KR101600658B1 - Spirobifluorene compound, copolymer thereof, photocurable composition comprising the same and encapsulated apparatus comprising the same - Google Patents

Abstract

The present invention relates to a spirobifluorene compound of formula (I), a copolymer thereof, a photocurable composition comprising the same, and an encapsulated device comprising the same.

Description

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

The present invention relates to a spirobifluorene compound, a copolymer thereof, a photocurable composition comprising the same, and an encapsulated device comprising 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 when the organic electroluminescent unit 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, thereby deteriorating the performance and lifetime. 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.

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.

An object of the present invention is to provide a spirobifluorene-based compound capable of realizing a layer having a low moisture permeability and an outgassing amount after curing and having a high adhesion to an inorganic barrier layer.

Another object of the present invention is to provide a spirobifluorene-based compound capable of realizing a layer in which shift due to hardening shrinkage stress after curing is not caused by increasing the photo-curing rate.

It is still another object of the present invention to provide a spirobifluorene-based compound capable of realizing a layer capable of extending the lifetime of a device at the time of device sealing.

It is still another object of the present invention to provide an encapsulated device comprising a photo-curable composition comprising the above spirobifluorene-based compound and a layer formed therefrom.

A spirobifluorene compound which is an aspect of the present invention may include a compound represented by the following formula (1)

≪ Formula 1 >

Another aspect of the present invention is a copolymer comprising a copolymer of a monomer mixture comprising the above spirobifluorene compound.

Another aspect of the present invention is a photocurable composition comprising the above spirobifluorene compound, a non-spirobifluorene photocurable monomer and an initiator.

An encapsulated device, which is another aspect of the present invention, comprises a device member; And a barrier stack formed on the device for the device, the barrier stack including an inorganic barrier layer and an organic barrier layer, wherein the organic barrier layer may comprise a cured product of the photocurable composition.

The present invention provides a spirobifluorene-based compound capable of realizing a layer having a low moisture permeability and an outgassing amount after curing and having a high adhesion to an inorganic barrier layer. Further, the present invention provides a spirobifluorene-based compound capable of realizing a layer which does not cause shift due to hardening shrinkage stress after curing by increasing the photo-curing rate.

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 ¹ H-NMR result of the formula 16 of Example 1. Fig.
Fig. 4 shows ¹ H-NMR results of the formula 17 of Example 2. Fig.
5 is a ¹ H-NMR result of the formula 19 of Example 3. Fig.
6 is a ¹ H-NMR result of the chemical formula 20 of Example 4. Fig.

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 cycloalkyl group having 3 to 30 carbon atoms, substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, or substituted or unsubstituted heterocycloalkyl group having 2 to 30 carbon atoms.

In the present specification, "hetero" means that a carbon atom is substituted with any one atom selected from the group consisting of N, O, S and P.

In this specification, '*' may mean a connecting portion of an element.

The spirobifluorene-based compound, which is one aspect of the present invention, may have both a spirobifluorene group and a photocurable functional group. In an embodiment, the photocurable functional group may include at least one of a vinyl group, an acrylate group, and a methacrylate group.

In an embodiment, the spirobifluorene compound may be represented by the following formula (1): < EMI ID =

≪ Formula 1 >

(Wherein R ₁ , R ₂ , R ₃ and R ₄ are the same or different and each represents a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, the carbon number of 3 to 10 cycloalkyl group, a substituted or unsubstituted C7 to C20 aryl group, a hydroxy group, a halogen, or to a general formula (2), R _1, R _2, R _3, R one or more of the ₄ to formula (2) ego,

(2)

(Wherein * is a linking group to the aromatic carbon of Formula 1,

Y is O, S, NH, or N-R (wherein R is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms)

R ₅ is a substituted or unsubstituted aliphatic hydrocarbon having 1 to 30 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon having 6 to 30 carbon atoms, or a substituted or unsubstituted alicyclic hydrocarbon having 3 to 20 carbon atoms,

