KR101566059B1 - Photocurable composition, barrier layer comprising the same and encapsulated apparatus comprising the same - Google Patents

Abstract

The present invention relates to a photocurable composition comprising (A) a photocurable monomer and (B) a monomer containing a hydroxy group of the general formula (1), a barrier layer comprising the same, and an encapsulated device comprising the same.

Description

FIELD OF THE INVENTION [0001] The present invention relates to a photocurable composition, a barrier layer containing the same, and an encapsulated device comprising the same. BACKGROUND OF THE INVENTION < RTI ID =

The present invention relates to a photocurable composition, a barrier layer comprising the same, and an encapsulated device comprising the same. More specifically, the present invention can realize an organic barrier layer having a low outgassing amount after curing and high adhesion to an inorganic barrier layer, a high photo-curability, and a low hardening shrinkage stress, so that an organic electroluminescent portion, It is possible to minimize the damage to the member for the apparatus including the apparatus and prolong the life thereof.

An organic light emitting diode (OLED) is a structure in which a functional organic layer is interposed between an anode and a cathode, and excitons having a high energy are recombined by holes injected into the anode and electrons injected into the cathode. Respectively. The exciton formed moves to the ground state and generates light of a specific wavelength. The organic electroluminescent part has advantages of self-emission, fast response, wide viewing angle, ultra-thin, high image quality and durability.

However, even when the organic electroluminescence portion is sealed, there is a problem that the organic material and / or the electrode material are oxidized due to moisture or oxygen introduced from the outside, or outgas generated from the outside or the inside, and the performance and lifetime of the organic electroluminescence portion are deteriorated. In order to overcome such a problem, a method of applying a photocurable sealing agent to a substrate on which an organic electroluminescent unit is formed, attaching a transparent or opaque moisture absorber, or forming a frit has been proposed.

Recently, a method of encapsulating an organic electroluminescent portion with an organic barrier layer and an inorganic barrier layer has been developed. The organic electroluminescent portion is encapsulated by complementing the organic barrier layer and the inorganic barrier layer. For this purpose, the organic barrier layer must have low outgassing amount and low moisture permeability as described above, but should have high adhesion to the inorganic barrier layer. If the adhesive strength is low, separation between the barrier layers may occur, and ultimately, sealing of the organic electroluminescent portion may be difficult.

For example, Korean Unexamined Patent Publication No. 2006-0084978 proposes an encapsulation structure of an organic light emitting diode device using a sealing film formed of a moisture-permeation inhibiting material of any one of a silicone compound and a polymer resin.

It is an object of the present invention to provide a photocurable composition capable of realizing an organic barrier layer having a significantly low outgassing amount and high adhesion to an inorganic barrier layer.

It is another object of the present invention to provide a photocurable composition capable of realizing an organic barrier layer which is high in photo-curability and does not cause shift due to curing shrinkage stress after curing.

It is yet another object of the present invention to provide an encapsulated device comprising an organic barrier layer formed of the photocurable composition, a barrier stack comprising the organic barrier layer, and the barrier stack.

One aspect of the present invention is a photocurable composition comprising (A) a photocurable monomer, (B) a monomer of the following general formula:

≪ Formula 1 >

An encapsulated device according to another aspect of the present invention comprises a member for an apparatus; And a barrier stack comprising an inorganic barrier layer and an organic barrier layer formed on the device member, wherein the organic barrier layer has an adhesion to the inorganic barrier layer of 7-50 kgf / (mm) ² .

The present invention provides an organic barrier layer capable of realizing an organic barrier layer having a remarkably low outgassing amount and a high adhesion to an inorganic barrier layer and having a high photo curability so that no shift due to hardening shrinkage stress occurs after curing. 0.0 > photocurable < / RTI >

1 is a cross-sectional view of an encapsulated device of one embodiment of the present invention.
2 is a cross-sectional view of an encapsulated device of another embodiment of the present invention.
3 is a cross-sectional view of an encapsulated device of another embodiment of the present invention.

As used herein, unless otherwise defined, at least one hydrogen atom of the functional groups of the present invention is optionally substituted with at least one substituent selected from the group consisting of halogen (F, Cl, Br or I), a hydroxy group, a nitro group, a cyano group, (R "), R ', R" and R "' each independently represent an alkyl group having 1 to 10 carbon atoms, A substituted or unsubstituted alkyl group having 1-20 carbon atoms, a substituted or unsubstituted aryl group having 6-30 carbon atoms, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryl group having 1-20 carbon atoms, a substituted or unsubstituted aryl group having 1-20 carbon atoms, an amidino group, a hydrazine or hydrazone group, Substituted or unsubstituted C3-C30 cycloalkyl group, substituted or unsubstituted C3-C30 heteroaryl group, or substituted or unsubstituted C2-C30 heterocycloalkyl group.

