KR101609410B1 - 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 comprising silicon 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 barrier layer, a barrier stack comprising the same, an encapsulated device comprising the same, and a method of encapsulating the device using the same. More specifically, the present invention can realize an organic barrier layer having a low moisture permeability and an outgassing amount, a high adhesion to an inorganic barrier layer, a high photo-curability and a low curing shrinkage stress, The damage to the member for the apparatus including the light emitting diode and the like can be minimized and the service life thereof can be prolonged.

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.

One aspect of the present invention is a photocurable composition comprising (A) a photocurable monomer and (B) a photocurable monomer comprising silicon of formula (1): < EMI ID =

≪ Formula 1 >

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 comprising an inorganic barrier layer and an organic barrier layer formed over the device member, wherein the organic barrier layer may comprise a cured product of the photocurable composition.

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. 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 invention is a photocurable composition comprising (A) a photocurable monomer and (B) a photocurable monomer comprising silicon.

(A) Photocurable Monomer

The photo-curable monomer may be a non-silicon-based monomer which does not contain silicon and a photo-curable functional group such as a monomer having a (meth) acrylate group or a vinyl group.

In embodiments, the photocurable monomer may be a monomer having 1-30, preferably 1-20, more preferably 1-5, substituted or unsubstituted vinyl, acrylate, or methacrylate groups .

The photocurable monomer may include a monofunctional monomer having an unsaturated group, a polyfunctional monomer, or a mixture thereof.

In embodiments, the photocurable monomer may comprise a mixture of a monofunctional monomer and a bifunctional monomer and a monomer having three or more functionalities (preferably 3-5 functionalities).

0 to 90 parts by weight of the monofunctional monomer, 0 to 100 parts by weight of the bifunctional monomer, and 0 to 30 parts by weight of the monomer having three or more functional groups may be contained in the mixture. Preferably, the monofunctional monomer may be 0.1 to 80 parts by weight, the bifunctional monomer may be 0.1 to 99.8 parts by weight, and the trifunctional or higher monomers may be used in an amount of 0.1 to 50 parts by weight.

The photocurable monomer may be an aromatic compound having 6-20 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 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 (e.g., (meth) acrylate) 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 (Propyleneglycol) di (meth) acrylate, tri (ethylene glycol) di (meth) acrylate, (Meth) acrylate of a monohydric alcohol or 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.

The photocurable monomer may be a monofunctional or polyfunctional (meth) acrylate that does not contain an epoxy group.

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.

The photocurable monomer may be contained in an amount of 1 to 99.9 parts by weight based on 100 parts by weight of (A) + (B) in the composition. Preferably 30 to 99 parts by weight, more preferably 60 to 95 parts 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) Silicon included Photocurable Monomer

The silicon-containing photocurable monomer comprises -Si-Si- or -Si-X-Si- (X is O, S, -NR- and R is hydrogen or an alkyl group having 1-30 carbon atoms) (For example, a (meth) acrylate group, a vinyl group, etc.) as a monomer having a structure represented by the following formula (1)

≪ Formula 1 >

(Wherein R ₁ is a substituted or unsubstituted alkylene group having 1-20 carbon atoms, a substituted or unsubstituted alkyl ether group having 1-30 carbon atoms, a substituted or unsubstituted alkylamine group having 1-30 carbon atoms, A substituted or unsubstituted arylene group having 6 to 30 carbon atoms, a substituted or unsubstituted arylalkylene group having 7 to 30 carbon atoms, a substituted or unsubstituted alkoxysilane having 1 to 20 carbon atoms Lt; / RTI &

Y ₁ , Y ₂ And Y ₃ is the same or different and represents hydrogen, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted monoalkylamine having 1 to 30 carbon atoms or a dialkyl An amino group, a substituted or unsubstituted thioalkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted arylalkyl group having 7 to 30 carbon atoms,

(2)

(3)

(Wherein * is a Si bonding site of the above formula (1)

R ₂ , R ₃ , R ₄ , R ₅ , R ₆ and R ₇ are the same or different and each represents hydrogen, a substituted or unsubstituted alkyl group having 1-30 carbon atoms, a substituted or unsubstituted alkyl ether group having 1-30 carbon atoms , A substituted or unsubstituted monoalkylamine or dialkylamine group having 1 to 30 carbon atoms, a substituted or unsubstituted thioalkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, A substituted or unsubstituted alkoxy group having 1-30 carbon atoms, X is O, S, -NR- (R is hydrogen or an alkyl group having 1-30 carbon atoms)

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

Z is the following formula (4).

≪ Formula 4 >

(Wherein * is the connecting site of the carbon of R ₁ ,

And R < ₈ > is hydrogen or a substituted or unsubstituted alkyl group having 1-30 carbon atoms)).

Preferably, R ₁ may be an alkylene group having 1 to 10 carbon atoms or an alkylene group having 1 to 6 carbon atoms.