X ₁ and X ₂ are the same or different and independently of one another O, S, NH, or NR (wherein R is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms or a substituted or unsubstituted 6 to 30 aryl group )ego,

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

(3)

(Wherein * is a connector to X ₁ or a connector to X ₂ ,

And R < ₆ > is hydrogen or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms)

≪ Formula 4 >

(Wherein * is a connector to X ₁ or a connector to X ₂ ,

R ₇ is a substituted or unsubstituted C 1 -C 30 alkylene group, a substituted or unsubstituted C 5 -C 20 cycloalkylene group, a substituted or unsubstituted C 6 -C 20 arylene group, a substituted or unsubstituted C 7 -C To 20 carbon atoms,

R ₈ is hydrogen or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms,

X ₃ is O, S, NH, or NR (wherein R is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms)

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

n ₁ and n ₂ are integers of 0 to 4, at least one of n ₁ and n ₂ is an integer of 1 to 4,

m ₁ , m ₂ , m ₃ and m ₄ are the same or different and are an integer of 0 to 4, and at least one of m ₁ , m ₂ , m ₃ and m ₄ is an integer of 1 to 4.

The compound of formula (1) may comprise one or more compounds of formula (3) or one or more compounds of formula (4).

In one embodiment, Z < ₁ > is hydrogen and Z < ₂ >

Or in another embodiment, Z ₁ is Formula 3 above, and Z ₂ can be hydrogen.

Or in another embodiment, Z ₁ may be the formula 3 and Z ₂ may be the formula 4.

Preferably, m ₂ and m ₄ are 0, and m ₁ and m ₃ may be integers of 1 to 4. Or m ₁ and m ₃ are 0, and m ₂ and m ₄ are integers of 1 to 4.

Preferably, n ₁ and n ₂ may be an integer of 1 to 4.

Preferably, R ₅ is an alkyl group having 1 to 10 carbon atoms, an alkylene group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, a cycloalkylene group having 5 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, An arylene group having 20 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, and an arylalkylene group having 7 to 20 carbon atoms.

Preferably, R ₆ and R ₈ may be hydrogen or a methyl group.

Preferably, the formula 1 may be represented by the following formula 1-1:

≪ Formula 1-1 >

(Wherein R &_lt; ₁ > and R &_lt; ₃ > are as defined above,

At least one of R < ₁ > and R < ₃ >

The above spirobifluorene compound can be prepared by a conventional method. In an embodiment, the compound of formula (1), wherein m ₂ and m ₄ are 0, m ₁ and m ₃ are 1, and Y is O, X ₁ and X ₂ are both O, Can be manufactured:

≪ Formula 5 >

The compound of formula (5) can be prepared by a conventional method. For example, 9,9'-spirobifluorene can be prepared by reacting 9,9'-spirobifluorene with acetyl chloride to prepare 9,9'-spirobifluorene having an acetyl group introduced therein, peroxidizing the acetyl group with a peroxy compound, By hydrolysis.

In embodiments, the spirobifluorene-based compound may be prepared from any of the following Schemes 1 to 4, but is not limited thereto:

<Reaction Scheme 1>

(Wherein R ₉ is hydrogen or a methyl group).

The compound of Formula 5 may be prepared (Step II) by reacting the compound of Formula 5 with epichlorohydrin to prepare a compound of Formula 6 (Step I) and then reacting the compound of Formula 6 with (meth) acrylic acid have.

<Reaction Scheme 2>

(Wherein R ₉ is hydrogen or a methyl group,

And R &lt; ₁₀ &gt; is an alkylene group having 1 to 30 carbon atoms.

