularly limited as long as it can produce Lewis acid or Bronsted acid by exposure, and onium compounds such as an organic sulfonic acid and a sulfur flame compound and an onium salt can be used. Preferably, it is preferably at least one selected from phthalimidotrifluoromethane sulfonate, dinitrobenzyltosylate, n-decyldisulfone, naphthylimidotrifluoromethane sulfonate, diphenyl iodide salt, hexafluorophosphate, diphenyl iodide salt, But are not limited to, triphenylphosphine, triphenylphosphine, triphenylphosphine, triphenylphosphine, triphenylphosphine, triphenylphosphine, triphenylphosphine, triphenylphosphine, triphenylphosphine, Triphenylsulfonium hexafluoroantimonate, triphenylsulfonium triflate, dibutylnaphthylsulfonium triflate, and mixtures thereof can be used as the catalyst.

The radical initiator may be used together with a photoacid generator. The radical polymerization initiator used in the curable resin composition may be a radical photopolymerization initiator that decomposes by electromagnetic energy rays such as UV light to generate radicals, And may be a thermally decomposing radical polymerization initiator that generates a radical. Examples of the radical photopolymerization initiator include acetophenone derivatives such as 2-hydroxy-2-methylpropiophenone and 1-hydroxycyclohexyl phenyl ketone; Acylphosphine oxide derivatives such as bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide; And type I alpha cleavage initiators such as benzoin ether derivatives such as benzoin methyl ether and benzoin ethyl ether. Representative examples of commercially available radical photoinitiators are IRGACURE 651, IRGACURE 184, IRGACURE 907, DAROCUR 1173 and IRGACURE 819 from Ciba Specialty Chemical. Type II photoinitiators may also be used, such as benzophenone, isopropylthioxanthone, and anthroquinone. Various substituted derivatives of such basic compounds may also be used. Examples of thermally decomposable radical polymerization initiators include 1,1,3,3-tetramethylbutylperoxy-2-ethyl-hexanoate, 1,1-bis (t-butylperoxy) cyclohexane, 1,1 T-butylperoxy benzoate, dicumyl peroxide, t-butyl cumyl peroxide, 2,5-dimethyl-2 (t-butylperoxy) , 2,5-dimethyl-2,5-di (t-butylperoxy) -3-hexyne and cumene hydroperoxide. The amount of the radical polymerization initiator is an effective amount, for example, in the range of about 0.01 to about 5 parts by weight based on 100 parts by weight of the photocurable resin in the photocurable resin composition.

Examples of the solvent that can be used in the composition for preparing the first and second filling and bonding layers 31 and 32 and the second filling adhesive layer 33 include methyl ethyl ketone (MEK), tetrahydrofuran (THF), toluene, It is not particularly limited as long as it is a solvent capable of forming a coating solution for forming a coating film. In order to obtain excellent coating film characteristics, one or more kinds of solvents may be mixed and used.

The compositions for preparing the first and second adhesive layers 31 and 32 and the second adhesive layer 33 are coated on the substrate films 111 and 112 and then dried to form a sheet. And the production method is not particularly limited, and can be variously manufactured according to known methods. If the sheet can be formed and the characteristics can be realized, it can be made into an uncured gel state, a solid state, and can be produced in a liquid state and post-treated. The lamination method of laminating the produced moisture-absorbing adhesive sheet and the filled adhesive sheet to form the adhesive layer can be carried out according to a known method, and is not limited to a specific method. For example, a hygroscopic adhesive sheet, a filled adhesive sheet, and a hygroscopic adhesive sheet are sequentially laminated by roll to roll, roll to glass, press bonding or diaphragm process to form an adhesive layer ( 30) may be manufactured so that each sheet forms a hygroscopic adhesive layer or a filler adhesive layer.

2 is a schematic view showing a method of forming the adhesive layer 130 according to another embodiment. First, a composition for forming a hygroscopic adhesive layer containing a hygroscopic material is applied to the base film 111 to form a hygroscopic adhesive sheet. On the other hand, a composition for forming a filling adhesive layer containing a filling material is applied to another base film 112 to form a filling adhesive sheet. The hygroscopic adhesive sheet and the filled adhesive sheet produced as described above are laminated. The laminated moisture absorbing adhesive sheet and the filled adhesive sheet are laminated by a roll to roll, a roll to glass, a press lap or a diaphragm process to produce the adhesive layer 130.

Thus, by using the adhesive layer 130 as one integrated sheet, process advantages and structural advantages can be obtained.

3 is a cross-sectional view of the organic light emitting diode display 200 manufactured using the adhesive layer 130 as shown in FIG.