Preferably, the Y _1, Y _2, and Y ₃ is an aryl group of an alkyl group, having a carbon number of 6-14 in carbon number of _{1-10, R 2, R 3,} R 4, R 5, R 6, R 7 is C 1 R ₂ , R ₃ , R ₄ , R ₅ , R ₆ and R ₇ are an alkyl group having 1 to ₆ carbon atoms, or an alkyl group having 1 to ₆ carbon atoms; 3 < / RTI >

Z may be the formula (4), wherein R ₈ is hydrogen or an alkyl group having 1-5 carbon atoms.

In embodiments, the silicon-containing photocurable monomer may comprise at least one of 3- [tris (trimethylsiloxy) silyl] propyl (meth) acrylate, 3- (meth) acryloxypropylbis (trimethylsiloxy) have.

Silicon-containing photo-curable monomers can be synthesized by conventional synthesis methods or commercially available products can be used.

The photocurable monomer containing silicon is included in the photocurable composition together with the photocurable monomer to realize a layer having a low moisture permeability and an outgassing amount, and the photocuring ratio can be increased. In addition, the photocurable monomer containing silicon can realize an organic barrier layer having 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 silicon-containing photocurable monomer may be contained in an amount of 0.1 to 99 parts by weight based on 100 parts by weight of (A) + (B) in the composition. Preferably from 1 to 70 parts by weight, more preferably from 5 to 40 parts by weight. Within the above range, the photo-curing composition enhances the adhesion to the inorganic barrier layer, thereby enhancing adhesion to the substrate during the manufacture of the thin film sealing layer, thereby effectively protecting the device member by shutting off water and gas.

The composition may further comprise 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 contained in an amount of 0.1-30 parts by weight based on 100 parts by weight of (A) + (B) in the composition. 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 0.5 to 20 parts by weight, more preferably 1 to 10 parts by weight.

In the photocurable composition, a photoacid generator or initiator such as a carbazole series, a diketone series, a sulfonium series, an iodonium series, a diazo series, and a diimidazole series may be used instead of the initiator.

The photo-curable composition may have a photo-curing rate of 80% 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 85-100%, and more preferably 90-100%.

The photo-curing rate can be measured by a usual method. For example, the application of the photocurable composition on a glass substrate and cured for 100J / cm ² and 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, 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 organic barrier layer may refer to an encapsulating layer comprising a member for the device. 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 - 20 占 퐉, preferably 1 占 퐉 - 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 preferably has an adhesion to an inorganic barrier layer, for example, aluminum oxide, silicon nitride, silicon oxide or the like of 20 kgf / (mm) ² or more, preferably 30 kgf / (mm) ² or more, more preferably 30-100 kgf / (mm) ² .

The organic barrier layer may have an outgassing amount of less than 2000 ppm. In the above-mentioned range, there is little effect when applied to members, and the life can be lengthened. Preferably 1000 ppm or less, more preferably 750 ppm or less, and most preferably 10 ppb to 750 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 an organic barrier layer of 20 cm x 20 cm x 3 m (width x length x thickness). 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 5.0 g / m ² .24 hr or less with respect to the thickness direction of the organic barrier layer. M ²揃 24 hr or less, more preferably 3.9 g / m ²揃 24 hr or less, and most preferably 0.001 to 3.9 g / m ² ㆍ It can be 24hr.

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 < 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 100-1,000,000, preferably 1000-50,000.

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 may each be deposited in two or more layers alternately 10 times or less (e.g., 2-10 times), preferably 7 times or less (e.g., 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 is 100-1,000,000 A, preferably 1,000-200,000 A, more preferably 1000-50,000 A, 10,000-100,000 A, and the thickness of one inorganic barrier layer is 10-5,000 A .

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.

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 >

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

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 2,000 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 20 kgf / (mm) ² or more.

A method of encapsulating a member for an apparatus, which is another aspect of the present invention, can include the steps of: laminating a member for one or more devices 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.

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.

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 photocurable monomer containing silicon: (B1) 3- [tris (trimethylsiloxy) silyl] propyl methacrylate (TCI), (B2) 3-methacryloxypropylbis (trimethylsiloxy) methylsilane Gelest)

(C) Initiator: Darocur TPO (BASF)

Examples Comparative Example

(A) photocurable monomer, (B) a photocurable monomer containing silicon, and (C) an initiator were placed in a 125 ml brown polypropylene bottle in the content (unit: parts by weight) shown in the following Table 2 and mixed using a shaker for 3 hours To prepare a composition.

The following properties of the compositions prepared in Examples and Comparative Examples were evaluated, and the results are shown in Table 3 below.

1. Water permeability: Use a moisture permeability meter (PERMATRAN-W 3/33, MOCON). The photocurable composition was applied by spraying on an Al sample holder and irradiated at 100 mW / cm < ² > 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: A photo-curing composition is applied on a glass substrate by spraying and irradiated at 100 mW / cm ² and UV-cured to obtain a 20 cm × ²⁰ cm × 3 μm (width × length × thickness) organic barrier layer specimen. 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. Photocuring ratio: 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) 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)

4.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 having a size 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 / cm ² . (Kgf / (mm) ² ) was obtained by dividing the measured adhesion value (kgf) by the area value of 5 mm * 5 mm.