Reacting the compound of Formula 5 with epichlorohydrin to produce a compound of Formula 6 (Step I), reacting the compound of Formula 6 with (meth) acrylic acid to prepare a compound of Formula 7 (Step II) The compound of formula (7) may be reacted with isocyanate alkyl (meth) acrylate to prepare the compound of formula (8) (step III)

<Reaction Scheme 3>

(Wherein R ₅ is a substituted or unsubstituted aliphatic hydrocarbon having 1 to 30 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon having 6 to 30 carbon atoms, or a substituted or unsubstituted alicyclic hydrocarbon having 3 to 20 carbon atoms,

And R &lt; ₉ &gt; is hydrogen or a methyl group.

(Meth) acrylate is reacted with the compound of Formula 5 to obtain a compound of Formula 9 (Step IV) by reacting XR ₅ -OH (wherein X is halogen and R ₅ is as defined above) Acryloyl halide to give the compound of formula 10 (step V).

<Reaction Scheme 4>

(Wherein R ₅ is a substituted or unsubstituted aliphatic hydrocarbon having 1 to 30 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon having 6 to 30 carbon atoms, or a substituted or unsubstituted alicyclic hydrocarbon having 3 to 20 carbon atoms,

R ₉ is hydrogen or a methyl group,

And R &lt; ₁₀ &gt; is an alkylene group having 1 to 30 carbon atoms.

The compound of Formula 5 is reacted with XR ₅ -OH (wherein X is halogen and R ₅ is as defined above) to prepare the compound of Formula 9 (Step IV), and the compound of Formula 9 is reacted with isocyanatoalkyl (VI) by reacting a compound represented by the above formula (11).

Although a method for producing a part of the spirobifluorene compound has been described above, it would be obvious to those skilled in the art that the spirobifluorene compound is produced by modifying the above production method. In addition, in the above steps I to VI, the reaction conditions including the reaction temperature, the reaction time, the reaction pressure and the like and the selection of the reaction material will be apparent to those skilled in the art.

The spirobifluorene compound is contained in a photocurable composition which can be used for encapsulating a member for an apparatus including an organic light emitting device or the like, and has a low moisture permeability and an outgassing amount after curing, and a high A barrier layer having an adhesive force can be realized. Therefore, the above-mentioned spirobifluorene compound can be used as a component of a sealing composition of a member for an apparatus including an organic light emitting element or the like which can be damaged by moisture or the like.

In an embodiment, the photocurable composition containing the spirobifluorene compound has a photo-curability of 88% or more, the composition has an outgassing amount after curing of 1000 ppm or less, The adhesion to the inorganic barrier layer including silicon oxide or silicon nitride may be 4 kgf / (mm) ² or more, and the moisture permeability measured for 24 hours under the relative humidity conditions is 4.9 g / m ² .24 hr or less.

Another aspect of the present invention is a copolymer comprising a copolymer of a monomer mixture comprising the above formula (1).

In an embodiment, the copolymer may comprise a (meth) acrylic copolymer having a spirobifluorene group. In the copolymer, the monomers of Formula 1 may be polymerized singly or in combination of two or more.

The copolymer may have a weight average molecular weight (Mw) of 4,000 to 20,000 g / mol.

The copolymer may be prepared from the monomer mixture by a conventional polymerization method. In embodiments, the polymerization may include solution polymerization, suspension polymerization, and the like. For example, polymerization can be carried out by adding a soluble initiator to the monomer mixture and heating. The initiator is not limited, but typical initiators such as azobisisobutyronitrile, benzoyl peroxide and the like can be used. The polymerization may be carried out at a polymerization temperature of 70 to 120 캜 for 3 to 12 hours.

The monomer mixture may further contain a conventional polymerizable monomer in addition to the monomer of the formula (1). (Meth) acrylic monomer having an alkyl group having 1 to 10 carbon atoms, a (meth) acrylic monomer having an alkyl group having 1 to 10 carbon atoms having a hydroxyl group, a (meth) acrylic monomer having an alicyclic group, (Meth) acrylic monomer, and (meth) acrylic monomer having a carboxylic acid group.

The copolymer may have an effect of increasing adhesion to a substrate (for example, an inorganic barrier layer), reducing the amount of generated outgas, and blocking moisture.

