KR101580351B1 - 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 photocurable monomer containing a carboxylic acid group, wherein the photocurable monomer containing a carboxylic acid group (B) To 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 barrier layer, a barrier stack comprising the same, an encapsulated device comprising the same, and a method of encapsulating the device using the same.

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 if the organic electroluminescence portion is sealed, there is a problem that the organic material and / or the electrode material is oxidized by moisture or oxygen introduced from the outside, or outgas generated from the outside or the inside, and the performance and lifetime 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 and low moisture permeability as described above, but it must have high adhesion to the inorganic barrier layer. If the adhesion is low, separation between the barrier layers may occur, and ultimately it may be difficult to seal the organic electroluminescent portion.

Korean Unexamined Patent Publication No. 2005-0021054 discloses an organic electroluminescent device which comprises a front substrate on which an inner space containing an organic electroluminescence portion is sealed and a porous oxide layer containing alumina is formed on the inner surface of the front substrate, And an organic electroluminescent device including the same.

It is an object of the present invention to provide a photocurable composition capable of realizing an organic barrier layer having a low moisture permeability and an outgassing amount and a 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 a further object of the present invention to provide a method of encapsulating a barrier layer formed of the photocurable composition, a barrier stack comprising the organic barrier layer, an encapsulated device comprising the barrier stack, and a device using the barrier stack.

A photocurable composition which is one aspect of the present invention comprises (A) a photocurable monomer and (B) a photocurable monomer containing a carboxylic acid group, and the photocurable monomer containing a carboxylic acid group as the (B)

≪ Formula 1 >

(Wherein Z ₁ is represented by the following formula (2) or (3)

(2)

(3)

(Wherein * is a linking site for -O- in -O- (C = O) - of formula 1,

R ₁ is hydrogen or a substituted or unsubstituted alkyl group having 1-20 carbon atoms,

R ₂ is a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms or a substituted or unsubstituted arylene group having 6 to 20 carbon atoms,

n is an integer of 1-20)

X _1, X ₂ are the same or different, hydrogen, a substituted or unsubstituted alkyl group having a carbon number of 1 to 20 in, * - (C = O) -OR ₃ and -OR _4, or *, wherein R _3, R ₄ is a substituted or Unsubstituted alkyl group having 1-20 carbon atoms).

A barrier layer, which is another aspect of the present invention, may comprise a cured product of the photocurable composition.

An encapsulated device, which is another aspect of the present invention, comprises a device member; And a barrier stack formed on the device member and including an inorganic barrier layer and an organic barrier layer, wherein the organic barrier layer has an adhesion to the inorganic barrier layer of 20 kgf / (mm) ² or more .

The present invention provides an organic barrier layer which can realize an organic barrier layer having a low moisture permeability and an outgassing amount and a high adhesion to an inorganic barrier layer and a high photo-curability so that no shift due to curing shrinkage stress occurs after curing. The present invention provides a photocurable composition capable of minimizing damage to a member for an apparatus including an organic electroluminescent unit, an organic solar cell, and the like, thereby prolonging its service life.

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.

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 photocurable monomer including a carboxylic acid group.

(A) Photocurable Monomer

The photocurable monomer is a non-carboxylic acid-free monomer having no carboxylic acid group, and may have a photo-curable functional group. In an embodiment, the photo-curable functional group may have 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.

For example, the photocurable monomer may be an aromatic compound having 6 to 20 carbon atoms having a substituted or unsubstituted vinyl group; An unsaturated carboxylic acid ester having an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or 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 6-20 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, (Meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, bisphenol A di Monoalcohols or polyhydric alcohols including (meth) acrylic esters such as lactone (meth) acrylate, diethylene glycol di (meth) acrylate, tri (propylene glycol) di (meth) acrylate, Monofunctional or polyfunctional (meth) acrylate, and the like. 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 is a (meth) acrylate having an alkyl group of 1-20 carbon atoms, a di (meth) acrylate of a diol having 2-20 carbon atoms, a tri (meth) Tetra (meth) acrylate of tetraol having a carbon number of 4-20.

In embodiments, the photocurable monomer may comprise a mixture of a monofunctional monomer and a multifunctional monomer. In an embodiment, the monofunctional monomer: multifunctional monomer in the mixture is used in a ratio of 0: 100 to 50:50, preferably 5:95 to 30:70, more preferably 0:50 to 50:50 in 100 parts by weight of the sum of the monofunctional monomer and the polyfunctional monomer May be included in a weight ratio of 10:90 to 15:85.