In this specification, 'hetero' means at least one of N, O, S, P.

In the present specification, '*' denotes an inter-element linkage site in a molecule.

One aspect of the present invention is a photocurable composition comprising (A) a photocurable monomer and (B) a monomer containing a hydroxy group.

(A) Photocurable Monomer

The photocurable monomer may be a photocurable functional group, for example, a monomer having a (meth) acrylate group, a vinyl group, or the like.

The photocurable monomer may include a monofunctional monomer having an unsaturated group, a polyfunctional monomer, or a mixture thereof. Preferably, the photocurable monomer comprises a monomer having 1-30, preferably 1-20, more preferably 1-5, substituted or unsubstituted vinyl, acrylate, or methacrylate groups can do.

Photocurable monomers may comprise a mixture of monofunctional monomers and polyfunctional monomers. The monofunctional monomer: polyfunctional monomer in the mixture may be contained in a weight ratio of 1: 0.1 to 1:10, preferably 1: 2 to 1: 5, more preferably 1: 3 to 1: 4.

The photocurable monomer is an aromatic compound having 6 to 20 carbon atoms and having a substituted or unsubstituted vinyl group; An alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or an unsaturated carboxylic acid ester having a hydroxy group and an alkyl group having 1 to 20 carbon atoms; An unsaturated carboxylic acid ester having an aminoalkyl group having from 1 to 20 carbon atoms; Vinyl esters of saturated or unsaturated carboxylic acids having from 1 to 20 carbon atoms; Unsaturated carboxylic acid glycidyl esters having 1 to 20 carbon atoms; Vinyl cyanide compounds; Unsaturated amide compounds; A mono-alcohol or a polyfunctional (meth) acrylate of a polyhydric alcohol, and the like.

For example, the photocurable monomer may be an aromatic compound having 6 to 20 carbon atoms and having an alkenyl group including a vinyl group such as styrene,? -Methylstyrene, vinyltoluene, vinylbenzyl ether, and vinylbenzyl methyl ether; (Meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) (Meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, decyl (meth) acrylate, Unsaturated carboxylic acid esters such as acrylate and phenyl (meth) acrylate; Unsaturated carboxylic acid aminoalkyl esters such as 2-aminoethyl (meth) acrylate and 2-dimethylaminoethyl (meth) acrylate; Saturated or unsaturated carboxylic acid vinyl esters such as vinyl acetate and vinyl benzoate; Unsaturated carboxylic acid glycidyl esters having 1 to 20 carbon atoms such as glycidyl acrylate and glycidyl methacrylate; Vinyl cyanide compounds such as acrylonitrile and methacrylonitrile; Unsaturated amide compounds such as acrylamide and methacrylamide; Acrylates such as ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, 1,4-butanediol di (Meth) acrylate, octyldiol di (meth) acrylate, nonyldiol di (meth) acrylate, decanyl diol di (meth) acrylate, (Meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol di (meth) acrylate, Acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol hexa (meth) acrylate, bisphenol A di (meth) (Meth) acrylate, novolak epoxy (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (Meth) acrylate and the like, monofunctional or polyfunctional (meth) acrylate of a polyhydric alcohol, and the like, but is not limited thereto. The 'polyhydric alcohol' may be an alcohol having two or more hydroxyl groups and having 2 to 20, preferably 2 to 10, more preferably 2 to 6 alcohols.

Preferably, the photo-curable monomer may comprise a non-hydroxyl clock monomer that does not contain a hydroxy group. (Meth) acrylate having an alkyl group of 1-20 carbon atoms, di (meth) acrylate of a diol having 2-20 carbon atoms, tri (meth) acrylate of triol having 3-20 carbon atoms, Of tetra (meth) acrylate of tetraol.

The photocurable monomer may be contained in the composition in an amount of 1 to 99 parts by weight based on 100 parts by weight of (A) + (B). Preferably 20 to 95 parts by weight, more preferably 30 to 95 parts by weight, and most preferably 60 to 80 parts by weight. In this range, the photo-curable composition is resistant to plasma, and it is possible to lower or prevent degradation of outgas and moisture permeability that may be generated from plasma generated in manufacturing the thin film encapsulation layer.

(B) containing a hydroxy group Monomer

The hydroxyl group-containing monomer may be a photocurable monomer containing a hydroxy group and having a photocurable functional group (e.g., a (meth) acrylate group, a vinyl group, etc.).