The photocuring composition, which is another aspect of the present invention, may comprise the above spirobifluorene-based compound.

(A) Spirobifluorene series  compound

The spirobifluorene compound may include a spirobifluorene group and a spirobifluorene photocurable monomer having a photocurable functional group.

In an embodiment, the spirobifluorene compound may be represented by the formula (1). Details of the above spirobifluorene compound are as described above.

The spirobifluorene compound is included in the photocurable composition together with the photo-curing monomer to increase the photo-curability. After the curing, the barrier layer having a low moisture permeability and an outgassing amount is remarkably low, Can be implemented.

The spirobifluorene compound may be contained in an amount of 5 to 90% by weight, preferably 5 to 35% by weight, based on the solid content of the composition.

The composition may further comprise (B) a photocurable monomer.

(B) Photocurable Monomer

The photo-curable monomer may be a non-fluorene-based, non-fluorene-based or non-spirobifluorene-based compound free of a fluorene group, a nonfluorene group, a spirobifluorene group, Containing monomers. In embodiments, the photocurable functional group may mean a vinyl group, an acrylate group, or a methacrylate group.

The photocurable monomer may comprise a monofunctional monomer, a multifunctional monomer, or a mixture thereof. Preferably, the photocurable monomer is a monomer having 1 to 30, preferably 1 to 20, more preferably 1 to 6, substituted or unsubstituted vinyl, acrylate or methacrylate groups .

The photocurable monomer may comprise a mixture of a monofunctional monomer and a multifunctional monomer. The monofunctional monomer: polyfunctional monomer may be contained in the mixture in a weight ratio of 1: 0.1 to 1:10, and a weight ratio of 1: 5 to 1: 8.

In an embodiment, the photocurable monomer is an aromatic compound having 6 to 20 carbon atoms 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.

In an embodiment, the photocurable monomer is an aromatic compound having 6 to 20 carbon atoms and having an alkenyl group including a vinyl group such as styrene, alpha-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 (meth) acrylate; A vinyl cyanide compound such as (meth) acrylonitrile; Unsaturated amide compounds such as (meth) acrylamide; 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 tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (Propylene glycol) di (meth) acrylate, novolac epoxy (meth) acrylate, diethylene glycol di (meth) acrylate, tri (Meth) acrylate and the like, or a 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 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 the photocurable composition in an amount of 1 to 99 parts by weight based on 100 parts by weight of the sum (A) + (B) of the components (A) and (B). Preferably 20 to 95 parts by weight, more preferably 30 to 95 parts by weight, and most preferably 70 to 90 parts by weight.

The spirobifluorene compound may be contained in an amount of 1 to 99 parts by weight based on 100 parts by weight of (A) + (B) in the photocurable composition. Preferably 5 to 80 parts by weight, more preferably 5 to 70 parts by weight, and most preferably 10 to 30 parts by weight. Within the above range, the photo-curing composition is resistant to plasma, and it is possible to lower or prevent deterioration of the out gas and the moisture permeability that may be generated from the plasma generated in the manufacture of the thin film encapsulation layer.

The composition may further comprise (C) 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 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 photocurable 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 0.5 to 10 parts by weight, more preferably 1 to 8 parts by weight.

The photocurable composition may contain 5 to 90% by weight of the component (A), 5 to 90% by weight of the component (B), and 0.1 to 10% by weight of the component (C) on a solid basis. Within this range, there may be an adhesive force to the substrate (e.g., an inorganic barrier layer) and a moisture blocking effect. Preferably 5 to 35% by weight of the component (A), 60 to 90% by weight of the component (B), and 1 to 5% by weight of the component (C).

The photocurable composition may have a photo-curing rate of 88% 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 88 to 99%, and more preferably 88 to 97%.

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.

On the other hand, the components for the device, in particular the components for the display device, can be decomposed or defective by the permeation of gases or liquids in the surrounding environment, for example oxygen and / or moisture and / . To this end, the display device needs to be encapsulated or encapsulated.

