KR20140073268A - Thin film encapsulation for organic electronic device, encapsulation products for organic electronic device containing the same and encapsulating method of organic electronic device - Google Patents

Abstract

The present invention relates to a thin film encapsulation element for an organic electronic device, an encapsulation product for the organic electronic device including the same, and an encapsulating method of the organic electronic device. The thin film encapsulation element according to the present invention has high gas and moisture-proof properties and is applied to various products to be protected against oxygen or vapor. The lifetime and durability of the product are remarkably improved by applying the thin film encapsulation element to a device substrate or the encapsulation of a display device like the organic electrode device which is vulnerable to the oxygen or vapor. A defective product is minimized or prevented by effectively removing bubbles in an encapsulation process.

Description

TECHNICAL FIELD [0001] The present invention relates to a thin film bag for an organic electronic device, an organic electronic device encapsulating product including the same, and a sealing method of an organic electronic device,

The present invention relates to a thin film bag for organic electronic devices which is excellent in gas / moisture barrier properties, long-term stability, flexibility and adhesiveness, and easily removes bubbles generated in the sealing of organic electronic devices, ≪ / RTI >

An organic electronic device (OED) refers to an apparatus that includes an organic material layer that generates an alternating current of charge using electrons and holes, and examples thereof include a photovoltaic device, a transmitter, And organic light emitting diodes (OLEDs).

Organic light emitting diodes (OLEDs) among the above organic electronic devices have a faster response speed, lower power consumption, and are more advantageous for thinning than existing light sources. In addition, OLEDs are expected to be used in various fields across displays such as portable devices, monitors, and televisions, since they can be made thinner.

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.

Conventionally, a method of processing a metal can or a glass into a cap shape with a groove, mounting a moisture-absorbing agent for absorbing moisture in a powder form, or making a film form and bonding it with a double-sided tape is used. There is a problem that sufficient performance can not be exhibited.

Further, in the case of the conventional sealing material, when the organic electronic device is sealed, bubbles are generated when the sealing material is bonded (or pressure-bonded) to the organic electronic device and the bubble is left between the sealing material and the organic electronic device There has been a problem that defective products frequently occur.

Therefore, there is a need to develop a new encapsulant that can effectively prevent moisture penetration, reduce damage to the organic electronic device, and minimize or prevent the occurrence of bubbles.

Accordingly, the present inventors have found that the sealing layer is divided into two layers, one of which is introduced into the layer for moisture permeation prevention, and the other one layer And to provide a novel thin film bag for organic electronic devices in which a base portion is introduced on the surface.

According to an aspect of the present invention, there is provided a thin film encapsulant for an organic electronic device, which comprises a first copolymer having a base porcelain base portion 25 formed on one surface thereof and polymerized with an epoxy resin and a polyimide resin, A resin encapsulation layer (20); And a moisture permeation preventive layer (30) comprising a second copolymer obtained by polymerization of an epoxy resin and a polyimide resin and a moisture adsorbent (40).

As a preferred embodiment of the present invention, the thin film plug of the present invention may further include at least one layer selected from the pattern release layer 10 and the patternless release layer 50.

In one preferred embodiment of the present invention, the pattern releasing layer comprises a releasing layer 1 on which a pattern is formed or a pattern is not formed on one surface; And an adhesive layer 2 having a pattern formed on one surface thereof.

In another preferred embodiment of the present invention, the sealing layer and the water-impermeability preventing layer may comprise the same or different silane-modified epoxy resin, and the silane-modified epoxy resin may be a dicyclopentadiene-type epoxy resin, a dicyclopentadiene- At least one epoxy silane selected from phenol type epoxy, biphenyl type epoxy, naphthalene type epoxy, cresol type epoxy, bisphenol type epoxy, xylox type epoxy, phenol novolac epoxy, triphenol methane type epoxy and alkyl modified triphenol methane epoxy Group-introduced epoxy resin.

The silane-modified epoxy resin may include a copolymer containing a unit represented by the following formula (1) and a unit represented by the following formula (2).

[Chemical Formula 1]

In the above Formula 1, R ¹ is a hydrogen atom, C1 ~ C5 alkyl group, a C5 ~ C6 cycloalkyl group, a naphthalene group or a cycloalkylene group, a phenyl group, a C5 ~ C6 bisphenol group, wherein R ² is a C1 ~ C5 Lt; / RTI >

(2)

In the general formula 2, R ³ and R ⁴ are independent as, R ³ and R ⁴ each represent a hydrogen atom, an alkyl group of C1 ~ C5, cycloalkyl of C5 ~ C6, C5 ~ C6 cycloalkyl group, a phenyl group, a naphthalene Or a bisphenol group.

In another preferred embodiment of the present invention, the moisture permeation preventive layer 30 may include 60 to 100 parts by weight of the moisture adsorbent per 100 parts by weight of the second copolymer.

In another preferred embodiment of the present invention, the encapsulation layer 20 may not contain a moisture adsorbent. When the encapsulating layer 20 further comprises a moisture adsorbent, the encapsulating layer 20 may contain 0.1 to 20 wt% Section.

In another preferred embodiment of the present invention, the polyimide resin of the encapsulating layer and the water-impermeable layer is independent of each other, and may include a compound represented by the following formula (3).

(3)

이고, 상기 R⁵ 및 R⁶은 독립적인 것으로서, R⁵은 -CF₃ 또는 -CF₂CF₃이고, R⁶는 수소원자, -CF_{3 ,} -CF₂CF₃, C1~C6의 알킬기 또는 페닐기이며, Y는 3가 내지 6가 유기기로서,

,

,

,

,

,

또는

이고, m은 1≤m≤4를 만족하는 정수이다.In Formula 3, X is

And, as the R are independently selected from ⁵ and R ^6, R ⁵ is -CF ₃ or -CF ₂ CF _3, and R ⁶ is a hydrogen _{atom, -CF 3, -CF 2 CF 3} , an alkyl group or a phenyl group of C1 ~ C6 Y is a trivalent to hexavalent organic group,

,

,

,

,

,

or

And m is an integer satisfying 1? M? 4.

In another preferred embodiment of the present invention, the first copolymer is a copolymer comprising a unit represented by the following formula (4), and the second copolymer is a copolymer comprising a unit represented by the following formula .

[Chemical Formula 4]

[Chemical Formula 5]

이고, 상기 R⁵ 및 R⁶은 독립적인 것으로서, R⁵은 -CF₃ 또는 -CF₂CF₃이고, R⁶는 수소원자, -CF_{3 ,} -CF₂CF₃, C1~C6의 알킬기 또는 페닐기이며, Y는 3가 내지 6가 유기기로서,

,

,

,

,

,

또는

이고, Z는

이며, 상기 a 및 b 는 독립적인 것으로서, a는 0≤a≤5를, b는 0≤b≤5를 만족하는 정수이고, 상기 화학식 4에 있어서, m은 1≤m≤4를 만족하는 정수이며, 상기 화학식 5에 있어서, M은 1 또는 2이고, L은 1≤L≤3을 만족하는 정수이다.In the above formulas (4) and (5), X is

And, as the R are independently selected from ⁵ and R ^6, R ⁵ is -CF ₃ or -CF ₂ CF _3, and R ⁶ is a hydrogen _{atom, -CF 3, -CF 2 CF 3} , an alkyl group or a phenyl group of C1 ~ C6 Y is a trivalent to hexavalent organic group,

,

,

,

,

,

or

And Z is

A and b are independent, a is an integer satisfying 0? A? 5 and b is an integer satisfying 0? B? 5, and m is an integer satisfying 1? M? , M is 1 or 2, and L is an integer satisfying 1? L? 3.