In an embodiment, the hydroxy-containing monomer may be represented by the formula:

≪ Formula 1 >

(Wherein R ₁ is a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, or a substituted or unsubstituted cycloalkylene group having 5 to 20 carbon atoms,

R ₂ represents a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms or a group represented by -O-, -S- or -NR- (R is hydrogen, an alkyl group having 1-10 carbon atoms, an aryl group having 6-20 carbon atoms Is an alkylene group having from 1 to 10 carbon atoms,

X ₁ and X ₂ are the same or different and each represents hydrogen, a substituted or unsubstituted alkyl group having 1-20 carbon atoms, a substituted or unsubstituted aryl group having 6-20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 5-20 carbon atoms, Or a hydroxy group,

At least one of X ₁ and X ₂ is a hydroxy group,

Z ₁ and Z ₂ are the same or different and represent hydrogen, the following formula 2, 3 or 4,

(2)

(3)

≪ Formula 4 >

(Wherein * is a connecting site of carbon of R ² and R ³ ,

R ₄ and R ₅ are a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, a substituted or unsubstituted arylene group having 6 to 20 carbon atoms,

R < ₆ > is hydrogen or a substituted or unsubstituted alkyl group having 1-10 carbon atoms,

and n is an integer of 0 to 20)

At least one of Z ₁ and Z ₂ is the above-described formula (2), (3) or (4)

Preferably, the hydroxyl group-containing monomer may be represented by the following formula (1-1):

≪ Formula 1-1 >

(Wherein Z ₁ , Z ₂ , X ₁ , X ₂ and R ₁ are as defined above,

R ₂₁ and R ₂₂ are the same or different and are each a substituted or unsubstituted alkylene group having 1-20 carbon atoms,

X is O, S or NR (R is hydrogen, an alkyl group having 1-10 carbon atoms, or an aryl group having 6-20 carbon atoms)).

Specifically, the hydroxyl group-containing monomer may be represented by any one of the following formulas (5) to (9):

≪ Formula 5 >

(6)

≪ Formula 7 >

(8)

≪ Formula 9 >

The hydroxyl group-containing monomer may be synthesized by a conventional synthetic method, or a commercially available product may be purchased and used.

The hydroxyl group-containing monomer is included in the photocurable composition together with the photocurable monomer, so that a layer having a significantly low outgassing amount can be realized and the photo-curability can be increased. In addition, the monomer having a hydroxyl group can realize an organic barrier layer having a high adhesion to the inorganic barrier layer in a sealing structure in which the conventional inorganic barrier layer and the organic barrier layer are deposited.

The hydroxy group-containing monomer may be contained in the composition in an amount of 1 to 99 parts by weight based on 100 parts by weight of (A) + (B). Preferably 5-80 parts by weight, more preferably 5-70 parts by weight, and most preferably 20-40 parts by weight. Within this range, the photocurable composition can increase the adhesion to the inorganic barrier layer.

The composition may further comprise (C) an initiator.

(C) Initiator

The initiator may include, without limitation, conventional photopolymerization initiators capable of carrying out photo-curable reactions.

For example, the photopolymerization initiator may include triazine, acetophenone, benzophenone, thioxanthone, benzoin, phosphorus, oxime, or a mixture thereof.

 Examples of triazine derivatives include 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (3 ', 4'-dimethoxysti (Trichloromethyl) -s-triazine, 2- (4'-methoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) (Trichloromethyl) -s-triazine, bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphtho- Bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphtho-1-yl) -4,6- (Piperonyl) -6-triazine, 2,4- (trichloromethyl (4'-methoxystyryl) -6-triazine or mixtures thereof.

Examples of the acetophenone-based solvents include 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyltrichloroacetophenone, pt-butyldichloro 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropane-1-one, 2,2'-dichloroacetophenone, Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, or mixtures thereof.

Examples of the benzophenone-based compounds include benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4,4'-bis (dimethylamino) benzophenone, 4,4'-dichlorobenzo Phenone, 3,3'-dimethyl-2-methoxybenzophenone, or a mixture thereof.

Examples of thioxanthone include thioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2-chlorothioxanthone or And mixtures thereof.

The benzoin group may be benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal or a mixture thereof.

Phosphorous can be bisbenzoylphenylphosphine oxide, benzoyldiphenylphosphine oxide or mixtures thereof.

The oxime system was prepared by reacting 2- (o-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione and 1- (o-acetyloxime) 2-methylbenzoyl) -9H-carbazol-3-yl] ethanone, or mixtures thereof.

 The initiator may be included in the composition in an amount of 0.1 to 20 parts by weight based on 100 parts by weight of (A) + (B). Within the above range, photopolymerization can sufficiently take place at the time of exposure, and the transmittance can be prevented from being lowered due to the unreacted initiator remaining after the photopolymerization. Preferably from 0.5 to 10 parts by weight, more preferably from 1 to 8 parts by weight.

The photo-curing composition may have a photo-curing rate of 90% or more. In the above range, a layer in which a shift is not generated due to a low hardening shrinkage stress after curing can be implemented and used for sealing the device. Preferably 90-99%.