Such a device member may be an organic light emitting diode (OLED), a lighting device, a flexible organic light emitting diode display, a metal sensor pad, a microdisk laser, an electrochromic device, a photochromic device, a microelectromechanical system, , A charge coupled device, a light emitting polymer, a light emitting diode, and the like.

The photocurable composition satisfies both the adhesion to the inorganic barrier layer, the photo-curability and the transmittance described above, so that it can be used for the encapsulation or encapsulation of the device, in particular, a flexible display device, And the like.

An organic barrier layer, which is another aspect of the present invention, may be formed from the composition.

The organic barrier layer can be formed by photocuring the photocurable composition described above. Although not limited, the photocurable composition can be coated to a thickness of 0.1 탆 -20 탆 and cured by irradiation at 10-500 mW / cm ² for 1-50 seconds.

The organic barrier layer has the physical properties of the photocurable composition after curing as described above. Thus, a barrier stack can be formed with the inorganic barrier layer described below to be used for encapsulation of the device.

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 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. More specifically, the inorganic barrier layer may be a ₂ O _3, SnO ₂ of silicon oxide, silicon nitride, silicon oxygen nitride, ZnSe, ZnO, Sb ₂ O _3, Al ₂ O _3, In.

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 organic barrier layer minimizes the outgassing effect on the device due to its low outgassing, which can prevent the device from degrading or degrading performance against outgas. Specifically, the organic barrier layer may have an outgassing amount of 0 to 1000 ppm or less, preferably 0 to 600 ppm or less. Within the above range, there is little effect when applied to the device, and the life of the device can be prolonged. For example, 10-1,000 ppm, for example, 70-600 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.

Further, the organic barrier layer has a low water vapor transmission rate (WVTR) and water vapor transmission rate, so that the influence of moisture on the device can be minimized. The moisture permeability may be 0 to 4.9 g / m ² .24 hr or less with respect to the thickness direction of the organic barrier layer. In this range, it can be used for the sealing of the element, e.g., 1.0-4.9g / m ² 24hr and, for example, be a 2.5-4.6g / m ² and 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 &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.

Further, the organic barrier layer may have an adhesion force of 4 kgf / (mm) ² or more to the inorganic barrier layer. If the adhesive force is less than 4 kgf / (mm) ² , moisture or oxygen penetrated from the outside easily penetrates between the barrier layers, resulting in reliability failure. The inorganic barrier layer is an inorganic barrier layer which is described below: may comprise (for example, _{SiOx, SiNx, Al 2 O 3} ), but is not limited thereto. Preferably, the adhesive force may be 4-100 kgf / (mm) ² , more preferably 4-25 kgf / (mm) ² .

In one embodiment, the inorganic barrier layer may be silicon oxide, aluminum oxide, or silicon nitride. The adhesive force can be measured with reference to the following experimental examples.

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 be deposited in two or more layers, respectively, in total with no more than 10 layers (e.g., 2-10 layers), preferably no more than 7 layers (e.g., 2-7 layers) .

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.

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 is not limited as long as it includes a member for the apparatus, and may include, for example, a display apparatus.

The encapsulated device comprises a member for the device; And a barrier stack formed on the device for the device, the barrier stack including an inorganic barrier layer and an organic barrier layer.

1 and 2 are cross-sectional views of an encapsulated device of one embodiment of the present invention.

1, an encapsulated device 100 includes a substrate 10; (For example, organic light emitting element) 20 formed on the substrate 10; And a barrier stack 30 formed on the device member 20 and consisting of an inorganic barrier layer 31 and an organic barrier layer 32.

2, the encapsulated device 200 includes a substrate 10; (For example, organic light emitting element) 20 formed on the substrate 10; And a barrier stack 30 formed on the device member 20 and consisting of an inorganic barrier layer 31 and an organic barrier layer 32.

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

The contents 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 photo-curable 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.

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

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.