In another preferred embodiment of the present invention, the moisture adsorbent is selected from the group consisting of zeolite, montmorillonite, TiO ₂ , ZrO ₂ , Al ₂ O ₃ , SiO ₂ , P ₂ O ₅ , Li ₂ O, Na ₂ O, BaO, CaO _{, MgO, Li 2 SO 4,} Na 2 SO 4, CaSO 4, MgSO 4, CoSO 4, Ga 2 (SO 4) 3, Ti (SO 4) 2, NiSO 4, CaCl 2, MgCl 2, SrCl 2, YCl _{3, CuCl 2, CsF, TaF} 5, NbF 5, LiBr, CaBr 2, CeBr 3, SeBr 4, VBr 3, MgBr 2, BaI2, MgI 2, Ba (ClO 4) 2 and Mg (ClO _{4) 2} in a selected And may include one or more species.

Further, as a preferred embodiment of the present invention, each of the sealing layer and the moisture-permeation preventive layer comprises a curing agent containing at least one selected from an amine curing agent, an imidazole curing agent, a phenol curing agent, a phosphorus curing agent and an acid anhydride curing agent; Thermal crosslinking agents containing blocked isocyanates and polyhydroxystyrene; A stability improver containing at least one selected from a phenoxy resin, an acrylate resin, a high molecular weight epoxy resin and an ultra high molecular weight epoxy resin; And a viscosity diluent containing at least one selected from methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone and ethyl acetate; And at least one additive selected from the group consisting of:

As another preferred embodiment of the present invention, the non-patterned release layer 50 and the release layer 1 of the patterned release layer are independent, and each of them may be formed of polyethylene terephthalate (PET), polymethylmethacrylate PMMA), polyethylene naphthalate (PEN), and polycarbonate (PC).

In another preferred embodiment of the present invention, the thin film encapsulant of the present invention includes a sealing layer 20, a moisture permeation preventing layer 30, an encapsulating layer 20, > The moisture permeation preventing layer 30 are stacked in this order.

In another preferred embodiment of the present invention, the aforementioned thin film encapsulant is cured and measured according to ASTM F1249 in terms of the water vapor transmission rate (WVTR) of 10 to 50 g / m < 2 > day . ≪ / RTI >

Another aspect of the present invention relates to an organic electronic device encapsulation product, comprising: a substrate; An organic electronic device (100) formed on the substrate; And the thin film encapsulant for encapsulating the organic electronic device, wherein the encapsulating layer of the thin film encapsulant covers the organic electronic device. The organic electronic device may include at least one selected from a photovoltaic device, a transmitter, and an organic light emitting diode (OLED).

Another aspect of the present invention relates to a method of encapsulating an organic electronic device, which comprises covering the organic electronic device with the thin film encapsulation material of the present invention, wherein the encapsulation layer of the thin film encapsulation material is contacted with the organic electronic device, To an organic electronic device; And performing a pressing operation.

As a preferred embodiment of the present invention, the step of performing the pressing may be performed by at least one method selected from a hot roll laminate, a hot press, or a vacuum press.

The encapsulating method may further include a step of curing the thin film encapsulant by heat curing or ultraviolet (UV) curing at 70 ° C to 110 ° C, Curing method.

INDUSTRIAL APPLICABILITY The thin film closure for an organic electronic device of the present invention is excellent in gas and moisture barrier properties and can be effectively used in various products requiring protection from oxygen or water vapor. In particular, a thin film closure for a display device such as an organic electronic device vulnerable to oxygen or water vapor Or the element substrate, the lifetime and durability thereof can be greatly improved. Further, when the thin film closure is applied to an organic electronic device and sealed, bubbles generated can be effectively removed, and generation of defective products can be minimized and prevented.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic view of a thin film bag of the present invention including an encapsulating layer and a moisture-permeation preventing layer. FIG.
Figs. 2A to 2F are illustrative examples of various shapes of the baseport base formed in the sealing layer. Fig.
3 A and B are schematic views of one surface of the sealing layer in which the porcelain base is formed.
Fig. 4 is a schematic view of a thin film bag of the present invention including a pattern releasing layer, an encapsulating layer, and a moisture permeation preventing layer, in which a pattern is formed on the adhesive layer 2. Fig.
5 is a schematic view of a thin film bag of the present invention including a pattern releasing layer, an encapsulating layer and a moisture permeation preventing layer, wherein (2) patterns are formed in the releasing layer 1 and the pressure-sensitive adhesive layer.
6 is a schematic view of a thin film bag of the present invention including a pattern releasing layer, a sealing layer, a moisture-permeation preventing layer and a patternless releasing layer.
7 is an organic electronic device encapsulation product to which the thin film bag of the present invention is applied.

The term organic electronic device (OED) as used in the present invention means an apparatus including an organic material layer that generates alternating electric charges by using electrons and holes, and more specifically, photovoltaic devices device, a transmitter, and an organic light emitting diode (OLED).

Hereinafter, the present invention will be described in more detail.

As shown in FIG. 1, the thin film closure for organic electronic devices according to the present invention includes a first sealing layer 20 and a moisture permeation preventing layer 30, and a porcelain base portion 25 is formed on one surface of the sealing layer . The base portion may be formed in various shapes such as a triangular, semicircular, quadrangular, pentagonal, and conical shape as illustrated in FIG. 2, and may be formed in one direction on the surface of the sealing layer, Or bubble can be smoothly escaped when the organic electronic device is compressed and sealed by the thin film encapsulation material of the present invention through the base port base portion.

As an example of forming the base porcelain base, a calender roll having a convex pattern having the same shape as that of the base porcelain base can be used on one side of the sealing layer after the sealing layer is formed.

Another method is to coat the one surface of the release layer 1 with a pressure sensitive adhesive to form the pressure sensitive adhesive layer 2 and then form a porcelain base pattern (convex pattern) on one surface of the pressure sensitive adhesive layer using a calender roll or the like The pattern releasing layer 10 may be formed as shown in FIG. If a sealing layer is formed on one side of the adhesive layer on which the pattern is formed, a depressed base porcelain base can be formed on one side of the sealing layer. The method of forming the porcelain base portion is an example, and the present invention is not limited thereto.

As another method, a base porcelain pattern (convex pattern) is formed on one surface of the release layer 1 by using a calender roll or the like on the release layer 1, and then an adhesive is coated on the patterned surface, It is possible to obtain the pattern release layer 10 in which the adhesive layer 2 and the release layer 1 are patterned in such a manner that a convex pattern is formed on the adhered surface direction as shown in FIG.

4 and 5, the pattern releasing layer 10 may include a pattern releasing layer 10 having no pattern or having a pattern formed on a surface thereof, (One); And an adhesive layer 2 having a pattern formed on one surface thereof.