The photo-curing rate can be measured by a usual method. For example, the photocurable composition is applied onto a glass substrate and cured at 100 mW / cm < ² > for 10 seconds. The cured film is collected and the photo-curability is measured using FT-IR. The photo-curing rate is obtained under the conditions described in the following experimental examples.

The photocurable composition of the present invention may be a composition for encapsulation capable of forming an organic barrier layer which encapsulates a member for an apparatus. The device member may be an organic electroluminescent unit, an organic light emitting device, a flexible organic light emitting device, a lighting device, a metal sensor pad, a micro disk laser, an electrochromic device, a photochromic device, a microelectromechanical system, Circuit, a charge coupled device, a light emitting polymer, and a light emitting diode.

An organic barrier layer, which is another aspect of the present invention, may be formed from the photocurable composition. The organic barrier layer can be formed by photo-curing the composition described above. The composition can be coated to a thickness of 0.1 탆 to 20 탆 and cured by irradiation at 10-500 mW / cm 2 for 1-50 seconds. The organic barrier layer can be used as an encapsulation of the device member by forming a barrier stack with the inorganic barrier layer described below.

The organic barrier layer may have an adhesion to an inorganic barrier layer, for example aluminum oxide, silicon nitride, of 7-50 kgf / (mm) ² , preferably 7-26 kgf / (mm) ² .

 The organic barrier layer minimizes the outgassing effect on the device member due to the small amount of outgas generation, thereby preventing the member from being decomposed by outgas or degraded in performance. Specifically, the organic barrier layer may have an outgassing amount of 1000 ppm or less. In the above-mentioned range, there is little effect when applied to members, and the life can be lengthened. Preferably from 10 to 1000 ppm, more preferably from 100 to 300 ppm.

The amount of generated outgas can be measured by a conventional method. For example, a photocurable composition is applied onto a glass substrate and irradiated with 100 mW / cm ² for 10 seconds to be UV-cured to obtain a 20 cm x 20 cm x 3 m (width x length x thickness) organic barrier layer. The specimen is obtained under the conditions described in the following experimental examples.

The organic barrier layer is low in moisture permeability and can minimize the effect of moisture on the device. The moisture permeability may be 4.5 g / m ² .24 hr or less with respect to the thickness direction of the organic barrier layer. Within this range, it can be used for sealing of the device, preferably 1.0-4.5 g / m ² .24 hr, more preferably 2.1-4.1 g / m ² .24 hr.

The moisture permeability can be measured by a conventional method. For example, the moisture permeability is measured using a moisture permeability meter (PERMATRAN-W 3/33, MOCON) shown in Fig. The photocurable composition is applied onto the Al sample holder of Fig. 1 and irradiated with 100 mW / cm < ² > for 10 seconds to be UV-cured to form a cured specimen having a film thickness of 5 mu m. The moisture permeability is measured for 24 hours at 37.8 캜 and 100% relative humidity for a film thickness of 5 탆.

The thickness of the organic barrier layer is not particularly limited, but may be 0.1 탆 to 20 탆, preferably 1 탆 to 10 탆.

A barrier stack, another aspect of the present invention, can comprise the organic barrier layer and the inorganic barrier layer.

The inorganic barrier layer may be formed of an inorganic layer different from the organic barrier layer, so that the effect of the organic barrier layer can be compensated.

The inorganic barrier layer is not particularly limited but may be a metal, a metal oxide, a metal nitride, a metal carbide, a metal oxynitride, a metal oxygen boride, or a mixture thereof. The metal may be silicon, selenium, zinc, antimony, aluminum, transition metal, lanthanide, indium, germanium, tin, bismuth, However, it is not limited thereto. And specifically, the inorganic barrier layer is SiOx, SizNx, SiOxNy, ZnSe, ZnO, Sb 2 O 3, Al 2 O 3, In 2 O 3, SnO 2 ( In the above, x is 1-5, y is 1-5, And z is 1-2), and the like.

The inorganic barrier layer and the organic barrier layer may be deposited by a vacuum process, such as sputtering, chemical vapor deposition, plasma chemical vapor deposition, evaporation, sublimation, electron cyclotron resonance-plasma vapor deposition, and combinations thereof.

The organic barrier layer secures the above-mentioned physical properties. As a result, when the organic barrier layer is deposited alternately with the inorganic barrier layer, the smoothing property of the inorganic barrier layer can be secured. In addition, the organic barrier layer can prevent the defects of the inorganic barrier layer from propagating to another inorganic barrier layer.

The barrier stack includes the organic barrier layer and the inorganic barrier layer, but the number of barrier stacks is not limited. And the level of permeation resistance to oxygen and / or moisture and / or water vapor and / or chemicals of the combination of barrier stacks.