Example  1: Preparation of compound of formula 16

&Lt; Synthesis Example 1 >: Preparation of Compound (12)

(Aldrich), 50 g of 9,9'-spirobifluorene (TCI) was placed in 500 ml of carbon disulfide (Aldrich), and the mixture was heated to 45 DEG C. Then, 31 g of acetyl chloride (Aldrich) And the mixture was stirred for 10 hours. After completion of the reaction, the carbon disulfide was distilled off under reduced pressure, 500 ml of dichloromethane was added, and 300 ml of water was added. After stirring at room temperature for 2 hours, the organic layer was distilled off under reduced pressure, and the compound of formula (12) was obtained through a silica gel column.

[Chemical Formula 12]

Synthesis Example 2: Preparation of a compound of the formula 13

In a 1 L reactor, 60 g of the compound of the formula 12 obtained in Synthesis Example 1 was added, 40 g of metachloroperoxybenzoic acid (Aldrich) was added, 500 ml of dichloromethane was added, and the mixture was heated to 43 캜 and stirred for 8 hours. And the mixture was stirred at room temperature for 30 minutes. Then, the organic layer was taken and distilled under reduced pressure, and the compound of Formula 13 was obtained through a silica gel column.

[Chemical Formula 13]

Synthesis Example 3: Synthesis of Compound (14)

In a 500 ml reactor, 50 g of the compound of the formula 13 obtained in Synthesis Example 2 was added, and 300 ml of methanol (Aldrich) and 200 ml of a 6N aqueous NaOH solution were added. The mixture was stirred at room temperature for 20 hours, distilled under reduced pressure, adjusted to pH 5 with 1N aqueous HCl solution, Methane (500 ml) was used for extraction into an organic layer. The organic layer was taken, and the residue was distilled under reduced pressure to obtain a compound of formula (14) through a silica gel column.

[Chemical Formula 14]

Synthesis Example 4: Synthesis of Compound (15)

In a 1 L reactor, 50 g of the compound of the formula 14 obtained in Synthesis Example 3, 40 g of epichlorohydrin (Aldrich) and 60 g of anhydrous potassium carbonate were placed in 500 ml of dimethylformamide, the temperature was raised to 80 캜 and the mixture was stirred for 8 hours. Was added dropwise to a stirring reactor equipped with 3 L of water for 2 hours to obtain crystals. The obtained crystals were recrystallized from dichloromethane and diethyl ether to obtain the compound of the following formula (15).

[Chemical Formula 15]

&Lt; Synthesis Example 5 >: Preparation of the compound of Formula 16

A 1 L reactor was charged with 50 g of the compound of the formula 15 obtained in Synthesis Example 4, 16.5 g of acrylic acid (Aldrich), 1 g of triphenylphosphine (Aldrich) and 200 g of propylene glycol methyl ether acetate (Daicel) And the mixture was stirred for 8 hours to obtain a reaction solution containing the compound of the following formula (16). The structure of Chemical Formula 16 was confirmed by ¹ H-NMR as shown in Fig.

[Chemical Formula 16]

Example  2: Preparation of compound of formula 17

&Lt; Synthesis Example 6 >: Preparation of Compound (17)

50 g of the compound of the formula 16 obtained in Synthesis Example 5, 25.7 g of 2-isocyanate ethyl methacrylate (manufactured by Showa Denko K.K.) and 50 g of MEK (methyl ethyl ketone) were placed in a 250 mm1 reactor and stirred at 40 DEG C for 12 hours, A compound of the following formula (17) can be obtained. The structure of Chemical Formula 17 was confirmed by ¹ H-NMR as shown in Fig.

[Chemical Formula 17]

Example  3: Preparation of compound of formula 19

&Lt; Synthesis Example 7 >: Preparation of compound of formula 18

50 g of the compound of the formula 14 obtained in Synthesis Example 3, 24 g of 2-hydroxyethyl chloride (Aldrich), 300 g of potassium carbonate (anhydrous) (Aldrich) and 300 g of dimethylformaldehyde (Aldrich) After cooling for 6 hours and cooling, the reaction solution was poured into 2 L of water for 1 hour to precipitate crystals, followed by filtration, washing and drying in a vacuum oven at 50 캜 for 12 hours to obtain a compound of the following formula (18).

