KR20120021436A - Moisture absorbent particles, composition for organic electroluminescence getter containing the same and organic electroluminescence device using thereof - Google Patents

Abstract

PURPOSE: Moisture absorbent particles, a composition for organic electroluminescence(EL) getter containing the same, and an organic EL device using the same are provided to prevent the generation of dark spots and the damage of the device. CONSTITUTION: Moisture absorbent particles(10) include an absorbing agent(1) and polymer resin(2). The polymer resin is continuously or non-continuously formed on the surface of the absorbing agent. The glass transition temperature of the polymer resin is between -60 and 170 degrees Celsius. The polymer resin is the polymer of one or more cross-linking monomers, the polymer of one or more vinyl monomers, and the copolymer of one or more cross-linking monomers and one or more vinyl monomers. The cross-linkage of the polymer resin is between 0.5 and 50%.

Description

Moisture Absorbent Particles, Composition for Organic Electroluminescence Getter Containing the Same and Organic Electroluminescence Device Using Thereof}

The present invention relates to a moisture absorbing particle, a composition for an organic EL getter including the same, and an organic EL device using the same. More specifically, the present invention is to continuously or discontinuously fix the surface of the moisture absorbent used in the composition for the organic EL getter with a polymer resin so that the moisture absorbent does not directly contact the device, so as not to damage the device to the organic EL device moisture and The present invention relates to a hygroscopic particle capable of protecting against impact, a composition for an organic EL getter including the same, and an organic EL device using the same.

The organic EL device (hereinafter referred to as an organic EL device) has a structure in which an organic EL layer, which is a thin film containing a fluorescent organic compound, is sandwiched between an anode and a cathode, which form a pair of electrodes, and holes and electrons are injected into the thin film. It is a self-luminous element which produces | generates an exciton by recombination, and uses light emission (fluorescence-phosphorescence) when this exciton is inactivated.

When the organic EL device is driven for a certain period of time, the organic film and the metal film, which are components of the organic EL device, are gradually oxidized due to the penetration of moisture or generation of oxygen, carbon monoxide, moisture, and the like. There is a problem that the light emission characteristics are significantly degraded. In other words, the light emitting material reacts with moisture to be converted into non-advertised molecules to form dark spots, thereby lowering the luminous efficiency, and also lowering the charge transport ability, thereby increasing the impedance of the device. Due to this phenomenon, the phenomenon of peeling from the organic film occurs, and the electron injection efficiency is drastically reduced and the life is gradually decreased.

As such, the organic EL device is vulnerable to moisture and oxygen, and thus a method of mounting a getter including a drying means capable of absorbing moisture in an encapsulation process for blocking moisture and oxygen is used inside the device.

Recently, many getters are applied by sticking to the device's surface in the form of stickers.However, as OLED devices become larger, it is difficult to increase the moisture absorption rate per unit area. There is a need for a protective layer to protect against.

Fig. 1 schematically shows a sealing structure of an organic EL element equipped with a getter. As shown in the drawing, a conventional organic EL device includes a substrate 110 and an organic light emitting unit 130 formed on one surface of the substrate, and a sealing cap 120 coupled to the substrate to accommodate the organic light emitting unit. Is formed. At least a portion of the sealing cap 120 is formed with a drying means 140 for absorbing moisture.

The drying means may be installed by sealing the absorbent powder in a water-permeable bag, or pelletizing the powder, or mixing the powder with a polymer binder to form a film.

Among the absorbents studied so far, CaO is the most preferred as the absorbent which does not generate outgas during the absorption and does not return the absorbed moisture. However, metal oxide powders such as calcium oxide (CaO) absorb moisture through chemical reactions, and exothermic heat occurs. Therefore, it is necessary to drop the absorbent powder from the device in order to increase the loading amount of the absorbent powder while not damaging the device. In addition, when the hygroscopic filler composition having a viscosity is prepared to fill the sealing cap, the hygroscopic powder is soaked before the curing and in the curing process because the specific gravity is high. At this time There is a need for a solution in which the absorbent powder is distributed near the device but does not damage the device.