In the barrier stack, the organic barrier layer and the inorganic barrier layer can be alternately deposited. This is due to the effect on the organic barrier layer produced due to the physical properties of the composition described above. As a result, the organic barrier layer and the inorganic barrier layer can complement or enhance the sealing effect on the device.

In the barrier stack, the organic barrier layer and the inorganic barrier layer may be deposited a total of 10 times or less (e.g., 2-10 times), preferably 7 times or less (e.g., 2-7 times).

Preferably, the organic barrier layer and the inorganic barrier layer may be alternately deposited in two or more layers, and more preferably, the inorganic barrier layer-organic barrier layer-inorganic barrier layer-organic barrier layer-inorganic barrier layer- - inorganic barrier layer. Most preferably, it may be a seven-layer structure of a first inorganic barrier layer-organic barrier layer-second inorganic barrier layer-organic barrier layer-third inorganic barrier layer-organic barrier layer-fourth inorganic barrier layer. The first and fourth inorganic barrier layers may be aluminum oxide, and the second and third inorganic barrier layers may be silicon nitride.

In the barrier stack, the thickness of one organic barrier layer may be 0.1 占 퐉 -20 占 퐉, preferably 1 占 퐉 -10 占 퐉, and the thickness of one inorganic barrier layer may be 5 nm-500 nm, more preferably 5 nm-200 nm.

The barrier stack may be a thin-film encapsulant and have a thickness of 5 占 퐉 or less, preferably 1.5 占 퐉 to 5 占 퐉.

A sealed device, which is another aspect of the present invention, may comprise a member for the device, and the barrier layer. The device may include a member for the device and may include a display device.

1 to 3 are sectional views of an encapsulated device of one embodiment of the present invention.

1, an encapsulated device 100 is fabricated by depositing a device member (e.g., an organic light emitting device) 20 on a substrate 10 and depositing an inorganic barrier layer 31 and an organic barrier layer 32 thereon, Lt; RTI ID = 0.0 > 30 < / RTI >

2, an encapsulated device 200 is fabricated by depositing a device member (e.g., an organic light emitting device) 20 over a substrate 10 and depositing an inorganic barrier layer 31 and an organic barrier layer 32 thereon, Lt; RTI ID = 0.0 > 30 < / RTI >

1 is a specific example in which the device member 20 and the inorganic barrier layer 31 are in contact with each other. 2 shows an embodiment in which an empty space 40 is formed between the device member 20 and the inorganic barrier layer 31. In Fig.

3, an encapsulated device 300 is fabricated by depositing a device member (e.g., an organic light emitting device) 20 over a substrate 10 and depositing an inorganic barrier layer 31a-organic barrier layer 32a thereover, -Inorganic barrier layer 31b -Organic barrier layer 32b -Inorganic barrier layer 31c -Organic barrier layer 32c -Inorganic barrier layer 31d are sequentially deposited (seven-layer structure) to form a barrier stack This is an example.

The materials for the device, the organic barrier layer, the inorganic barrier layer, and the barrier stack are as described above.

The substrate is not particularly limited as long as it is a substrate on which a member for an apparatus can be laminated. For example, a transparent glass, a plastic sheet, a silicon or metal substrate, or the like.

Depending on the type of the member for the apparatus, the substrate may not be included.

The encapsulated device can be manufactured in a conventional manner. A device member is formed on the substrate and an inorganic barrier layer is formed. The sealing composition can be applied by spin coating, slit coating or the like, and the organic barrier layer can be formed by irradiating light. The formation process of the inorganic barrier layer and the organic barrier layer may be repeated (preferably, the inorganic barrier layer-organic barrier layer-inorganic barrier layer-organic barrier layer-inorganic barrier layer-organic barrier layer-inorganic barrier layer) ).

Methods for forming the inorganic barrier layer and the organic barrier layer are not limited, but may include deposition.

In one embodiment, the encapsulated device comprises an organic electroluminescent display device, a substrate, an organic electroluminescent portion formed on the substrate, an inorganic barrier layer that encapsulates the organic electroluminescent portion, and an organic Barrier layer, and the organic barrier layer may have an outgassing amount of 1000 ppm or less.

In another embodiment, the encapsulated device comprises an organic electroluminescent display device, a substrate, an organic electroluminescent portion formed on the substrate, an inorganic barrier layer that encapsulates the organic electroluminescent portion, and an organic Barrier layer, and the organic barrier layer may have an adhesion to the inorganic barrier layer of 7-50 kgf / (mm) ² , preferably 7-26 kgf / (mm) ² .

A method of encapsulating an apparatus, which is another aspect of the present invention, may comprise the steps of:

Positioning or laminating adjacent one or more device members to a substrate; And

Forming at least one barrier stack that includes at least one inorganic barrier layer and an organic barrier layer and is adjacent to the device member.

 Details of the substrate, the device member, the inorganic barrier layer, the organic barrier layer, and the barrier stack are as described above.