The photocurable monomer may be contained in an amount of 1 to 99% by weight based on the solid content of (A) + (B). Preferably from 20 to 95% by weight, more preferably from 70 to 90% by weight. In the above range, the photo-curable composition has a high resistance to plasma, so that the out gas and moisture permeability, which can be generated from the plasma generated in the manufacture of the thin film encapsulation layer, can be lowered.

(B) Carboxylic acid group  include Photocurable Monomer

The photocurable monomer containing a carboxylic acid group includes a carboxylic acid group and may include a photocurable monomer having a photocurable functional group. In an embodiment, the photo-curable functional group may have a (meth) acrylate group, a vinyl group, or the like.

In an embodiment, the photo-curable monomer containing a carboxylic acid group may be a monomer containing a carboxylic acid group having a non-cyclized double bond.

The 'cyclization' may mean that the double bond or the single bond is contained in an aryl group having 6 to 20 carbon atoms or a cycloalkyl group having 6 to 20 carbon atoms.

In one embodiment, the photocurable monomer containing a carboxylic acid group may be represented by the following formula (1): < EMI ID =

≪ Formula 1 >

(Wherein Z ₁ is represented by the following formula (2) or (3)

(2)

(3)

(Wherein * is a linking site for -O- in -O- (C = O) - of formula 1,

R ₁ is hydrogen or a substituted or unsubstituted alkyl group having 1-20 carbon atoms

R ₂ is a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms or a substituted or unsubstituted arylene group having 6 to 20 carbon atoms,

n is an integer of 1-20)

X _1, X ₂ are the same or different, hydrogen, a substituted or unsubstituted alkyl group having a carbon number of 1 to 20 in, * - (C = O) -OR ₃ and -OR _4, or *, wherein R _3, R ₄ is a substituted or Unsubstituted alkyl group having 1-20 carbon atoms, and * is a linking site for a double bond in the above formula (1)

The formula 1 may include a carboxylic acid group having a non-cyclized double bond of the following formula a:

<Formula a>

(Wherein X &_lt; ₁ &gt; and X &_lt; ₂ &gt; are as defined above)

Preferably, R &lt; ₁ &gt; may be hydrogen or an alkyl group having 1-5 carbon atoms.

Preferably, R ₂ may be an alkylene group having 1 to 6 carbon atoms.

Preferably, X ₁ and X ₂ may be hydrogen.

The photo-curing monomer containing the carboxylic acid group may be synthesized by a conventional synthetic method, or a commercially available product may be purchased and used. For example, it may be formed by the reaction of (meth) acrylate having dicarboxylic acid or dicarboxylic acid anhydride with an alkyl group having 1-20 carbon atoms having a hydroxy group or an aryl group having 6-20 carbon atoms having a hydroxy group.

The photocurable monomer containing the carboxylic acid group is included in the photocurable composition together with the photocurable monomer to increase the adhesion to the inorganic barrier layer after curing and to realize a layer having a remarkably low moisture permeability and outgassing amount, .

The photocurable monomer containing the carboxylic acid group may be contained in an amount of 1-99% by weight based on the solid content of (A) + (B). Preferably 5-80% by weight, more preferably 10-30% by weight. In the above range, the photo-curing composition enhances the adhesion to the inorganic barrier layer, so that the adhesive strength to the substrate during the production of the thin film encapsulation layer is high.

The composition may further comprise an initiator.

(C) Initiator

The initiator may include, without limitation, conventional photopolymerization initiators capable of carrying out a photo-curable reaction. For example, the photopolymerization initiator may include triazine, acetophenone, benzophenone, thioxanthone, benzoin, phosphorus, oxime, or a mixture thereof.

Examples of the triazine type include 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) (Trichloromethyl) -s-triazine, 2- (4'-methoxynaphthyl) -4,6-bis (trichloromethyl) (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) Bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphtho-1-yl) -4,6 (Trichloromethyl) -s-triazine, 2- (4-methoxynaphtho-1-yl) -4,6-bis Methyl (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 an amount of 0.1 to 20 parts by weight based on 100 parts by weight of the composition (A) + (B) based on the solid content. In 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 can have a photo-curing rate of 89% 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 89 to 99%, and more preferably 89 to 95%.