The present inventors fixed the surface of the absorbent particles in a continuous or discontinuously fixed to the surface of the absorbent particles with a polymer resin in order to protect the direct contact with the absorbent from the device, but does not reduce the absorption efficiency, organic EL getter composition comprising the same And organic EL devices using the same.

An object of the present invention is to provide a moisture-absorbing particles excellent in moisture absorption efficiency without dark spots.

Another object of the present invention is to provide a hygroscopic particle having an excellent moisture absorption rate.

Still another object of the present invention is to provide moisture-absorbing particles which are excellent in moisture absorption efficiency even if they are distributed close to the device.

Still another object of the present invention is to provide a hygroscopic particle having improved hygroscopic efficiency.

Still another object of the present invention is to provide an organic EL getter composition including the hygroscopic particles, which has excellent workability and a filler function capable of protecting the device against external impact.

Still another object of the present invention is to provide an organic EL device having improved light emission characteristics and lifetime characteristics of the device by applying the organic EL getter composition.

Technical problems to be achieved by the present invention are not limited to the technical problems mentioned above, and other technical problems not mentioned will be clearly understood by those skilled in the art from the following description.

One aspect of the invention relates to hygroscopic particles. The hygroscopic particles are hygroscopic; And a polymer resin formed continuously or discontinuously on the surface of the moisture absorbent.

In one embodiment, the polymer resin may be a resin having a glass transition temperature of -60 to 170 ° C.

In an embodiment the polymer resin may be a polymer of at least one crosslinkable monomer, a polymer of at least one vinyl monomer or a copolymer of at least one crosslinkable monomer and at least one vinyl monomer. The polymer resin may have a crosslinking degree of 0.5 to 50%. In addition, the polymer resin may be porous.

In an embodiment, the polymer resin may be coated and fixed on the surface of the absorbent. The polymer resin may be fixed to 5 to 100% of the surface of the absorbent.

In another embodiment, the polymer resin may be fixed to the surface of the moisture absorbent as protrusions. The protruding fine particles may be fixed at 0.1 ~ 99.9% of the surface of the moisture absorbent. The protruding fine particles may be 0.1 to 50% of the diameter of the moisture absorbent.

In an embodiment of the present invention, the moisture absorbent may be a molecular sieve zeolite, silica gel, carbonate, clay, metal oxide, metal hydroxide, alkaline earth metal oxide, sulfate, metal halide, perchlorate, organometallic or the like.

Another aspect of the invention relates to a composition for an organic EL getter comprising the moisture absorbing particles. The composition for the organic EL getter may include the resin and the protruding moisture absorbing particles of the present invention, and has a viscosity (80 ° C.) of 10 to 100,000 cps. The resin may be a curable or non-curable resin.

 The organic EL getter composition may include 10 to 90 parts by weight of the hygroscopic particles based on 100 parts by weight of the resin.

In one embodiment, the organic EL getter composition may include 10 to 90 parts by weight of the hygroscopic particles based on 100 parts by weight of the curable resin. In another embodiment, the organic EL getter composition may include 10 to 90 parts by weight of the hygroscopic particles based on 100 parts by weight of the non-curable resin.

In embodiments, the resin may be a non-curable resin, the composition for the organic EL getter may have a thixotropy index (T / I) of 1.0 to 7.0 at room temperature (25 ℃).

The organic EL getter composition may include one or more additives such as a curing catalyst, a viscosity modifier, a curing agent, an initiator, a dispersant, a stabilizer, a curing accelerator, and the like.

Another aspect of the present invention relates to an organic EL device using the composition for organic EL getters.

The organic EL device comprises a substrate; An organic light emitting unit formed on one surface of the substrate and including a first electrode, an organic light emitting layer, and a second electrode; A sealing cap coupled to the substrate to accommodate the organic light emitting unit; And an organic EL getter composition formed between the substrate and the sealing cap and covering the organic light emitting part.