7, the release layer 1 serves to protect the support and the sealing layer of the adhesive layer 2, and when applied to an organic electronic device, when the thin film encapsulant of the present invention is applied to the pattern release layer 10 ) Is removed to seal the organic electronic device. Therefore, the pressure-sensitive adhesive layer 2 may be formed of a pressure-sensitive adhesive or an adhesive component. Preferably, the pressure-sensitive adhesive layer 2 is formed as a pressure-sensitive adhesive component for separation from the sealing layer.

As shown in FIG. 6, the thin film closure of the present invention may further include a patternless release layer 50, which protects the sealing layer and the moisture permeation preventive layer, It can be removed when applied to electronic devices.

In addition, the thin film closure of the present invention may be in the form of alternately stacking the sealing layer and the moisture-permeation preventing layer. For example, the sealing layer 20 may be in the opposite direction from the direction in which it contacts the organic electronic device, The barrier layer 30, the moisture barrier layer 30, and the moisture barrier layer 30 may be stacked in this order. The structure or form of the thin film encapsulant of the present invention is not limited thereto, But may be a laminated structure in various forms depending on the application, provided that the sealing layer 20 is at the bottom.

In the present invention, the sealing layer prevents the organic electronic device from being greatly influenced by the volume expansion due to the surface contacting the organic electronic device, and acts to block ultimate oxygen and moisture, thereby causing physical chemical damage of the organic electronic device And the moisture permeation preventive layer functions to effectively inhibit penetration of moisture, moisture or oxygen into the organic electronic device. Therefore, the compositions and composition ratios used in the production of the respective layers for imparting such a common role and / or other roles to the sealing layer and the moisture permeation preventive layer are as follows.

In the thin film closure for an organic electronic device according to the present invention, the sealing layer preferably has an average thickness of 1 to 20 μm, and when it is used as an encapsulating material for organic electronic devices, it can be protected from damage factors of the moisture permeation- It is difficult to perform a physical and chemical function. If it exceeds 20 탆, there is a problem that the efficiency of the water blocking ability may be lowered. Therefore, it is preferable to use within the above range.

The moisture permeation preventive layer preferably has an average thickness of 5 to 100 占 퐉. If it is less than 5 占 퐉, it can not exhibit moisture blocking ability and thus it is difficult to prevent oxygen and moisture. If it exceeds 100 占 퐉, And it may be difficult to peel off the film, and the thickness expansion due to moisture reactivity may be large, thereby damaging the vapor deposition layer of the organic light emitting device, resulting in poor economical efficiency.

The release layer 1 of the pattern release layer 10 preferably has an average thickness of 5 to 80 탆 and the pressure-sensitive adhesive layer 2 has an average thickness of 2 to 20 탆, preferably 2 to 10 탆 If it is less than 2 탆, it is too thin to exhibit sufficient adhesive strength, and if it exceeds 20 탆, economical efficiency is low.

In addition, the non-patterned release layer 50 has an average thickness of 1 to 10 탆 in terms of securing the protection and fairness of the organic light emitting device.

Hereinafter, the composition of each layer constituting the thin film closure of the present invention will be described in more detail.

[ Seal layer ]

In the thin film bag of the present invention, the sealing layer may include a first copolymer containing an epoxy resin and a polyimide resin as a layer located closest to (or bonding with) the organic electronic device. The epoxy resin and the polyimide resin are used in an amount of 100: 1 to 40 parts by weight, preferably 100: 1 to 30 parts by weight, more preferably 100: 5 to 20 parts by weight, And polyimide resin is less than 100: 1 by weight, the amount of polyimide resin used is too small to improve the heat resistance. When the amount of polyimide resin is more than 100: 40, the volume expansion due to moisture adsorption affects the organic light emitting device. It is preferable to use an epoxy resin and a polyimide resin within the above range.

Here, the epoxy resin may have an epoxy compound concentration of 50 to 80% by weight, and the polyimide resin preferably has a polyimide compound concentration of 20 to 30% by weight.

The epoxy resin is not particularly limited, but a silane-modified epoxy resin can be used. Preferred examples of the epoxy resin include dicyclopentadiene type epoxy, dicyclopentadiene modified phenol type epoxy, biphenyl type epoxy, naphthalene type epoxy, cresol type epoxy, A silane-modified epoxy resin having a silane group introduced into at least one epoxy selected from a bisphenol-based epoxy, a xylyl-based epoxy, a phenol novolak epoxy, a triphenolmethane-type epoxy and an alkyl-modified triphenolmethane epoxy can be used, A silane-modified epoxy resin containing a compound containing a unit represented by the formula (1) can be used.

 [Chemical Formula 1]

In the above Formula 1, R ¹ is a hydrogen atom, C1 ~ C5 alkyl group, a C5 ~ C6 cycloalkyl group, a naphthalene group or a cycloalkylene group, a phenyl group, a C5 ~ C6 bisphenol group, wherein R ² is a C1 ~ C5 Lt; / RTI > In Formula 1, R ¹ is preferably a C1-C3 alkyl group or a C5-C6 cycloalkyl group, and R ² is a C1-C3 linear alkyl group.

Further, the compound is preferably a copolymer containing the unit represented by the formula (1) and the unit represented by the following formula (2).

 (2)

In Formula 2, R ³ and R ⁴ are independent and R ³ and R ⁴ Each of which is a hydrogen atom, a C1 to C5 alkyl group, a C5 to C6 cycloalkyl group, a C5 to C6 cycloalkylene group, a phenyl group, a naphthalene group or a bisphenol group, preferably R ³ and R ⁴ Each is a C1 to C3 alkyl group or a C5 to C6 cycloalkyl group, more preferably R ³ and R ⁴ Each is a C1 to C3 alkyl group.

The epoxy resin preferably has an epoxy equivalent of 180 g / eq to 1,000 g / eq, preferably 200 g / eq to 800 g / eq, more preferably 200 g / eq to 500 g / eq If the epoxy equivalent of the epoxy resin is less than 180 g / eq, there may be a problem of chemical problems with the organic electronic device due to recrystallization and moisture adsorption of the unreacted material. If the epoxy equivalent is less than 1,000 g / eq, it may be easily cracked due to over-curing, and there may be a problem in the process. Therefore, it is preferable to use an epoxy resin containing an epoxy equivalent within the above range.

The sealing layer may further include a polyimide resin generally used in the art in addition to the epoxy resin.

The polyimide resin plays a role of preventing the phenomenon of thinning in the wafer process and shrinkage in processing as an encapsulating material because the hydroxyl group in the polyimide functions to ring and link the epoxide ring of the epoxy, The polyimide resin may be characterized by containing a compound represented by the following formula (2).