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 &lt; ² &gt; 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 micro electro mechanical system, Circuit, a charge coupled device, a light emitting polymer, or 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 organic barrier layer may mean an encapsulating layer for encapsulating the device member. The organic barrier layer can prevent the member from being decomposed or oxidized by the external environment such as moisture and oxygen by sealing the device member and minimizes the outgas effect of the member due to a small amount of outgassing even under high humidity or high temperature and high humidity, It is possible to prevent performance degradation and shorten the service life.

The organic barrier layer can be cured by coating the composition with a thickness of 0.1 占 퐉 to 20 占 퐉, preferably 1 占 퐉 to 10 占 퐉, and irradiating at 10-500 mW / cm2 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 is an inorganic barrier layer, for example the adhesion to such as aluminum oxide, silicon nitride, silicon oxide 20kgf / (mm) ² or more, preferably 27kgf / (mm) ² or more, more preferably 27-100kgf / (mm) ² .

The organic barrier layer may have an outgassing amount of 1,000 ppm or less. In the above-mentioned range, there is little effect when applied to members, and the life can be lengthened. Preferably 200 ppm or less, more preferably 10-200 ppm, and most preferably 100-180 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 has a low moisture permeability, so that the influence of moisture on the device member can be minimized. 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. In the above range, it can be used for sealing the device, preferably 1.0-4.5 g / m ² 24 hr, more preferably 3.7-4.5 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). The photocurable composition is applied onto an Al sample holder and irradiated at 100 mW / cm &lt; ² &gt; 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 as an inorganic barrier 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 as long as it is an inorganic layer excellent in light transmittance and excellent in moisture and / or oxygen barrier properties. For example, a metal, an intermetallic compound or an alloy, an oxide of a metal or a mixed metal, a fluoride of a metal or a mixed metal, a nitride of a metal or a mixed metal, a metal carbide, an oxygen nitride of a metal or a mixed metal, Carbohydrates, oxygen borides of metals or mixed metals, silicides of metals or mixed metals, or mixtures thereof.

The metal may be selected from the group consisting of Si, Al, Se, Zn, Sb, In, Ge, Sn, Bi, , Lanthanide metals, and the like, but are 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 1-5), and the like.

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

The organic barrier layer can secure 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.

Preferably, the organic barrier layer and the inorganic barrier layer can each be deposited in two or more layers alternately 10 times or less (e.g., 2-10 times), preferably 7 times or less, more preferably 2-7 times, More preferably, it may be formed in a seven-layer structure of an inorganic barrier layer-organic barrier layer-inorganic barrier layer-organic barrier layer-inorganic barrier layer-organic barrier layer-inorganic barrier layer.

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

The barrier stack may be a thin-film encapsulant having a thickness of 100 mu m or less, preferably 1.5 mu m-50 mu m.

An encapsulated device, which is another aspect of the present invention, may comprise a member for the device, and the barrier layer or barrier stack. The apparatus may include a member for the apparatus. For example, a display device.

In an embodiment, the encapsulated device may comprise a member for the device, and a barrier stack formed over the member for the device, the barrier stack comprising an inorganic barrier layer and an organic barrier layer.

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a cross-sectional view of an encapsulated device of one embodiment of the present invention.

1, an encapsulated device 100 is formed 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 may be deposited.

2, the encapsulated device 200 is formed 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 may be deposited.

Figure 1 is an embodiment in which the device member 20 and the inorganic barrier layer 31 are in contact with each other and Figure 2 is an embodiment in which an empty space 40 is formed between the device member 20 and the inorganic barrier layer 31 .

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 inorganic protective layer and the organic protective layer may be contained a plurality of times at least twice. In one embodiment, the inorganic protective layer and the organic protective layer may be alternately deposited, such as an inorganic protective layer / an organic protective layer / an inorganic protective layer / an organic protective layer. Preferably, the inorganic protective layer and the organic protective layer may be contained in total not more than 10 times (for example, 2-10 times), more preferably not more than 7 times, for example, 2-7 times.

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 adhesion to the inorganic barrier layer of 20 kgf / (mm) ² or more.

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

Stacking a member for the at least one device on the 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.

A member for a device is laminated on a 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.

Synthetic example  1: Monomeric  synthesis

50 g of 4-hydroxybutyl acrylate (Aldrich), 35 g of maleic anhydride (Aldrich) and 1 g of p-toluenesulfonic acid (Aldrich) were placed in a 200 ml flask equipped with a cooling tube and a stirrer. 300 g of dichloromethane and 200 g of water were added. After stirring for 30 minutes, an organic layer was obtained, and the mixture was distilled under reduced pressure to obtain a monomer of formula (4) through a silica gel column.