In an embodiment, the composition for organic EL getters is cured. The organic EL getter composition is cured at 60 to 200 ° C. when curable.

The present invention does not generate dark spots, has excellent moisture absorption efficiency, excellent moisture absorption speed, and does not damage the device even when distributed near the device, moisture absorption particles having a moisture absorption and filler function, including the moisture absorption particles The organic EL getter composition having excellent workability and improved hygroscopic efficiency and the organic EL getter composition have the effect of providing an organic EL device having improved light emission characteristics and lifetime characteristics of the device.

Figure 1 schematically shows a sealing structure of a conventional organic light emitting device.
2 (a) to 2 (c) are cross-sectional views of the hygroscopic particles of the present invention.
Figure 3 (a) ~ (b) is a schematic diagram of the hygroscopic particles of the present invention.
Figure 4 shows the curing process of the composition for an organic EL getter of the present invention.
5 is a schematic cross-sectional view of an organic EL device according to an embodiment of the present invention.

Hygroscopic Particles

2 (a) to (c) is a schematic cross-sectional view of the hygroscopic particles of the present invention. As shown in Figure 2 (a) ~ (c), the moisture absorption particles 10 of the present invention is a moisture absorbent (1); And a polymer resin (2) formed continuously or discontinuously on the surface of the moisture absorbent.

By fixing the polymer resin 2 on the surface of the moisture absorbent 1 in this manner, even when the moisture absorbent 1 is distributed close to the element, moisture can be absorbed more effectively near the element while preventing direct contact with the element.

In embodiments, the moisture absorbent 1 may be a molecular sieve zeolite, silica gel, carbonate, clay, metal oxide, metal hydroxide, alkaline earth metal oxide, sulfate, metal halide, perchlorate, organometallic, or the like. These may be used alone or in combination of two or more.

The carbonates include sodium carbonate, sodium bicarbonate and the like.

The metal oxides include lithium oxide (Li ₂ O), sodium oxide (Na ₂ O), potassium oxide (K ₂ O), and the like, but are not necessarily limited thereto. Examples of the alkaline earth metal oxide include barium oxide (BaO), calcium oxide (CaO), magnesium oxide (MgO), and the like, but are not necessarily limited thereto. Examples of the metal hydroxides include calcium hydroxide and potassium hydroxide. Examples of the sulfate 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 ), and gallium sulfate (Ga ₂ ( SO ₄ ) ₃ ), titanium sulfate (Ti (SO 4) ₂ ), or nickel sulfate (NiSO ₄ ). Examples of the metal halide include calcium chloride (CaCl ₂ ), magnesium chloride (MgCl ₂ ), strontium chloride (SrCl ₂ ), yttrium chloride (YCl ₂ ), copper chloride (CuCl ₂ ), cesium fluoride (CsF), and fluoride Tantalum (TaF ₅ ), niobium fluoride (NbF ₅ ), lithium bromide (LiBr), calcium bromide (CaBr ₃ ), cerium bromide (CeBr ₄ ), selenium bromide (SeBr ₂ ), vanadium bromide (VBr ₂ ), magnesium bromide (VBr ₂ ) MgBr ₂ ), barium iodide (BaI ₂ ) or magnesium iodide (MgI ₂ ), and examples of the perchlorate include barium perchlorate (Ba (ClO ₄ ) ₂ ) or magnesium perchlorate (Mg (ClO ₄ ) ₂ ). .

Among these are preferably metal oxides, metal hydroxides, alkaline earth metal oxides, sulfates or combinations thereof.

The moisture absorbent 1 may have an average particle diameter range of 0.01 to 200 μm. Preferably it is 0.05-100 micrometers, More preferably, it is 0.1-50 micrometers, Most preferably, it is 0.1-25 micrometers. There is an advantage in the handling is easy without lowering the moisture absorption efficiency in the above range.