The device member is positioned or laminated adjacent to the substrate. This can be performed in the same manner as the inorganic barrier layer and the organic barrier layer formation method, but is not limited thereto.

The inorganic barrier layer and the organic barrier layer may be formed by a vacuum process, such as sputtering, chemical vapor deposition, plasma chemical vapor deposition, evaporation, sublimation, electron cyclotron resonance-plasma vapor deposition, and combinations thereof.

Hereinafter, the configuration and operation of the present invention will be described in more detail with reference to preferred embodiments of the present invention. It is to be understood, however, that the same is by way of illustration and example only and is not to be construed in a limiting sense.

[Synthesis Example 1] [Synthesis of Compound of Formula 5]

50 g of glycidyl methacrylate (Aldrich), 41 g of 2-hydroxyethyl acrylate (Aldrich) and 1 g of triphenylphosphine were placed in a 500 ml flask equipped with a cooling tube and a stirrer, and stirred at 100 ° C for 6 hours After cooling, a GC purity of 96% was obtained through a silica gel column to obtain 75 g of a compound of the formula (5).

[Synthesis Example 2] [Synthesis of Compound of Formula 6]

50 g of glycidyl methacrylate (Aldrich), 46 g of 2-hydroxyethyl methacrylate (Aldrich) and 1 g of triphenylphosphine (Aldrich) were placed in a 500 ml flask equipped with a cooling tube and a stirrer, After stirring for 6 hours, the solution was cooled, and a GC purity of 95% was obtained through a silica gel column to obtain 78 g of a compound of the formula (6).

[Synthesis Example 3] [Synthesis of Compound of Formula 7]

50 g of glycidyl methacrylate (Aldrich), 26 g of acrylic acid (Aldrich) and 1 g of triphenylphosphine (Aldrich) were added to a 500 ml flask equipped with a cooling tube and a stirrer, and the mixture was stirred at 100 ° C. for 6 hours, A GC purity of 98% 81 g of the compound of the formula 7 can be obtained through a silica gel column.

[Synthesis Example 4] [Synthesis of Compound of Formula 8]

50 g of glycidyl methacrylate (Aldrich), 31 g of methacrylic acid (Aldrich) and 1 g of triphenylphosphine (Aldrich) were placed in a 500 ml flask equipped with a cooling tube and a stirrer, and stirred at 100 ° C for 6 hours After cooling, a GC purity of 98% 79 g of the compound of the formula 8 can be obtained through a silica gel column.

[Synthesis Example 5] [Synthesis of Compound of Formula 9]

50 g of glycidyl methacrylate (Aldrich), 51 g of 4-hydroxybutyl acrylate (LG Chemical) and 1 g of triphenylphosphine (Aldrich) were placed in a 500 ml flask equipped with a cooling tube and a stirrer, After stirring for 6 hours, the mixture was cooled, and a GC purity of 94% was obtained through a silica gel column to obtain 79 g of a compound represented by the formula (9).

≪ Formula 5 >

(6)

≪ Formula 7 >

(8)

≪ Formula 9 >

Specific specifications of the components used in the following examples and comparative examples are as follows.

(A1) hexyl acrylate, (A2) hexanediol diacrylate, (A3) pentaerythritol tetraacrylate (above, Aldrich)

(B4) a compound of Synthesis Example 4, (B5) a compound of Synthesis Example 5 (B) a compound of Synthesis Example 3, compound

(C) Initiator: Darocur TPO (BASF)

Examples Comparative Example

(B) a hydroxyl group-containing monomer, and (C) an initiator were placed in a 125 ml brown polypropylene bottle in the contents (unit: parts by weight) shown in the following Table 2 and mixed for 3 hours using a shaker, .

The following properties of the compositions prepared in Examples and Comparative Examples were evaluated, and the results are shown in Table 2 below.

1. Outgassing amount of organic barrier layer: A photocurable composition was applied on a glass substrate by spraying, and irradiated at 100 mW / cm < ² > to be UV-cured to obtain an organic barrier layer sample 20 cm x 20 cm x 3 m (width x length x thickness) . For the specimen, use a GC / MS instrument (Perkin Elmer Clarus 600). As GC / MS, a helium gas (flow rate: 1.0 mL / min, average velocity = 32 cm / s) was used as a mobile phase using a DB-5MS column (length: 30 m, diameter: 0.25 mm, ), The split ratio is 20: 1, the temperature condition is kept at 40 ° C for 3 minutes, then the temperature is raised at a rate of 10 ° C / minute, and then the temperature is maintained at 320 ° C for 6 minutes. The adsorbent was Tenax GR (5% phenylmethylpolysiloxane), and the adsorbent was N2 purge at a flow rate of 300 mL / min. . As a standard solution, a calibration curve is prepared at 150 ppm, 400 ppm, and 800 ppm of a toluene solution in n-hexane, and R2 value is obtained as 0.9987. The above conditions are summarized in Table 1 below.