이고, 상기 R⁵ 및 R⁶은 독립적인 것으로서, R⁵은 -CF₃ 또는 -CF₂CF₃이고, 바람직하게는 -CF₃ 이다. 그리고, R⁶은 수소원자, -CF_3, -CF₂CF₃, C1~C6의 알킬기 또는 페닐기이며, 바람직하게는 -CF_{3 ,} -CF₂CF₃ 또는 페닐기이다. 그리고 Y는

,

,

,

,

,

또는

이고, 바람직하게는

,

,

또는

이다. 또한, m은 1≤m≤4를 만족하는 정수이며, 바람직하게는 m은 1≤m≤2를 만족하는 정수이다.In the formula (3), X is

, R ⁵ and R ⁶ are independent and R ⁵ is -CF ₃ or -CF ₂ CF ₃ , preferably -CF ₃ to be. And R ⁶ is a hydrogen atom, -CF _3, -CF ₂ CF ₃ , a C 1 -C 6 alkyl group or a phenyl group, preferably -CF _{3 ,} -CF ₂ CF ₃ or a phenyl group. And Y is

,

,

,

,

,

or

, And preferably

,

,

or

to be. M is an integer satisfying 1? M? 4, and preferably m is an integer satisfying 1? M? 2.

 (3)

The first copolymer may be a copolymer of the epoxy resin and the polyimide resin including the compound represented by the formula (3), and may be a copolymer comprising a unit represented by the following formula (4) Lt; / RTI >

[Chemical Formula 4]

이고, 상기 R⁵ 및 R⁶은 독립적인 것으로서, R⁵은 -CF₃ 또는 -CF₂CF₃이고, 바람직하게는 -CF₃이다. 그리고, R⁶는 수소원자, -CF_3, -CF₂CF₃, C1~C6의 알킬기 또는 페닐기이며, 바람직하게는 -CF_{3 ,} -CF₂CF₃ 또는 페닐기이다. 또한, 상기 Y는 3가 내지 6가 유기기로서,

,

,

,

,

,

또는

이고, 바람직하게는

,

,

또는

이다. 그리고, 상기 Z는

이며, 상기 a 및 b 는 독립적인 것으로서, a는 0≤a≤5를, b는 0≤b≤5를 만족하는 정수, 바람직하게는 a는 0≤a≤3를, b는 0≤b≤3을 만족하는 정수이다. 또한, 상기 화학식 4에 있어서, m은 1≤m≤4를, 바람직하게는 1≤m≤2를 만족하는 정수이다. In Formula 4, X is

, R ⁵ and R ⁶ are independent and R ⁵ is -CF ₃ or -CF ₂ CF ₃ , preferably -CF ₃ . And R ⁶ is a hydrogen atom, -CF _3, -CF ₂ CF ₃ , a C 1 -C 6 alkyl group or a phenyl group, preferably -CF _{3 ,} -CF ₂ CF ₃ or a phenyl group. Y is a trivalent to hexavalent organic group,

,

,

,

,

,

or

, And preferably

,

,

or

to be. And Z represents

A and b are independent, a is an integer satisfying 0? A? 5 and b is an integer satisfying 0? B? 5, preferably a is 0? A? 3, b is 0? 3. In Formula 4, m is an integer satisfying 1? M? 4, preferably 1? M? 2.

In addition, when the moisture absorbent is used, the encapsulating layer may not contain a moisture adsorbent. The moisture absorbent may further include a small amount of moisture absorbent. The moisture permeated from the moisture permeation preventing layer 30 penetrates into the organic electronic device, It is possible to prevent damage from occurring.

The moisture adsorbent is zeolite, _{montmorillonite, TiO 2, ZrO 2, Al} 2 O 3, SiO 2, P 2 O 5, Li 2 O, Na 2 O, BaO, CaO, MgO, Li 2 SO 4, Na 2 SO 4 , CaSO ₄ , MgSO ₄ , CoSO ₄ , Ga ₂ (SO ₄ ) ₃ , Ti (SO ₄ ) ₂ , NiSO ₄ , CaCl ₂ , MgCl ₂ , SrCl ₂ , YCl ₃ , CuCl ₂ , CsF, TaF ₅ , NbF ₅ At least one selected from LiBr, CaBr ₂ , CeBr ₃ , SeBr ₄ , VBr ₃ , MgBr ₂ , BaI ₂ , MgI ₂ , Ba (ClO ₄ ) ₂ and Mg (ClO ₄ ) ₂ , preferably TiO ₂ , ZrO _{2, Al 2 O 3, SiO} 2, P 2 O 5, Li 2 O, Na 2 O, BaO, CaO, MgO, Li 2 SO 4, Na 2 SO 4, CaSO 4, MgSO 4, CoSO 4, Ga 2 _{(SO 4) 3, Ti (} SO 4) 2 and NiSO ₄ is TiO _2, at least one member selected from the group consisting of, and more preferably _{ZrO 2, Al 2 O 3,} SiO 2, P 2 O 5, Li 2 O, Na ₂ O, BaO, CaO, and MgO.

The amount of the moisture adsorbent to be used is preferably 0.1 to 20 parts by weight, preferably 1 to 15 parts by weight, more preferably 1 to 10 parts by weight, of the moisture adsorbent per 100 parts by weight of the first copolymer. If the amount of the moisture adsorbent used is less than 0.1 part by weight, the amount of the moisture adsorbent to be used is so small that there is little effect of further use of the moisture adsorbent. When the amount of the water absorbent is more than 20 parts by weight, There may be a problem of causing cracks in the film of the apparatus, so it is preferable to use within the above range.

The sealing layer may further contain additives such as a curing agent, a thermal cross-linking agent, a stability improver, a viscosity diluent and the like, and the type and amount of the additives may be arbitrarily adjusted within a range not adversely affecting the effect to be obtained by the present invention Can be used.

Among the additives, the curing agent may include at least one selected from amine-based curing agents, imidazole-based curing agents, phenol-based curing agents, phosphorus-based curing agents and acid anhydride-based curing agents, 10 parts by weight.

The thermal cross-linking agent may be a conventional thermal cross-linking agent used in the art, and includes, but is not limited to, blocked isocyanate and polyhydroxystyrene or a thermal cross-linking agent containing a carboxyl group, an amide group, It is preferable to use at least one selected from the group consisting of epoxidized copolymers of aromatic hydrocarbons, epichlorohydrin and phenol formaldehyde polymers, and 1,1,1-tris (p-hydroxyphenyl) ethane triglycidyl ether Do.

The stability improving agent is used for imparting thermal and chemical stability improving effects to the encapsulating layer, and at least one selected from phenoxy resin, acrylate resin, high molecular weight epoxy resin and ultrahigh molecular weight epoxy resin can be used.

The viscosity diluent is used for diluting the viscosity of the encapsulating layer component to facilitate processing such as thinning of the encapsulating layer, molding and the like. The diluent is selected from the group consisting of methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone and ethyl acetate Or better.

[ Moisture permeation prevention layer ]

In the thin film closure for an organic electronic device according to the present invention, the moisture permeation preventive layer may comprise a second copolymer of an epoxy resin and a polyimide resin and a moisture adsorbent. In the kind of the moisture adsorbent mentioned in the sealing layer The same or different ones can be used.

The second copolymer contains the epoxy resin and the polyimide resin in a weight ratio of 100: 10 to 80, preferably 100: 40 to 80, more preferably 100: 50 to 80, If the amount of the epoxy resin and the polyimide resin is less than 100:10 by weight, the amount of the polyimide resin used may be too small to cause problems in heat resistance and moisture adsorption. If the amount exceeds 100: 80, It is preferable to use an epoxy resin and a polyimide resin within the above range.