In an embodiment, the polymer resin 2 may be porous to increase hygroscopic efficiency, and in this case, the porosity may be 0.1 to 50%.

The polymer resin 2 may be crosslinked. In this case, the degree of crosslinking may be 0.5 to 50%, preferably 1 to 30%, and more preferably 2 to 20%. In the above range, the polymer resin (2) formed on the surface of the absorbent is stable at the time of polymerization and may be attached to the surface well.

The polymer resin that can be used at this time may include a polymer of a crosslinkable monomer, a polymer of a vinyl monomer or a copolymer of a crosslinkable monomer and a vinyl monomer. The polymer of the crosslinkable monomer may be a polymer of one or more crosslinkable monomers, and the polymer of the vinyl monomer may be a polymer of one or more vinyl monomers. In addition, the copolymer of the crosslinkable monomer and the vinyl monomer may be a copolymer of at least one crosslinkable monomer and at least one vinyl monomer. These may be used alone or in combination of two or more. In an embodiment, the polymer resin may be a resin having a glass transition temperature of -60 ° C to 170 ° C. In the above range, there is no phenomenon in which the polymer resins aggregate together, and the polymer resin may be fixed to the surface of the absorbent.

The crosslinkable monomers include divinylbenzene, divinylsulphone, allyl (meth) acrylate, diallyl phthalate, diallyl acrylamide, triallyl (iso) cyanurate, trially trimellitate; Ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (Meth) acrylate, pentaaryl tritol tetra (meth) acrylate, pentaaryl tritol tri (meth) acrylate, pentaaryl tritol di (dec) acrylate, trimethylolpropane tri (meth) acrylic Rate, ditrimethoxypropane tetra (meth) acrylate, tetramethylolpropane tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaeryryltritol penta (meth) acrylate , Glycerol tri (meth) acrylate and the like can be used, these can be prepared alone or by mixing two or more kinds.

The vinyl monomer is capable of radical polymerization, and specific examples thereof include aromatic vinyl monomers such as styrene, ethyl vinyl benzene, α-methyl styrene, and m-chloromethyl styrene; Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethyl (Meth) acrylate type monomers, such as hexyl (meth) acrylate, n-octyl (meth) acrylate, lauryl (meth) acrylate, and stearyl (meth) acrylate; Vinyl acetate, vinyl propionate, vinyl butyrate, vinyl ether, allyl butyl ether, and the like.

In one embodiment, the polymer resin may include a functional group having a hard property and a strong bond and affinity with an inorganic material such as a metal. That is, the surface of the polymer resin is a thiol group, a nucleophilic group and a metal affinity functional group carboxyl group, hydroxy group, glycol group, aldehyde group, oxazole group, amine group, amide group, imide group, nitro group, nitrile group, sulfone group And the like can be used.

The polymer resin (2) may be fixed continuously or discontinuously on the surface of the moisture absorbent (1).

In an embodiment, the polymer resin 2 may be fixed by coating on the surface of the moisture absorbent 1 or in the form of protruding fine particles.

In embodiments, when the polymer resin (2) is coated and fixed to the surface of the moisture absorbent (1), it may be fixed in the form of all coated or partially coated, the polymer resin may be fixed to 5 ~ 100% of the surface of the moisture absorbent Can be.

The coating method may be prepared by mixing mixing and spraying.

As shown in FIG. 2 (a), the polymer resin 2 may be continuously formed on the surface of the moisture absorbent 1. As described above, when the polymer resin 2 is continuously fixed to the surface of the moisture absorbent 1, the polymer resin 2 has a form of completely coating the surface of the polymer resin 2.

As shown in FIGS. 2B to 2C, the polymer resin 2 may be discontinuously formed on the surface of the moisture absorbent 1. As described above, when the polymer resin 2 is discontinuously fixed, a portion of the surface of the moisture absorbent 1 is coated in an irregular shape or the polymer resin 2 is irregularly formed as shown in FIG. 3 (a). As shown, the polymer resin 2 may be fixed to the surface of the moisture absorbent 1 in the form of particles to form protrusions.