division
Detail Collection conditions





Glass size: 20cm * 20cm Collecting container: Tedlar bag Collecting temperature: 90 ℃ Collection time: 30 min N2 purge flow rate: 300 mL / min Adsorbent: Tenax GR (5% phenylmethylpolysiloxane) Calibration Curve Condition


Standard solution: Toluene in n-Hexane Concentration range: 150 ppm, 400 ppm, 800 ppm R2: 0.9987 GC / MS conditions



Column DB-5MS? 30 m 0.25 mm 0.25 占 퐉
(5% phenylmethylpolysiloxane) Mobile phase He Flow 1.0 mL / min (Average velocity = 32 cm / s) Split Split ratio = 20: 1 method 40 캜 (3 min) -10 캜 / min? 320 캜 (6 min)

2. Light curing rate: The intensity of the absorption peak at around 1635 cm -1 (C = C) and around 1720 cm -1 (C = O) was measured using a FT-IR (NICOLET 4700, Thermo) do. The photocurable composition is applied on a glass substrate by spraying and irradiated at 100 J / cm < 2 > for 10 seconds to be UV-cured to obtain a specimen of 20 cm x 20 cm x 3 mu m (width x length x thickness). The cured film was collected and the intensity of the absorption peak at around 1635 cm -1 (C = C) and around 1720 cm -1 (C = O) was measured using FT-IR (NICOLET 4700, Thermo). The photo-curing rate is calculated according to the following formula (1).

<Formula 1>

Photocuring rate (%) = {1- (A / B)} x 100

(Where A is the ratio of the intensity of the absorption peak at around 1635 cm -1 to the intensity of the absorption peak at around 1720 cm -1 for the cured film,

B is the ratio of the intensity of the absorption peak at around 1635 cm -1 to the intensity of the absorption peak at around 1720 cm -1 for the photocurable composition)

3.Die share strength 0.01 g of the composition shown in Table 2 was applied to a glass plate having a thickness of 1: 5 mm * 5 mm * 2 mm and a glass plate of 20 mm * 80 mm * 2 mm (width * length * thickness) Leave. The die share strength was measured with a Daci 4000 bond tester after curing with a D-bulb light source at an intensity of 1000 J / cm2.

4. Dye share strength: 0.01 g of the composition of the following Table 2 was applied to a glass plate coated with silicon nitride and having a thickness of 5 mm * 5 mm * 2 mm (width * length * thickness), and 20 mm * 80 mm * 2 mm Place a glass plate coated with SiNx. The die share strength was measured with a Daci 4000 bond tester after curing with a D-bulb light source at an intensity of 1000 J / cm2.

Example Comparative Example One 2 3 4 5 6 7 8 9 10 One 2 A A1 15 15 15 15 15 15 15 15 15 15 15 30 A2 35 55 35 55 35 55 35 55 35 55 75 60 A3 10 10 10 10 10 10 10 10 10 10 10 10 B B1 40 20 - - - - - - - - - - B2 - - 40 20 - - - - - - - - B3 - - - - 40 20 - - - - - - B4 - - - - - - 40 20 - - - - B5 - - - - - - - - 40 20 - - C 5 5 5 5 5 5 5 5 5 5 5 5 Outgassing Amount (ppm) 110 120 110 170 160 190 210 240 290 320 340 1290 Light curing rate (%) 96.6 93.1 93.3 90.6 94.8 93.2 90.4 90.2 97.4 92.5 88.5 91.6 Die share strength 1 (kgf / (mm) ² ) 24.5 23.2 22.6 20.5 18.2 16.6 18.4 15.2 26.4 23.2 6.4 4.9 Die share strength 2 (kgf / (mm) ² ) 16.3 15.9 15.5 13.8 12.1 10.8 11.9 8.1 17.2 15.8 4.1 2.3

As shown in Table 2, the coating formed from the photocurable compositions of the present invention had a low outgass evaluation value and a high photo-curability when outgassing the comparative example. In addition, the coating film formed of the photocurable composition of the present invention had a very high adhesion to the inorganic barrier layer including silicon oxide and silicon nitride, compared with the comparative example.

It is to be understood that the present invention is not limited to the above embodiments and drawings and that various changes and modifications may be made therein without departing from the spirit and scope of the present invention. As will be understood by those skilled in the art. Therefore, it should be understood that the above-described embodiments and drawings are to be considered in all respects as illustrative and not restrictive.