5. Die Share Strength A glass sheet coated with silicon nitride having a thickness of 5 mm * 5 mm * 2 mm and having a thickness of 20 mm * 80 mm * 2 mm (width * length * thickness) Place a glass plate coated with silicon nitride. 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 / cm ² . (Kgf / (mm) ² ) was obtained by dividing the measured adhesion value (kgf) by the area value of 5 mm * 5 mm.

Example Comparative Example One 2 3 4 5 6 7 One 2 3 A A1 - - - - - - - 5 20 40 A2 50 50 50 70 70 85 85 85 70 50 A3 10 10 10 10 10 10 10 10 10 10 B B1 40 - 20 20 - 5 - - - - B2 - 40 20 - 20 - 5 - - - C 5 5 5 5 5 5 5 5 5 5

Example Comparative Example One 2 3 4 5 6 7 One 2 3 Moisture permeability
(g / m ² ㆍ 24 hr) 2.7 2.5 2.1 2.4 3.1 3.9 3.6 7.1 7.8 9.9 Outgassing Amount (ppm) 410 730 580 320 270 560 390 2310 2520 3020 Light curing rate (%) 94.1 95.2 96.2 93.1 96.3 92.6 96.7 89.1 87.8 82.1 Die share strength 1 conversion (kgf / (mm) ² ) 53.6 51.6 60.4 66.4 67.6 60.8 57.6 14.8 16.8 16.4 Die share strength 2 conversion (kgf / (mm) ² ) 29.6 28.4 30.4 34.0 33.2 31.6 29.6 5.2 6.4 7.1

As shown in Table 3, the coating films formed from the photocurable compositions of the present invention had low water vapor permeability and outgassing evaluation and comparatively high photosensitivity. 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 photocurable monomer, and (B) a photocurable monomer containing silicon of the following general formula (1)
The photocurable monomer (A) is non-silicon-
The photocurable monomer (A) is prepared by reacting 0-90 parts by weight of a monofunctional (meth) acrylate monomer, 0.1-99.8 parts by weight of a bifunctional (meth) acrylate monomer, and 0.1-99.8 parts by weight of a trifunctional to pentafunctional (meth) 50 parts by weight of a photocurable composition:
≪ Formula 1 >

(Wherein R < _{1 >} is a substituted or unsubstituted alkylene group having 1-20 carbon atoms,
Y ₁ , Y ₂ and Y ₃ are the same or different and each represents a substituted or unsubstituted alkyl group having 1-30 carbon atoms, a substituted or unsubstituted aryl group having 6-30 carbon atoms,
(3)

(Wherein * is a Si bonding site of the above formula (1)
R ₅ , R ₆ and R ₇ are the same or different and each represents a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms,
X is O)
At least one of Y ₁ , Y ₂ and Y ₃ is the above-described formula (3)
Z is represented by the following formula 4
&Lt; Formula 4 >

(Wherein * is the connecting site of the carbon of R ₁ ,
And R &lt; ₈ &gt; is hydrogen or a methyl group)).
The positive resist composition according to claim 1, wherein the monomer (B) is at least one of 3- [tris (trimethylsiloxy) silyl] propyl (meth) acrylate and 3- (meth) acryloxypropylbis (trimethylsiloxy) &Lt; / RTI &gt;
delete The method according to claim 1,
The monofunctional (meth) acrylate monomer is a (meth) acrylate having an alkyl group having 1-20 carbon atoms,
The bifunctional (meth) acrylate monomer is a di (meth) acrylate of a diol having 2 to 20 carbon atoms,
The trifunctional (meth) acrylate monomer is tri (meth) acrylate of triol having 3 to 20 carbon atoms,
Wherein the tetrafunctional (meth) acrylate monomer is tetra (meth) acrylate of tetraol having 4-20 carbon atoms.
The photocurable composition of claim 1, wherein the photocurable composition comprises 1-99 parts by weight of (A) 100 parts by weight of (A) + (B) and 1-99 parts by weight of (B).
The photocurable composition of claim 1, wherein the photocurable composition further comprises (C) an initiator.
7. The photocurable composition of claim 6, wherein the initiator comprises a photopolymerization initiator.
The photocurable composition according to claim 6, wherein the photocurable composition comprises 1-99 parts by weight of (A) and 1-99 parts by weight of (B) in 100 parts by weight of (A) + (B) 0.1 to 20 parts by weight of the above (C) relative to 100 parts by weight of the photocurable composition.
A cured barrier layer using the photocurable composition of any one of claims 1, 2 and 4 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 is an encapsulated device having an adhesion to the inorganic barrier layer of at least 20 kgf / (mm) ² ,
Wherein the organic barrier layer comprises a cured product of the photocurable composition of any one of claims 1, 2, 4 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 2,000 ppm or less.
The organic barrier layer according to claim 10, wherein the organic barrier layer has a moisture permeability of 5.0 g / m ² 24 hr or less measured at 37.8 캜, 100% relative humidity, and 24 hours under a thickness of 5 탆 in a 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 thickness of the organic barrier layer is 100-1,000,000 A and the thickness of the inorganic barrier layer is 10-5,000 ANGSTROM.
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 integrated circuit, a charge coupled device, an encapsulated device that is a light emitting polymer or 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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