As described above, when the polymer resin 2 is fixed to the surface of the moisture absorbent 1 in the form of protrusions, the protrusions are 0.1 to 99.9%, preferably 1 to 99%, more preferably 5 to 5% of the surface of the moisture absorbent. It can be fixed at 90%. There is an advantage that can protect the device from the moisture absorbent without lowering the moisture absorption efficiency in the above range. Most preferably, it is 10 to 80%.

In embodiments, the shape of the protruding fine particles may be spherical, elliptical, hemispherical, columnar, triangular pyramid, square pyramidal, peanut, star, cluster, irregular, and the like, but is not necessarily limited thereto.

In addition, the protruding fine particles may have a single particle form or a core-shell form.

In embodiments, the protruding microparticles are discontinuously fixed on the surface of the moisture absorbent at an average of 1 to 500 particles / μm ² , preferably 5 to 200 particles / μm ² , more preferably 10 to 100 particles / μm ^2. Can be. There is an advantage that can protect the device without lowering the moisture absorption efficiency in the above range.

In embodiments, the size of the protruding fine particles may have a particle diameter of 0.1 to 50%, preferably 0.5 to 30% of the diameter of the moisture absorbent. When the particle diameter of the projection-forming fine particles is in the above range, it exhibits the effect of protecting the device as a projection, and can maintain the projection shape.

In one embodiment, the size of the protruding fine particles may have an average particle size range of 0.005 to 40 ㎛. Preferably, the size of the protruding fine particles is 0.05 to 10 μm, more preferably 0.01 to 5 μm, most preferably 0.01 to 1 μm. There is an advantage that can protect the device without deteriorating the performance of the absorbent in the above range. The size of the protrusion-forming microparticles is smaller than the size of the moisture absorbent (1), the porosity may be 0.1 to 50%.

There is no particular limitation on the polymerization method of the protrusion-forming microparticles, but it may be prepared by emulsion polymerization, emulsion-free polymerization or dispersion polymerization. The process for producing the protruding microparticles is described in Korean Patent Nos. 772423 and 503343, and the present invention is incorporated by reference.

In another embodiment, the protruding microparticles are added to a vinyl monomer mixture comprising a crosslinkable monomer and a mixture of the oil-soluble initiator in an aqueous solution in which the surfactant is dissolved to prepare an aqueous emulsion, and the aqueous emulsion is a monodisperse seed particle dispersion. After addition to swelling, the swollen mixture can be prepared by polymerization.

The method of fixing the protruding microparticles on the surface of the moisture absorbent (1) may be performed by using a method such as dry method using physical / mechanical friction, dry method using physical / chemical friction, fixing by wet treatment, etc. Can be fixed to the surface. In the specific example, by using the method using a hybridization system (Nara Machinery Co.), the projection-forming fine particles can be fixed to the surface of the moisture absorbent (1).

The weight ratio between the polymer resin 2 and the moisture absorbent 1 fixed in the form of coating or protruding fine particles may be 99: 1 to 50:50, preferably 95: 5 to 70:30. There is an advantage that can protect the device from the absorbent without deteriorating the performance of the absorbent in the above range.

abandonment EL For getters  Composition

Another aspect of the invention is a composition for an organic EL getter comprising the hygroscopic particles.

The organic EL getter composition may include a resin and the moisture absorbing particles of the present invention. The composition for the organic EL getter may have a viscosity (80 ° C.) of 10 to 100,000 cps, and may be in an injection type in the above range.

The resin may be a curable resin or a non-curable resin. In a specific embodiment, the composition for organic EL getters includes 10 to 90 parts by weight, preferably 15 to 75 parts by weight, and more preferably 20 to 55 parts by weight of the protrusion-type moisture absorbing particles based on 100 parts by weight of the curable resin or the non-curable resin. can do. In the above range there is an advantage to ensure the usability and sufficient moisture absorption efficiency of the resin.