Claims (18)

(A) a photo-curable monomer and (B) a monomer having a hydroxyl group of the following formula (1):
&Lt; Formula 1 >

(Wherein R ₁ is a substituted or unsubstituted alkylene group having 1-20 carbon atoms, a substituted or unsubstituted arylene group having 6-20 carbon atoms or a substituted or unsubstituted cycloalkylene group having 5-20 carbon atoms,
R ₂ represents a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms or a group represented by -O-, -S- or -NR- (R is hydrogen, an alkyl group having 1-10 carbon atoms, an aryl group having 6-20 carbon atoms Is an alkylene group having from 1 to 10 carbon atoms,
X ₁ and X ₂ are the same or different and each represents hydrogen, a substituted or unsubstituted alkyl group having 1-20 carbon atoms, a substituted or unsubstituted aryl group having 6-20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 5-20 carbon atoms, Lt; / RTI &gt;
At least one of X ₁ and X ₂ is a hydroxy group,
Z ₁ and Z ₂ are the same or different and represent hydrogen, the following formula 2, 3 or 4,
(2)

(3)

&Lt; Formula 4 &gt;

(Wherein R ₄ and R ₅ are each independently a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms or a substituted or unsubstituted arylene group having ₆ to 20 carbon atoms and R ₆ is hydrogen or substituted or unsubstituted And n is an integer of 0 to 20,
At least one of Z ₁ and Z ₂ is the above-described formula (2), (3) or (4). The photocurable composition for encapsulating an organic light emitting device according to claim 1, wherein the monomer (B) comprises at least one compound having one of the following formulas (5) to (9)
&Lt; Formula 5 >

(6)

&Lt; Formula 7 >

(8)

&Lt; Formula 9 >

.
The photocurable composition for encapsulating an organic light emitting device according to claim 1, wherein the photocurable monomer comprises a monomer having 1-30 substituted or unsubstituted vinyl groups, acrylate groups, or methacrylate groups.
The photocurable monomer according to claim 1, wherein the photocurable monomer is selected from the group consisting of (meta) acrylate having an alkyl group of 1-20 carbon atoms, di (meth) acrylate of a diol having 2-20 carbon atoms, tri ) Acrylate, and tetra (meth) acrylate of tetraol having 4-20 carbon atoms.
The organic electroluminescent device according to claim 1, wherein the photocurable composition for encapsulating an organic light emitting device comprises 1-99 parts by weight of (A) and 1-99 parts by weight of (B) in 100 parts by weight of (A) + (B) Curing composition for sealing.
The photocurable composition according to claim 1, wherein the photocurable composition for encapsulating an organic light emitting device further comprises (C) an initiator.
The photocurable composition according to claim 6, wherein the initiator comprises a photopolymerization initiator.
The composition according to claim 6, wherein the photocurable composition for encapsulating an organic light emitting device comprises 1-99 parts by weight of (A) and 1-99 parts by weight of (B) in 100 parts by weight of (A) + (B) A) + (B), and 0.1-20 parts by weight of the above (C) relative to 100 parts by weight of (B).
9. A barrier layer comprising a cured product of the photocurable composition for encapsulating an organic light emitting element according to any one of claims 1 to 8.
A member for a device; And
And a barrier stack formed on the member for the device, the barrier stack including an inorganic barrier layer and an organic barrier layer,
Wherein the organic barrier layer has an adhesion to the inorganic barrier layer of 7-50 kgf / (mm) ² ,
Wherein the organic barrier layer comprises a cured product of the photocurable composition for encapsulating an organic light emitting device according to any one of claims 1 to 8. [
delete 11. The encapsulated device of claim 10, wherein the organic barrier layer and the inorganic barrier layer are alternately formed.
11. The encapsulated device of claim 10, wherein the organic barrier layer has an outgassing amount of 1000 ppm or less.
The organic barrier layer according to claim 10, wherein the organic barrier layer has a moisture permeability of 4.5 g / m ² .24 hr or less measured at 37.8 캜, 100% relative humidity, and 24 hours against a coating thickness of 5 탆 in the thickness direction of the organic barrier layer Encapsulated device.
11. The method of claim 10, wherein the inorganic barrier layer comprises at least one of a metal, a metal oxide, a metal nitride, a metal carbide, a metal oxynitride, and a metal oxygen boride, An encapsulated device comprising zinc (Zn), antimony (Sb) or aluminum (Al).
11. The encapsulated device of claim 10, wherein the thickness of the organic barrier layer is 0.1 占 퐉 to 20 占 퐉 and the thickness of the inorganic barrier layer is 5 nm to 500 nm.
11. The device of claim 10, wherein the device member is a flexible organic light emitting device, an organic light emitting device, a lighting device, a metal sensor pad, a microdisk laser, an electrochromic device, a photochromic device, An encapsulated device comprising at least one of an integrated circuit, a charge coupled device, a light emitting polymer, and a light emitting diode.
11. The encapsulated device of claim 10, wherein the member for the device comprises a flexible organic light emitting device or an organic light emitting device.

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