The epoxy resin may have an epoxy compound concentration of 50 to 80% by weight, and the polyimide resin preferably has a polyimide compound concentration of 40 to 70% by weight.

In the second copolymer, the epoxy resin may be a silane-modified epoxy resin, preferably a dicyclopentadiene type epoxy, a dicyclopentadiene modified phenol type epoxy, a biphenyl type epoxy, a naphthalene type epoxy, a cresol type epoxy A silane-modified epoxy resin having a silane group introduced into at least one epoxy selected from an epoxy, a bisphenol-based epoxy, a xylox-based epoxy, a phenol novolac epoxy, a triphenolmethane-type epoxy, and an alkyl-modified triphenolmethane epoxy, A silane-modified epoxy resin containing a compound represented by the formula (1) may be used. The epoxy resin preferably has an epoxy equivalent of 160 g / eq to 1,200 g / eq, preferably 180 g / eq to 1,000 g / eq, more preferably 200 g / eq to 600 g / eq If the epoxy equivalent of the epoxy resin is less than 160 g / eq, there may be a problem of chemical problems with the organic electronic device due to the hardening and influence on the moisture adsorption of the unreacted material, and 1,200 g / eq, it may be easily cracked due to over-curing, and there may be a problem in the process. Therefore, it is preferable to use an epoxy resin containing an epoxy equivalent within the above range.

The epoxy resin used for the second copolymer may be the same or different from the epoxy resin used in the first copolymer.

In the second copolymer, the polyimide resin may be the same or different from the polyimide resin of the first copolymer among the compounds represented by the formula (2).

The second copolymer may be a copolymer of an epoxy resin containing a compound represented by the formula (1) and a polyimide resin containing a compound represented by the formula (3), and may be a copolymer represented by the following formula , A copolymer having a steric hindrance due to its structure.

[Chemical Formula 5]

이고, 상기 R⁵ 및 R⁶은 독립적인 것으로서, R⁵은 -CF₃ 또는 -CF₂CF₃이고, 바람직하게는 -CF₃이다. 그리고, R⁶는 수소원자, -CF_{3 ,} -CF₂CF₃, C1~C6의 알킬기 또는 페닐기이며, 바람직하게는 -CF_{3 ,} -CF₂CF₃ 또는 페닐기이다. 또한, 상기 Y는 3가 내지 6가 유기기로서,

,

,

,

,

,

또는

이고, 바람직하게는

,

,

또는

이다. 그리고, 상기 Z는

이며, 상기 a 및 b 는 독립적인 것으로서, a는 0≤a≤5를, b는 0≤b≤5를 만족하는 정수, 바람직하게는 a는 0≤a≤3를, b는 0≤b≤3을 만족하는 정수이다. In Formula 5, X is

, R ⁵ and R ⁶ are independent and R ⁵ is -CF ₃ or -CF ₂ CF ₃ , preferably -CF ₃ . And R ⁶ is a hydrogen atom, -CF _{3 ,} -CF ₂ CF ₃ , a C 1 -C 6 alkyl group or a phenyl group, preferably -CF _{3 ,} -CF ₂ CF ₃ or a phenyl group. Y is a trivalent to hexavalent organic group,

,

,

,

,

,

or

, And preferably

,

,

or

to be. And Z represents

A and b are independent, a is an integer satisfying 0? A? 5 and b is an integer satisfying 0? B? 5, preferably a is 0? A? 3, b is 0? 3.

In Formula 5, M is 1 or 2, and L is an integer satisfying 1 L 3.

The moisture permeation preventive layer may be the same or different in the kind of the moisture adsorbent mentioned in the sealing layer. The amount of the moisture permeation preventing layer may be 60 to 100 parts by weight, preferably 70 to 100 parts by weight, per 100 parts by weight of the second copolymer. To 100 parts by weight, and more preferably 80 to 100 parts by weight. If the amount of the moisture adsorbent used is less than 20 parts by weight, the amount of the moisture adsorbent used may be too small to sufficiently chemically adsorb (or absorb) the water penetrated into the organic light emitting device. If the amount is more than 100 parts by weight, The use amount of the second copolymer contained in the moisture permeation preventive layer is reduced and the physical properties such as heat resistance, insulation property, and water absorption property may be deteriorated.

The moisture permeation preventive layer may further contain additives such as a curing agent, a thermal crosslinking agent, a stability improver, a viscosity diluent, etc. mentioned in the description of the sealing layer, and may be added within a range that does not adversely affect the effect The type and amount of additives can be arbitrarily adjusted.

[pattern Heterogeneous layer  And No pattern Heterogeneous layer ]

The thin film closure of the present invention may further include at least one layer selected from the pattern release layer 10 and the patternless release layer 50. The release layer 10 may be formed of a release layer 1 ) Single layer or may further comprise an adhesive layer (2).

The release layer 1 and / or the pattern-free release layer 50 may be formed of at least one selected from the group consisting of polyethylene phthalate (PET), polymethyl methacrylate (PMMA), polyethylene naphthalate (PEN), and polycarbonate And the release layer 1 and / or the patternless release layer 50 may be the same or different materials.

The adhesive layer 2 of the pattern release layer may include at least one selected from an acrylic pressure sensitive adhesive, a silicone pressure sensitive adhesive and a urethane pressure sensitive adhesive.

For example, the release layer 1 may be formed by forming a coating layer 2 using a hot-melt adhesive on one surface of a sealing layer on which a base porcelain base is formed by a general method used in the art, The pattern release layer 10 can be formed.

Alternatively, the adhesive layer 2 is formed by coating a surface of the release layer 1 on which a pattern is formed, or a pattern thereof, with a pressure sensitive adhesive, and then forming a porcelain base pattern (convex pattern) on one surface of the pressure sensitive adhesive layer The pattern release layer 10 can be formed.

The thin film closure of the present invention having the above-described structure and composition has a water vapor transmission rate (WVTR) of 50 g / m 2 · day or less, preferably 10 to 50 g / m 2 · day g / m 2 · day, more preferably 10 to 30 g / m 2 · day.

Another aspect of the present invention relates to an organic electronic device encapsulation product such as a photovoltaic device, a transmitter, and an organic light emitting diode, and can be characterized by including the thin film encapsulant of the present invention in various forms described above.

More specifically, the organic electronic device encapsulation product of the present invention comprises a substrate 80 as shown in Fig. 6; An organic electronic device (100) formed on the substrate; And a thin film encapsulant for encapsulating the organic electronic device, wherein an encapsulating layer of the thin encapsulation material covers the organic electronic device.

In addition, the organic electronic device encapsulation product may further include a cover substrate 90.

Another aspect of the present invention relates to a method of encapsulating an organic electronic device using the thin film encapsulation material of the present invention, which comprises covering the organic electronic device with the thin encapsulation material of the present invention, Stacking the thin film plug on the organic electronic device so that the one surface and the organic electronic device are in contact with each other; And performing a pressing operation.

The step of performing the pressing may be carried out by a general method used in the related art. For example, it may be carried out by at least one method selected from a hot roll laminate, a hot press or a vacuum press, It is preferable to carry out vacuum pressing.