The curable resin may include a curable polymer or copolymer, and may further include an oligomer and a monomer. In specific embodiments, (meth) acrylate, urethane acrylate, epoxy acrylate, epoxy resin and mixtures thereof may be used. Preferably it is an epoxy resin, and phenol novolak-type epoxy resin, cresol novolak-type epoxy resin, bisphenol-based epoxy resin, for example, bisphenol A, bisphenol F, and bisphenol S-type epoxy resin, phenol or cresol-based functional group 3 or more multifunctional Epoxy resin, a biphenyl group, a naphthalene group, a dicyclopentadiene group, and the epoxy resin which has two or more glycidyl ether groups, etc. are mentioned. Moreover, it is preferable that hardening temperature is 60-200 degreeC.

The non-curable resins include polyolefins, (meth) acrylate resins, vinyl cyanide resins, aromatic vinyl resins, polyamide resins, polyester resins, polycarbonate resins, and the like, but are not necessarily limited thereto. . These may be used alone or in the form of two or more copolymers or mixtures.

In embodiments, the composition for an organic EL getter may have a thixotropy index (T / I) of 1.0 to 7.0 at room temperature (25 ° C.) when it is uncurable. There is an easy advantage when applying in the above range.

In addition, the composition for an organic EL getter may include 10 to 90 parts by weight of the hygroscopic particles based on 100 parts by weight of the non-curable resin.

In embodiments, the organic EL getter composition may include one or more additives such as a curing catalyst, a viscosity modifier, a curing agent, an initiator, a dispersant, a stabilizer, and a curing accelerator. These additives can be used individually or in mixture of 2 or more types.

The additives can be easily selected and used by those skilled in the art.

4 is a schematic diagram of a curing process of the composition for an organic EL getter of the present invention. As shown in FIG. 4, in the composition for organic EL getter of the present invention, the moisture absorbing particles 10 are dispersed in the curable resin 11, and the viscosity of the liquid curable resin is lowered during curing, so that the settling of the moisture absorbing particles 10 is achieved. And the fine particles 2 protect the element 20 from the moisture absorbent 1 while the moisture absorbent 1 is close to the element 20 to capture moisture more effectively.

abandonment EL  device

Another aspect of the present invention relates to an organic EL device using the composition for organic EL getters. 5 is a schematic cross-sectional view of an organic EL device according to an embodiment of the present invention.

In an embodiment, the organic EL device may include a substrate 110; An organic light emitting unit 130 formed on one surface of the substrate and including a first electrode, an organic light emitting layer, and a second electrode; A sealing cap 120 coupled to the substrate to accommodate the organic light emitting unit; And an organic EL getter composition formed between the substrate and the sealing cap and covering the organic light emitting part. The composition for organic EL getters includes the hygroscopic particles 10 and the resin 11 'of the present invention.

In a specific embodiment, the composition for the organic EL getter is cured, and the hygroscopic particles 10 are precipitated in the curing process and are distributed on the surface of the organic light emitting unit 130.

The organic EL device can be manufactured by a conventional method. In one embodiment, the composition for organic EL getters is coated on a sealing cap or a substrate, and then bonded to a substrate having an organic light emitting unit including a first electrode, an organic light emitting layer, and a second electrode, and then cured to form an organic EL. The device can be manufactured. The organic EL getter composition may be cured at 60 to 200 ° C.

Hereinafter, the configuration and operation of the present invention through the preferred embodiment of the present invention will be described in more detail. However, this is presented as a preferred example of the present invention and in no sense can be construed as limiting the present invention.

Details that are not described herein will be omitted since those skilled in the art can sufficiently infer technically.