3, a driving circuit unit DC and an organic light emitting diode 120 are formed on a substrate 110. The driving circuit unit DC drives the organic light emitting element 120. The organic light emitting diode 120 and the driving circuit DC are not limited to the structure shown in FIG. 3. The organic light emitting diode 120 emits light to easily display an image, And may be formed into various structures within a range that can be modified. For example, the adhesive layer 130 may be formed on a TFT substrate. The substrate 110 on which the organic light emitting diode 120 is formed and the sealing substrate 140 are bonded together using the adhesive layer 130 as shown in FIG. The bonding method can be carried out according to a known method and is not limited to a specific method. For example, a lamination process, a press process or a diaphragm process can be used.

According to another embodiment of the present invention, there is provided a method of manufacturing a light emitting device, comprising: forming an organic light emitting device on a substrate; Forming an adhesive layer by sequentially laminating a first filling adhesive layer, a filling adhesive layer, and a second filling adhesive layer on the substrate; and attaching the bonding layer between the substrate on which the organic light emitting device is formed and the sealing substrate through the adhesive layer A device manufacturing method is provided.

Hereinafter, the present invention will be described in more detail with reference to examples. The following examples are for illustrative purposes only and are not intended to limit the scope of the invention.

Example

Example  One

30 parts by weight of an epoxy resin EXA-835LV (Daikin ink), 45 parts by weight of a phenoxy resin Epikote-1256 (Japan Epoxy Co.), 5 parts by weight of a thermosetting agent C11Z-CNS (Shikoku), CaO 20 parts by weight of a water-insoluble polymer, particle size: about 1 to 2 μm) and 100 parts by weight of an organic solvent MEK were mixed to prepare a composition for a moisture-absorbing adhesive layer.

On the other hand, 30 parts by weight of an epoxy resin EXA-835LV (Daikin ink), 45 parts by weight of phenoxy resin Epikote-1256 (Japan Epoxy Co.), 5 parts by weight of a thermosetting agent C11Z-CNS (Shikoku) 15 parts by weight of a polyvinyl alcohol (manufactured by Nippon talc) (particle diameter: about 1 to 2 μm), 15 parts by weight of silane coupling agent KBM-403 (Shin-Etsu) and 100 parts by weight of organic solvent MEK were mixed to prepare a composition for a filling adhesive layer, To prepare a filled adhesive sheet.

A hygroscopic adhesive sheet and a filled adhesive sheet formed on the respective PET base films are laminated and laminated by a laminating process, and then the PET base film on the side of the filled adhesive sheet is removed. The PET base film was removed and the moisture-absorbing adhesive sheet formed on the PET base film was laminated again on the exposed surface of the filled adhesive sheet and laminated by a laminating process to form an adhesive layer laminated in three layers of the moisture-absorbing adhesive layer-filled adhesive layer- The base film is removed.

On the other hand, the organic light emitting device was formed on a glass substrate, and the prepared adhesive layer was interposed between the sealing substrates of the glass so as to cover the organic light emitting device, and was adhered with a diaphragm at a pressure of 60 Kpa.

Example  2

An organic light emitting display was manufactured in the same manner as in Example 1, except that 25 parts by weight of CaO and 20 parts by weight of Talc were used.

Example  3

An organic light emitting display was manufactured in the same manner as in Example 1 except that 30 parts by weight of CaO was used and 25 parts by weight of Talc was used

Comparative Example  One

In Example 1, except for the hygroscopic adhesive layer, an adhesive layer made of a filler adhesive layer was formed to have the same thickness to fabricate an organic light emitting display device.

Experimental Example  1: Life test

The organic light emitting display manufactured in Examples 1 to 3 and Comparative Example 1 was placed in a chamber (TH-TG_Jiotech) at 85 ° C and 85% RH (relative humidity) Are shown in Table 1 below.

Experimental Example  2: Water permeability

The water vapor transmission rate (WVTR: Water vapot transmission rate) of the film-shaped adhesive layer prepared in Examples 1 to 3 and Comparative Example 1 was measured (measuring instrument: permon 3/33 ma from mocon).

Experimental Example  3: Adhesive strength

Two sheets of the test pieces were laminated and bonded to each other in the cross-section of the adhesive layer prepared in Examples 1 to 3 and Comparative Example 1, and the strength for desorbing the two test pieces was measured using a UTM (Instron Model-5900) The adhesive strength was measured.