The method of encapsulating the organic electronic device according to the present invention may further include a step of curing the thin film encapsulant. The method of curing may include heating curing at 70 ° C to 110 ° C or ultraviolet (UV) curing . ≪ / RTI >

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

[ Example ]

Example  One

(One) For encapsulating layer  Preparation of solution

1) 22.21 g of 6FDA (4,4 '- (hexafluoroisopropylidene) diphthalic acid dianhydride) and 22.21 g of AHHFP (2,2'-bis (3-amino-4-hydroxyphenyl) -hexafluoropropane) Were added to 40 ml of NMP (N-methylpyrrolidone) and reacted to prepare a polyamic acid solution.

Next, the polyamic acid solution was thermally imidized at 150 ° C to convert it into the following polyimide compound. To heat-imidize the solvent, N-methylpyrrolidone (1-methyl-2- pyrrolidone) and the polyimide compound to prepare a 30 wt% polyimide resin.

2) Next, 10 g of the polyimide resin, 50 g of a silane-modified epoxy resin (epoxy equivalent weight: 200 g / eq) represented by the following formula 1-1 containing an 80 wt% epoxy, And 1 g of imidazole (a curing agent, manufactured by Shikoku Kasei Co., Ltd.) were placed in a reactor, and 224 g of methyl ethyl ketone (viscosity diluent) was added to dilute the inside of the reactor. Then, the inside of the reactor was replaced with nitrogen and homogenized.

 [Formula 1-1]

3) Next, the first copolymer solution containing the first copolymer represented by the following Chemical Formula 4-1 was prepared by stirring and polymerizing at a high speed for 1 hour in a nitrogen atmosphere.

[Formula 4-1]

이고, 상기 R⁵ 및 R⁶은 -CF₃이며, Y는 4가 유기기로서,

이고, Z는

이며, 상기 a은 1, b는 0이고, m은 2이다.In Formula 4-1, X is

, R ⁵ and R ⁶ are -CF ₃ , Y is a divalent organic group,

And Z is

, A is 1, b is 0, and m is 2.

(2) For moisture penetration prevention layer  Preparation of solution

1) 70 g of CaO (manufactured by Aldrich) as a moisture adsorbent was added to methyl ethyl ketone at a concentration of 30% by weight to prepare a water absorbent solution, and the water absorbent solution was milled for 24 hours by ball milling.

2) Separately from the above-mentioned moisture adsorbent solution, 30 g of the same polyimide resin prepared in the first copolymer solution, 50 g of a silane-modified epoxy resin (epoxy equivalent weight: 200 g / eq) containing 80 wt% 35 g of a resin (stability improver) and 1 g of imidazole (a curing agent, manufactured by Shikoku Chemical Co., Ltd.) were placed in a reactor, and 204 g of methyl ethyl ketone (viscosity diluent) was added to dilute the inside of the reactor. Homogenized, and then subjected to high-speed stirring and polymerization reaction for 1 hour to prepare a solution containing the second copolymer represented by the following formula (5-1).

 [Formula 5-1]

이고, 상기 R⁵ 및 R⁶은 -CF₃이며, Y는 4가 유기기로서,

이고, Z는

이며, 상기 a은 1, b는 0이고, M은 1이며, L은 1이다.
In Formula 5-1, X is

, R ⁵ and R ⁶ are -CF ₃ , Y is a divalent organic group,

And Z is

, A is 1, b is 0, M is 1, and L is 1.

3) Next, the solution containing the second copolymer and the water absorbent solution were mixed and mixed so that 75 parts by weight of the water absorbent was added to 100 parts by weight of the second copolymer to prepare a solution for the water permeation preventing layer.

(3) a pattern is formed Heterogeneous layer  And No pattern Of the release layer  Produce

1) Polyethylene terephthalate pellets were poured into an extruder set at 250 ° C, and a molten resin was discharged through a T-die. Thereafter, a convex pattern was formed on one surface of the release film using a calender roll equipped with a patterned polyethylene terephthalate resin (surface roughness Ra = 10 mu m), and then cooled to obtain a release layer 1 having a thickness of 20 mu m Prepared.

Next, an acrylic pressure-sensitive adhesive (trade name: DB-5S) was coated as an adhesive on the pattern forming surface of the release layer 1 on which the convex pattern was formed to form an adhesive layer 2 having a thickness of 5 탆, Or film).

2) The polyethylene terephthalate pellets were put into an extruder set at 250 DEG C, and the molten resin was discharged through a T-die. The discharged polyethylene terephthalate resin was then extruded through a patterned mirror-surface roll A non-patterned release layer 50 (or a pattern-free release film) having a thickness of 5 mu m was prepared.

(4) The membrane-  Produce

The solution for the sealing layer was coated on the convex pattern surface of the adhesive release layer of the pattern release layer using a comma coater and dried at 130 DEG C for 3 minutes to form an encapsulation layer having an average thickness of 15 mu m.

Next, a solution for the moisture permeation preventing layer was coated on one surface of the sealing layer using a comma coater, and dried at 130 DEG C for 3 minutes in a drier to form a moisture permeation preventing layer having an average thickness of 30 mu m.

Next, the non-patterned release layer 50 having the average thickness of 5 占 퐉 was laminated on one surface of the moisture permeation preventive layer to prepare a thin film plug for an organic electronic device.

Example  2

In the same manner as in Example 1, A solution for a sealing layer was prepared so that a polyimide resin was added in an amount of 10 parts by weight based on 100 parts by weight of the epoxy resin in the preparation of a solution for a sealing layer and then a thin film plug for an organic electronic device was prepared .

Example  3

In the same manner as in Example 1, A solution for the encapsulating layer was prepared so that the polyimide resin was added in an amount of 35 parts by weight based on 100 parts by weight of the epoxy resin in the preparation of the encapsulating layer solution and then a thin film encapsulating material for an organic electronic device was prepared .

Example  4

In the same manner as in Example 1, A polyimide resin was added in an amount of 50 parts by weight based on 100 parts by weight of the epoxy resin to prepare a solution for the moisture permeation preventive layer, .

Example  5

In the same manner as in Example 1, A polyimide resin was added in an amount of 80 parts by weight based on 100 parts by weight of the epoxy resin to prepare a solution for the moisture permeation preventive layer, .

Example  6

In the same manner as in Example 1, A water-impermeable layer was prepared by mixing the water-absorbent in an amount of 60 parts by weight based on 100 parts by weight of the second copolymer in the preparation of the water-impermeable layer solution, Was prepared.

Example  7

In the same manner as in Example 1, A water-impermeable layer solution was prepared by mixing the water-absorbing agent in an amount of 95 parts by weight based on 100 parts by weight of the second copolymer in the preparation of the water-immiscible layer solution, Was prepared.

Example  8

In the same manner as in Example 1, A membrane bag solution was prepared by mixing the water absorbent solution prepared in the solution for the moisture permeation preventive layer so that the moisture adsorbent was 10 parts by weight per 100 parts by weight of the first copolymer to prepare a solution for the encapsulating layer, To prepare a thin film plug for an organic electronic device.

Comparative Example  One

In the same manner as in Example 1, A butadiene-modified epoxy resin (manufactured by Kuko Chemical Co., Ltd., trade name: KD-175) was used in place of the silane-modified epoxy resin in the preparation of the solution for the sealing layer and the solution for the moisture permeation preventive layer.