&Lt; Formula 4 >

Synthetic example  2: Monomeric  synthesis

50 g of 2-hydroxyethyl methacrylate (Aldrich), 38 g of maleic anhydride (Aldrich) and 1 g of p-toluenesulfonic acid (Aldrich) were placed in a 200 ml flask equipped with a cooling tube and a stirrer. 300 g of dichloromethane and 200 g of water were added. After stirring for 30 minutes, an organic layer was obtained, and the mixture was distilled under reduced pressure to obtain a monomer of formula (5) through a silica gel column.

&Lt; Formula 5 >

Synthetic example  3: Monomer  synthesis

50 g of 4-hydroxybutyl acrylate (Aldrich), 52 g of phthalic anhydride (Aldrich) and 1 g of p-toluenesulfonic acid (Aldrich) were placed in a 200 ml flask equipped with a cooling tube and a stirrer. After stirring and cooling, 300 g of dichloromethane and 200 g of water were added. After stirring for 30 minutes, an organic layer was obtained, and the mixture was distilled under reduced pressure to obtain a monomer of Formula 6 through a silica gel column.

(6)

Synthetic example  4: Monomer  synthesis

50 g of 2-hydroxyethyl acrylate (Aldrich), 53 g of tetrahydrophthalic anhydride (Aldrich) and 1 g of p-toluenesulfonic acid (Aldrich) were placed in a 200 ml flask equipped with a cooling tube and a stirrer. 300 g of dichloromethane and 200 g of water were added. After stirring for 30 minutes, an organic layer was obtained, and the mixture was distilled under reduced pressure. Monomer of formula (7) was obtained through a silica gel column.

&Lt; Formula 7 >

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)

(B) a photo-curable monomer represented by formula (1): (B1) a monomer represented by formula (4) in Synthesis Example 1, (B2) a monomer represented by formula

(C) Initiator: Darocur TPO (BASF)

(D) a photo-curable monomer containing a carboxylic acid group: (D1) a monomer of the formula (6) in Synthesis Example 3, (D2) a monomer of the formula

Examples Comparative Example

The components (A), (B), (C) and (D) were placed in a 125 ml brown polypropylene bottle in the contents (unit: parts by weight, solids basis) shown in Table 2 below and mixed for 3 hours using a shaker A composition was prepared.

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

1. Water vapor permeability (g / m ² ㆍ 24 hr): Use a moisture permeability meter (PERMATRAN-W 3/33, MOCON). An Al sample holder was coated with a photo-curing composition by spraying and irradiated at 100 mW / cm &lt; 2 &gt; for 10 seconds to UV cure to form a cured specimen of 5 mu m thick. The moisture permeability is measured for 24 hours at 37.8 ° C and 100% relative humidity using a moisture permeability meter (PERMATRAN-W 3/33, MOCON) for a film thickness of 5 μm.

2. Outgassing amount (ppm): A photocurable composition was applied onto a glass substrate by spraying and irradiated at 100 mW / cm ² for 10 seconds to be UV-cured to form a 20 cm x 20 cm x 3 탆 (width x length x thickness) A layer specimen is obtained. 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)

3. sight rate (%) against the photocurable composition by using the FT-IR (NICOLET 4700, Thermo Co.) of the absorption peak in the vicinity of 1635cm ^-1 (C = C), 1720cm ^-1 vicinity (C = O) The strength is measured. A photocurable composition is applied on a glass substrate by spraying and irradiated at 100 mW / cm &lt; ² &gt; 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). Obtain a cured film and, FT-IR (NICOLET 4700, Thermo Co.) is used in the vicinity of 1635cm ^-1 (C = C), 1720cm ^-1 measured intensity of the absorption peak in the vicinity of the (C = O) a. 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 about 1635 cm ^-1 to the intensity of the absorption peak at about 1720 cm ^-1 for the cured film,

B is the ratio of the intensity of the absorption peak of 1635cm ^-1 in the vicinity of the intensity of the absorption peak at near 1720cm ^-1 against a photocurable composition)

4. Die share strength (kgf / (mm) 2): 5 mm * A glass having a width of 5 mm and a height of 2 mm was impregnated with 0.01 g of the compositions shown in Table 2 below, and a glass having a thickness of 20 mm * 80 mm and a height of 2 mm The die share strength of the Tachi 4000 bond tester was measured after curing with a D-bulb light source at an intensity of 1000 J / cm ² .