Example

Manufacturing example  1: projection Of hygroscopic particles  Produce

95 parts by weight of 3 μm CaO (Anfogen # 600H) as a moisture absorbent is mixed with 5 parts by weight of 0.3 μm-sized dendritic particles (made by Cheil Industries, styrene-divinylbenzene / styrene-divinylbenzene-acrylic acid) core-shell The immobilization was carried out using a hybridizer manufactured by Nara Machinery Co., Ltd. to produce protruding moisture absorbing particles. As a result of observing the produced protruding moisture absorbing particles, it was confirmed that the protruding microparticles were discontinuously fixed at an average of 10-30 particles / µm ² and fixed at 20-30% of the surface area of the absorbent.

Manufacturing example  2: surface Coated Hygroscopic Particles  Produce

As a moisture absorbent, 20 parts by weight of butyl acrylate resin was mixed with 80 parts by weight of CaO (Chemical Chemicals Anfogen # 600H) having a size of 3 μm, and immobilized on the surface to prepare coated moisture absorbing particles.

Example  One

Protrusion type manufactured in Preparation Example 1 Epoxy resin YDF0 8170 (manufactured by Kukdo Co., Ltd.), a curing agent (manufactured by PETMP: Bruno), and a curing catalyst (manufactured by PN-H: AJICURE) were mixed with the moisture absorbing particles to prepare a composition for an organic EL getter.

abandonment EL  Manufacture of device

The above-described composition for an organic EL getter was prepared on a glass substrate having an organic electroluminescent unit including a first electrode, an organic light emitting layer, and a second electrode, and coated on the glass substrate using a dispenser. Covering the sealing cap on this, the sealing cap with the composition for the organic EL getter and the substrate having the organic electroluminescent unit is bonded and heat-treated at 80 ℃ for 30 minutes, the organic EL device filled with the composition for the organic EL getter Was prepared.

Example  2

Except for changing the content of the protrusion-type absorbent particles in Table 1 was carried out in the same manner as in Example 1.

Example  3

The same procedure as in Example 1 was carried out except that the moisture-absorbing particles were replaced with the surface-coating moisture absorbing particles prepared in Preparation Example 2.

Comparative Example  One

The same procedure as in Example 1 was performed except that 3Om-sized CaO (Hansung Chemical Co., Ltd. Anfogen # 600H) was used instead of the protrusion-type moisture absorbing particles.

Comparative Example  2

The same procedure as in Example 2 was carried out except that CaO (Chemical Chemical Company Anfogen # 600H) having a size of 3 μm was not used instead of the protrusion type moisture absorbing particles.

Example Comparative example One 2 3 One 2 Curable resin 100 100 100 100 100 Hardener 80 80 80 80 80 Curing catalyst 0.1 0.1 0.1 0.1 0.1 Hygroscopic Particles Projection 50 30 - - - Coated - - 10 - - Protrusion Unformed CaO - - - 50 30 dark spot none none none Occur Occur Reliability (85/85, 168hr) pass pass pass - - Hygroscopic Efficiency (wt%) 13 7 5 13 8

(1) Dark spot measuring method: After sealing the sealing cap on the device and bonded it, heat treatment at 80 ℃ for 30 minutes to apply the voltage to the electrode of the device to check the presence of dark spot when the cell is turned on. If there is no dark spot, it was determined as pass.

(2) Reliability: After 168 hours of thermal shock test at 85 ℃ and 85RH% of relative humidity, check the presence of dark spot when the cell is turned on by applying voltage to the electrode. If there is no dark spot, it was determined as pass.

(3) Moisture absorption efficiency: After the composition was formed into a film on the film and cured under nitrogen atmosphere in a convection oven, the resulting coating film was prepared at 1g weight and the thermal shock test was performed at 85 ° C and relative humidity of 85RH% for 168 hours. After that, the weight ratio before and after the thermal shock test was calculated.

(Weight of coating after thermal shock-weight of coating before thermal shock) / weight of coating before thermal shock * 100

As shown in Table 1, when using the composition for an organic EL getter of the present invention, dark spots did not occur, it can be seen that the reliability is excellent. In particular, when applying the projection type moisture-absorbing particles it can be confirmed that the excellent moisture absorption efficiency.