Comparative Example  2

In the same manner as in Example 1, A thin membrane bag was prepared, but no moisture adsorbent was used in the preparation of the solution for the moisture permeation preventive layer.

Comparative Example  3

In the same manner as in Example 1, Except that the water-absorbing agent was added in an amount of 50 parts by weight based on 100 parts by weight of the second copolymer in the preparation of the solution for the water-impermeable layer, and a thin film bag was prepared using the second copolymer.

Comparative Example  4

In the same manner as in Example 1, A polyimide resin was not used in the preparation of the first copolymer solution.

Comparative Example  5

In the same manner as in Example 1, A thin membrane plug was prepared by preparing a solution for the encapsulation layer in the ratio of 100: 50 weight ratio of the silane-modified epoxy resin and the polyimide resin in preparing the solution for the encapsulation layer.

Comparative Example  6

In the same manner as in Example 1, A thin film bag was prepared by preparing a solution for the encapsulating layer in a 100: 5 weight ratio of the silane-modified epoxy resin and the polyimide resin when preparing the solution for the encapsulating layer.

Comparative Example  7

In the same manner as in Example 1, A patternless release layer (average thickness of 4 占 퐉) was prepared using a calender roll having no pattern in place of the release layer 1 having the convex pattern formed in Example 1, By fabricating the retardation, the base porcelain base was not formed in the sealing layer.

division Solution for encapsulating layer Solution for moisture permeation prevention layer Epoxy resin: Polyimide resin
(Weight ratio) Moisture adsorbent
(Parts by weight ⁽¹⁾ ) Epoxy resin: Polyimide resin
(Weight ratio) Moisture adsorbent
(Weight ^{portion (2)} ) Example 1 100: 20 Use X 100: 70 75 Example 2 100: 10 Use X 100: 70 75 Example 3 100: 35 Use X 100: 70 75 Example 4 100: 20 Use X 100: 50 75 Example 5 100: 20 Use X 100: 80 75 Example 6 100: 20 Use X 100: 70 60 Example 7 100: 20 Use X 100: 70 95 Example 8 100: 20 10 100: 70 75 Comparative Example 1 100: 20
(Butadiene-modified epoxy resin) Use X 100: 70 75 Comparative Example 2 100: 20 Use X 100: 70 Use X Comparative Example 3 100: 20 Use X 100: 70 50 Comparative Example 4 100: 0 Use X 100: 70 75 Comparative Example 5 100: 50 Use X 100: 70 75 Comparative Example 6 100: 20 Use X 100: 5 75 Comparative Example 7 100: 20 Use X 100: 70 75 (1): the amount (parts by weight) of the water adsorbent to 100 parts by weight of the first copolymer;
(2): the amount (parts by weight) of the water adsorbent to 100 parts by weight of the second copolymer;

Experimental Example  One : Moisture permeability  Measurement experiment

Measurement of the water vapor transmission rate (WVTR) and water vapor transmission rate (ASTM F1249) was performed. The thin film bag prepared in the above Examples and Comparative Examples was measured at a relative humidity of 38 ° C and 100% using a MOCON apparatus, And the moisture permeability was calculated. The results are shown in Table 2 below.

Experimental Example  2: Whether the physical damage of the organic electronic device occurred

The organic electroluminescent device was covered with the thin film encapsulant so that the sealing layer of the 3-inch organic light emitting device and the thin film encapsulant were in contact with each other using the thin film encapsulants prepared in the above Examples and Comparative Examples, The thin film encapsulation was cured by heating to 80 캜 to prepare an organic luminescent panel sealed with the thin encapsulation material of the present invention. Each of the organic light emitting panels manufactured in the following manner was allowed to stand in an environment of 85 ° C and 85% RH in a constant temperature and humidity chamber, and then the organic vapor deposition layer was observed to be broken. The results are shown in Table 2 below .

Experimental Example  3: Chemical damage of organic electronic devices

Silicon nitride (SiNx) used as a protective film of the organic electronic device was deposited to a thickness of 1 mu m in the glass. Next, each of the thin film encapsulants prepared in Examples and Comparative Examples was thermally compressed and cured on the SiNx evaporated film, and then allowed to stand at 85 ° C and 85% RH for 24 hours. Thereafter, a chemical change occurred in the SiNx evaporated film And the results are shown in Table 2 below.

division Moisture permeability
(g / m 2 · day) Organic vapor deposition
Whether physical damage occurred SiNx deposition film
Whether chemical damage has occurred Example 1 17 × × Example 2 39 × × Example 3 33 × × Example 4 45 × × Example 5 30 × × Example 6 49 × × Example 7 29 × × Example 8 21 × × Comparative Example 1 86 × △ Comparative Example 2 150 × ○ Comparative Example 3 95 × ○ Comparative Example 4 42 × △ Comparative Example 5 14 ○
(Thin film layer destruction) △ Comparative Example 6 180 △ △ Comparative Example 7 18 × △ X: No physical or chemical destruction occurred.
△: Physical or chemical destruction occurred slightly
○: Major physical or chemical destruction occurred

As a result of the experiment of Table 2, it was confirmed that the thin film encapsulant for organic electronic devices of the present invention has a very low moisture permeability of less than 50 g / m 2 · day. However, in Comparative Example 2 in which a moisture adsorbent was not used, Comparative Example 3 in which a moisture adsorbent was less contained in a moisture permeation preventive layer, and Comparative Example 6 in which a polyimide resin was used in a moisture permeation preventive layer, the moisture absorption rate was very high. Physical damage occurred to the organic vapor-deposited film of the luminescent panel or chemical damage occurred to the SiNx vapor-deposited film. The chemical damage is caused by the chemical component variation of the SiNx deposited film, and chemical damage occurs to the protective film (SiNx deposited film) due to the base component generation due to the hydration reaction.

In the case of Comparative Example 1 in which a butadiene-modified epoxy resin was used instead of the silane-modified epoxy resin, the moisture permeability was low and physical damage did not occur. However, due to the structural difference, Respectively.

In the case of Comparative Example 4 in which the polyimide resin was not used for the encapsulation layer, the moisture permeability was low, but some chemical damage occurred, which is considered to be caused by the volume expansion due to moisture permeation.

In the case of Comparative Example 5 in which the polyimide resin was used in an amount exceeding the proper amount as shown in the present invention in the encapsulation layer, the moisture permeability was very low, but physical damage occurred. This was due to the use of an excess amount of polyimide resin It is judged that this is due to adhesiveness problem.

In the case of Comparative Example 7 in which the base layer base was not formed in the sealing layer, bubbles remained, causing defects such as color distortion and defects when the organic electronic device was driven, and it was judged that the chemical damage caused by this occurred .

The thin film closure for an organic electronic device of the present invention having excellent moisture permeability is excellent in gas and moisture barrier properties, and can be used for encapsulating organic electronic devices (or organic electronic devices) such as display devices requiring protection against oxygen or water vapor, It is expected that the lifetime and the durability of these materials can be greatly improved.