Example 1 Example 2 Example 3 Comparative Example 1 WVTR
(g / m ² ) 8 7 5 10 Adhesive strength
(kgf / cm ² ) 23 23 23 23 Dark spot time
(time) 1,756 1,986 2,135 856

While the invention has been shown and described with reference to certain preferred embodiments thereof, it will be understood by those skilled in the art that various changes and modifications may be made therein without departing from the spirit and scope of the following claims. Those who are engaged in the technology field will understand easily.

10: substrate 20: organic light emitting element
30: adhesive layer 31: first filling adhesive layer
32: a hygroscopic adhesive layer 33: a second filled adhesive layer
40: sealing substrate 100: organic light emitting display
110: substrate 111: substrate film
112: base film 120: organic light emitting element
131: Filling adhesive layer 132:
140: sealing substrate 200: organic light emitting display

Claims (14)

Board;
An organic light emitting device formed on the substrate;
An encapsulation substrate formed on the organic light emitting device; And
An adhesive layer formed on the substrate and covering the organic light emitting device and bonding the substrate on which the organic light emitting device is formed to the sealing substrate;
/ RTI >
Wherein the adhesive layer comprises at least one filler-adhesive layer and at least one hygroscopic adhesive layer,
Wherein the adhesive layer comprises a thermosetting resin or a photocurable resin,
The moisture-
100 parts by weight of a thermosetting resin or a photocurable resin; And
5 to 50 parts by weight of a hygroscopic material
Organic light emitting display. The method according to claim 1,
The moisture-absorbing material is a silica gel _{(silica gel: SiO 2 · H} 2 O), alumino-silicate beads the zeolite (zeolite as the (alumino-silicate beads), montmorillonite (montmorillonite), molecular sieves (molecular sieve): Na ₁₂ At least one selected from the group consisting of AlO ₃ SiO ₂ .12H ₂ O, activated carbon, alkali metal oxides, alkaline earth metal oxides, metal sulfates, metal halides and metal perchlorates. The method according to claim 1,
The filling adhesive layer may be formed of a material selected from the group consisting of talc, silica, magnesium oxide, mica, montmorillonite, alumina, graphite, beryllium oxide, aluminum nitride, silicon carbide, mullite, And at least one filling material selected from the group consisting of: 3. The method of claim 2,
Wherein the moisture-absorbing material has a particle diameter of 10 nm to 20 mu m. 3. The method of claim 2,
Wherein the moisture absorbing material is a mesoporous, plate-like, spherical, rod, fiber, or core-shell type. The method of claim 3,
Wherein the filling material has a particle diameter of 10 nm to 20 mu m. The method of claim 3,
Wherein the filling material is a mesoporous type, a plate type, a spherical type, a rod type, a fiber type, or a core-shell type. The method according to claim 1,
Wherein the filling adhesive layer and the hygroscopic adhesive layer all comprise the same type of thermosetting resin or photo-curable resin, and the adhesive layer is formed as a single sheet which does not form an interlayer interface. The method according to claim 1,
The filler-
100 parts by weight of a thermosetting resin or a photocurable resin; And
5 to 50 parts by weight of a filler
And an organic light emitting diode (OLED). The method according to claim 1,
Wherein the thickness of the adhesive layer is 5 mu m to 30 mu m. The method according to claim 1,
Wherein the filling adhesive layer comprises a first filling adhesive layer and a second filling adhesive layer, the hygroscopic adhesive layer being located between the first filling adhesive layer and the second filling adhesive layer,
Wherein the thickness ratio of the first filling adhesive layer, the moisture absorbing adhesive layer and the second filling adhesive layer in the adhesive layer is 0.1 to 1.2: 0.1 to 1.2: 0.1 to 1.2. Forming an organic light emitting element on a substrate;
Laminating at least one filler adhesion layer and at least one hygroscopic adhesive layer to form an adhesive layer; and
A step of bonding the substrate on which the organic light emitting diode is formed and the sealing substrate through the adhesive layer
Lt; / RTI >
Wherein the adhesive layer comprises a thermosetting resin or a photocurable resin,
The moisture-
100 parts by weight of a thermosetting resin or a photocurable resin; And
5 to 50 parts by weight of a hygroscopic material
A method of manufacturing an organic light emitting display device. 13. The method of claim 12,
Forming at least one adhesive layer and at least one hygroscopic adhesive layer by a roll to roll, a roll to glass, a press bonding or a diaphragm process to form an adhesive layer Wherein the organic light emitting display device has a light emitting layer. 13. The method of claim 12,
Wherein the adhesive layer is formed on the encapsulation substrate, and then the encapsulation process is performed by a lamination process, a pressing process, or a diaphragm process.

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