Although the embodiments of the present invention have been described above with reference to the accompanying drawings and tables, the present invention is not limited to the above embodiments, but may be manufactured in various forms, and common knowledge in the art to which the present invention pertains. Those skilled in the art can understand that the present invention can be implemented in other specific forms without changing the technical spirit or essential features of the present invention. It is therefore to be understood that the embodiments described above are in all respects illustrative and not restrictive.

1: moisture absorbent 2: polymer resin
10: hygroscopic particles 11: curable resin
11 ': cured resin 20: element
100 composition for organic EL getter 110 substrate
120: sealing cap 130: organic light emitting unit
140: drying means

Claims (21)

Hygroscopic agents; And
A polymer resin formed continuously or discontinuously on the surface of the moisture absorbent;
Hygroscopic particles, characterized in that comprises a.
The hygroscopic particles of claim 1, wherein the polymer resin is a resin having a glass transition temperature of -60 to 170 ° C.
The hygroscopic particles according to claim 1, wherein the polymer resin is a polymer of at least one crosslinkable monomer, a polymer of at least one vinyl monomer or a copolymer of at least one crosslinkable monomer and at least one vinyl monomer.
The hygroscopic particles of claim 3, wherein the polymer resin has a crosslinking degree of 0.5 to 50%.
The hygroscopic particles of claim 1, wherein the polymer resin is porous.
The hygroscopic particles of claim 1, wherein the polymer resin is coated and fixed on the surface of the moisture absorbent.
The hygroscopic particles of claim 2, wherein the polymer resin is fixed at 5 to 100% of the surface of the moisture absorbent.
The hygroscopic particles of claim 1, wherein the polymer resin is fixed to the surface of the moisture absorbent with protrusion-forming microparticles.
10. The method of claim 8, wherein the projection-forming microparticles and projections, characterized in that the fixed moisture absorption particles of 0.1 ~ 99.9% of the surface of the moisture absorbent.
9. The hygroscopic particles according to claim 8, wherein the protruding fine particles are 0.1-50% of the diameter of the hygroscopic agent.
The method of claim 1, wherein the moisture absorbent is at least one selected from the group consisting of molecular sieve zeolite, silica gel, carbonate, clay, metal oxide, metal hydroxide, alkaline earth metal oxide, sulfate, metal halide, perchlorate and organometallic. Hygroscopic particles, characterized in that it comprises.
The composition for organic EL getters containing the moisture absorption particle of any one of Claims 1-11.
The composition for organic EL getters according to claim 12, wherein the composition for organic EL getters comprises 10 to 90 parts by weight of the hygroscopic particles with respect to 100 parts by weight of the resin.
13. The composition for organic EL getters according to claim 12, wherein the resin is a curable or non-curable resin.
15. The composition for organic EL getters according to claim 14, wherein the resin is a non-curable resin, and the composition for organic EL getters has a thixotropy index (T / I) of 1.0 to 7.0 at room temperature (25 ° C).
The composition for organic EL getters according to claim 13, wherein the composition for organic EL getters has a viscosity (80 ° C) of 10 to 100,000 cps.
The composition for organic EL getters according to claim 13, wherein the composition for organic EL getters comprises at least one additive selected from the group consisting of a curing catalyst, a viscosity modifier, a curing agent, an initiator, a dispersant, a stabilizer and a curing accelerator.
An organic EL device using the composition for organic EL getters of claim 12.
19. The organic EL device of claim 18, wherein the organic EL device is
Board;
An organic light emitting unit formed on one surface of the substrate and including a first electrode, an organic light emitting layer, and a second electrode;
A sealing cap coupled to the substrate to accommodate the organic light emitting unit; And
And an organic EL getter composition formed between the substrate and the sealing cap and covering the organic light emitting portion.
The organic EL device according to claim 19, wherein the composition for organic EL getters is cured.
21. The organic EL device according to claim 20, wherein the composition for organic EL getters is cured at a curing temperature of 60 to 200 deg.

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