Since the bubbles generated when the thin film closure body is sealed in the organic electronic device can be quickly removed, it is possible to solve the problem of causing color defects and defects when driving the organic electronic device due to bubbles. In addition, due to its excellent adhesive properties, heat resistance, and flexibility, it is possible to apply thin film coatings to electronic devices and wire packages as well as thin film packages through direct curing after spin coating.

1: release layer 2: adhesive layer
10: pattern releasing layer 20: sealing layer
25: base port base 30: water permeation prevention layer
40: Moisture absorbent 50: Non-pattern releasing layer
80: substrate 90: cover substrate
100: organic electronic device

Claims (15)

A resin encapsulation layer (20) comprising a first copolymer having a base porcelain base (25) formed on one surface thereof and polymerized with an epoxy resin and a polyimide resin; And
A moisture permeation preventive layer 30 comprising a second copolymer obtained by polymerizing an epoxy resin and a polyimide resin and a moisture adsorbent 40;
Wherein the thin film plug for organic electronic devices comprises: The thin film plug for organic electronic device according to claim 1, further comprising at least one layer selected from the pattern releasing layer (10) and the pattern free releasing layer (50). The method of claim 2, wherein the pattern release layer
A release layer (1) having a pattern formed on a surface of the substrate or a non-patterned surface; And
And a pressure-sensitive adhesive layer (2) having a pattern formed on one surface thereof. The epoxy resin composition according to claim 1, wherein the epoxy resin of the sealing layer and the water-
Dicyclopentadiene modified phenol type epoxy, biphenyl type epoxy, naphthalene type epoxy, cresol type epoxy, bisphenol type epoxy, xylox type epoxy, phenol novolac epoxy, triphenol methane type epoxy and alkyl modified And a silane-modified epoxy resin having a silane group introduced into at least one epoxy selected from triphenol methane epoxy,
Wherein the silane-modified epoxy resin of the sealing layer and the silane-modified epoxy resin of the moisture-permeation preventing layer are the same or different. 5. The organic electroluminescent device according to claim 4, wherein the silane-modified epoxy resin is a silane-modified epoxy resin comprising a copolymer containing a unit represented by the following formula (1) and a unit represented by the following formula retard;
[Chemical Formula 1]

In the above Formula 1, R ¹ is a hydrogen atom, C1 ~ C5 alkyl group, a C5 ~ C6 cycloalkyl group, a naphthalene group or a cycloalkylene group, a phenyl group, a C5 ~ C6 bisphenol group, wherein R ² is a C1 ~ C5 A straight-chain alkyl group,
(2)

In the general formula 2, R ³ and R ⁴ are independent as, R ³ and R ⁴ each represent a hydrogen atom, an alkyl group of C1 ~ C5, cycloalkyl of C5 ~ C6, C5 ~ C6 cycloalkyl group, a phenyl group, a naphthalene Or a bisphenol group.
The thin-film bag for organic electronic devices according to claim 1, wherein the moisture permeation preventive layer (30) comprises 60 to 100 parts by weight of the moisture adsorbent per 100 parts by weight of the second copolymer. The organic electroluminescent device according to claim 1, wherein the sealing layer (20) further comprises a moisture adsorbent, and the first copolymer layer comprises 0.1 to 20 parts by weight of a moisture adsorbent per 100 parts by weight of the first copolymer. Thin film plug for device. The organic electroluminescent device according to claim 1, wherein the polyimide resin of the sealing layer and the moisture permeation preventive layer are independent of each other and include a compound represented by the following formula (3):
(3)

In Formula 3, X is

And, as the R are independently selected from ⁵ and R ^6, R ⁵ is -CF ₃ or -CF ₂ CF _3, and R ⁶ is a hydrogen _{atom, -CF 3, -CF 2 CF 3} , an alkyl group or a phenyl group of C1 ~ C6 Y is a trivalent to hexavalent organic group,

,

,

,

,

,

or

And m is an integer satisfying 1? M? 4. The organic electroluminescent device according to claim 1, wherein the first copolymer is a copolymer comprising a unit represented by the following formula (4), and the second copolymer is a copolymer comprising a unit represented by the following formula A thin membrane plug for the device;
[Chemical Formula 4]

[Chemical Formula 5]

In the above formulas (4) and (5), X is

And, as the R are independently selected from ⁵ and R ^6, R ⁵ is -CF ₃ or -CF ₂ CF _3, and R ⁶ is a hydrogen _{atom, -CF 3, -CF 2 CF 3} , an alkyl group or a phenyl group of C1 ~ C6 Y is a trivalent to hexavalent organic group,

,

,

,

,

,

or

And Z is

A and b are independent, a is an integer satisfying 0? A? 5 and b is an integer satisfying 0? B? 5, and m is an integer satisfying 1? M? , M is 1 or 2, and L is an integer satisfying 1? L? 3. The method according to claim 1, wherein each of the sealing layer and the moisture permeation preventive layer is independent,
A curing agent containing at least one selected from amine-based curing agents, imidazole-based curing agents, phenol-based curing agents, phosphorus-based curing agents and acid anhydride-based curing agents;
Thermal crosslinking agents containing blocked isocyanates and polyhydroxystyrene;
A stability improver containing at least one selected from a phenoxy resin, an acrylate resin, a high molecular weight epoxy resin and an ultra high molecular weight epoxy resin; And
A viscosity diluent containing at least one selected from methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone and ethyl acetate;
Wherein the organic thin film encapsulant further comprises at least one selected from the group consisting of polyvinyl alcohol and polyvinyl alcohol. The method according to any one of claims 1, 6, and 7, wherein the moisture adsorbent
Zirconia, montmorillonite, TiO ₂ , ZrO ₂ , Al ₂ O ₃ , SiO ₂ , P ₂ O ₅ , Li ₂ O, Na ₂ O, BaO, CaO, MgO, Li ₂ SO ₄ , Na ₂ SO ₄ , CaSO ₄ , _{MgSO 4, CoSO 4, Ga 2} (SO 4) 3, Ti (SO 4) 2, NiSO 4, CaCl 2, MgCl 2, SrCl 2, YCl 3, CuCl 2, CsF, TaF 5, NbF 5, LiBr, CaBr ₂ , at least one selected from CeBr ₃ , SeBr ₄ , VBr ₃ , MgBr ₂ , BaI ₂ , MgI ₂ , Ba (ClO ₄ ) ₂ and Mg (ClO ₄ ) ₂ . retard. The thin film encapsulation material according to any one of claims 1 to 10,
Wherein the water vapor transmission rate (WVTR) is 10 to 50 g / m < 2 > · day in the measurement of the moisture permeability according to ASTM F1249 after curing. A substrate 80; An organic electronic device (100) formed on the substrate; And a thin film bag according to claim 12 for sealing the organic electronic device,
Wherein an encapsulating layer of the thin film encapsulation covers the organic electronic device. 14. The organic electronic device encapsulation product according to claim 13, wherein the organic electronic device comprises at least one selected from a photovoltaic device, a transmitter, and an organic light emitting diode (OLED). . Stacking the thin film encapsulant on the organic electronic device so that the organic electronic device is covered with the thin film encapsulant of claim 12, wherein the organic electronic device is in contact with one side of the encapsulating layer of the thin film encapsulant; And
Performing compression bonding;
Wherein the organic electroluminescent device is an organic electroluminescent device.

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