Example Comparative Example One 2 3 4 5 6 One 2 3 4 5 A A1 - - - - - - 10 20 30 - - A2 60 60 60 60 60 60 60 60 60 60 60 A3 30 20 10 30 20 10 30 20 10 30 30 B B1 10 20 30 - - - - - - - - B2 - - - 10 20 30 - - - - - C 5 5 5 5 5 5 5 5 5 5 5 D D1 - - - - - - - - - 10 - D2 - - - - - - - - - - 10 Water vapor permeability (g / m2 ㆍ 24 hr) 4.5 4.3 3.8 4.2 4.1 3.7 6.9 7.5 9.9 4.1 4.3 Outgassing Amount (ppm) 180 150 100 350 220 190 1290 1540 2980 150 210 Light curing rate (%) 94.3 92.6 89.3 93.5 92.2 89.4 82 88 89 91.4 90.7 Die share strength (kgf / (mm) 2) 27.4 34.5 45.7 28.6 35.6 46.8 5.8 6.3 6.1 17.5 16.4

As shown in Table 2, the coating film formed from the photocurable composition of the present invention had low water vapor permeability and outgass evaluation and comparatively high photo-curability compared to the comparative example. In addition, the coating film formed from the photocurable composition of the present invention had a very high adhesion to the inorganic barrier layer as compared with the comparative example. On the other hand, the composition of Comparative Example 4-5, which does not contain a photo-curable monomer containing a carboxylic acid group, and the photo-curable monomer having a carboxylic acid group having a cyclized double bond, And adhesion to inorganic barrier layer was low.

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 photocurable monomer, (B) a photocurable monomer containing a carboxylic acid group, and (C) an initiator,
The photocurable monomer (B) containing a carboxylic acid group is represented by the following general formula (1)
(A) and (B) are contained in an amount of 70 to 90% by weight and 10 to 30% by weight, respectively, in the sum (A) + (B)
(A) may be a di (meth) acrylate of a diol having 2 to 20 carbon atoms, a tri (meth) acrylate of a triol having 3 to 20 carbon atoms, or a tetra (meth) acrylate having a tetra &Lt; / RTI >
Photocurable composition for encapsulating an organic light emitting element:
&Lt; Formula 1 >

(Wherein Z1 is represented by the following formula 2 or 3,
(2)

(3)

(Wherein R ₁ is hydrogen or a substituted or unsubstituted alkyl group having 1-20 carbon atoms,
R ₂ is a substituted or unsubstituted alkylene group having 4-20 carbon atoms,
n is an integer of 1-20)
X _1, X ₂ are the same or different, hydrogen, a substituted or unsubstituted alkyl group having a carbon number of 1 to 20 in, * - (C = O) -OR ₃ and -OR _4, or *, wherein R _3, R ₄ is a substituted or Unsubstituted alkyl group having 1-20 carbon atoms).
The photocurable composition for encapsulating an organic light emitting device according to claim 1, wherein the photocurable monomer (B) containing a carboxylic acid group comprises the following formula (4):
&Lt; Formula 4 >

. delete delete delete delete The photocurable composition according to claim 1, wherein the initiator (C) comprises a photopolymerization initiator.
The photocurable composition for encapsulating an organic light emitting device according to claim 1, wherein the photocurable composition for encapsulating an organic light emitting device comprises 0.1-20 parts by weight of (C) relative to 100 parts by weight of (A) + (B).
A barrier layer comprising a cured product of the photo-curable composition for encapsulating an organic light-emitting device according to any one of claims 1, 2, 7, and 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 20 kgf / (mm) ² or more,
Wherein the organic barrier layer comprises a cured product of the photocurable composition for encapsulating an organic light emitting element according to any one of claims 1, 2, 7, and 8.
11. The encapsulated device of claim 10, wherein the organic barrier layer has an outgas generation of no more than 1,000 ppm.
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 to a 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,
The metal may be selected from the group consisting of Si, Al, Se, Zn, Sb, In, Ge, Sn, Bi, , And lanthanide metals.
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 and the inorganic barrier layer are less than 10 total layers.
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.
delete 11. The method of claim 10, wherein the device member is selected from the group consisting of an organic light emitting device, a flexible organic light emitting device, a lighting device, a metal sensor pad, a microdisk laser, an electrochromic device, a photochromic device, An integrated circuit, a charge coupled device, an encapsulated device that is a light emitting polymer or a light emitting diode.

Images