[Chemical Formula 18]

Synthesis Example 8: Preparation of compound of Formula 19

50 g of the compound of the formula 18 obtained in Synthesis Example 7, 21 g of acryloyl chloride (aldrich) and 100 g of MEK (methyl ethyl ketone) were added to a 250 mm1 reactor, and 24 g of triethylamine was added dropwise thereto at 40 DEG C for 1 hour. The resulting salt is filtered and the filtrate is distilled under reduced pressure to obtain the compound of the following formula (19). The structure of Chemical Formula 19 was confirmed by ¹ H-NMR as shown in Fig.

[Chemical Formula 19]

Example  4: Preparation of compound of formula 20

Synthesis Example 9: Preparation of compound of formula 20

50 g of the compound of the formula 18 obtained in Synthesis Example 7, 36 g of 2-isocyanate ethyl methacrylate (manufactured by Showa Denko K.K.) and 100 g of MEK (methyl ethyl ketone) were placed in a 250 mm1 reactor and stirred at 40 DEG C for 12 hours. A compound of formula 20 can be obtained. The structure of Chemical Formula 20 was confirmed by ¹ H-NMR as shown in Fig.

[Chemical Formula 20]

The specific specifications of the components used in Examples 5 to 16 and Comparative Examples 1 to 4 are as follows.

(A) a spirobifluorene compound: (A1) a compound of Formula 16 of Example 1, (A2) a compound of Formula 17 of Example 2, (A3) a compound of Formula 19 of Example 3, A4) Compound (20) of Example 4

(B1) hexyl acrylate, (B2) hexanediol diacrylate, (B3) pentaerythritol tetraacrylate (available from Aldrich)

(C) Initiator: Darocur TPO (BASF)

(D) Fluorene compound not bound to biphenyl: V259ME (Nippon Steel Chemical Co.)

Example  5 to 16 and Comparative Example  1 to 4

(B) a photo-curable monomer, (C) an initiator, and (D) a fluorene compound were placed in a 125 ml brown polypropylene bottle in the content (unit: parts by weight) , And 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 2 below.

1. Water vapor permeability (g / m ² ㆍ 24 hr): 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 &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 of organic protective layer (ppm): A photocurable composition was applied on 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 ) 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 X 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 x 0.25 mm x 0.25 m
(5% phenylmethylpolysiloxane) Mobile phase He Flow 1.0 mL / min (Average velocity = 32 cm / s) Split Split ratio = 20: 1 method 40 ° C (3 min)? 10 ° C / min? 320 ° C (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. Adhesion (kgf / (mm) ² ): A glass having a height of 2 mm and a width of 5 mm x 5 mm was impregnated with 0.01 g of the compositions shown in Table 2 below, and a glass-glass and SiNx-SiNx silicon nitride - after curing in the intensity of D-bulb 1000J / cm ² as a light source and then the obtained silicon nitride) were compared by measuring the dajji 4000 bond tester share Die strength.

Example Comparative Example 5 6 7 8 9 10 11 12 13 14 15 16 One 2 3 4 B B1 - 10 - 10 - - - 10 - - 10 - 10 20 30 - B2 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 B3 30 20 10 20 30 10 30 20 10 30 20 10 30 20 10 30 A A1 10 10 30 - - - - - - - - - - - - - A2 - - - 10 10 30 - - - - - - - - - - A3 - - - - - - 10 10 30 - - - - - - - A4 - - - - - - - - - 10 10 30 - - - - C 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 D - - - - - - - - - - - - - - - 10 Moisture permeability
(g / m ² ㆍ 24 hr) 3.9 3.3 2.5 4.3 4.1 3.5 3.9 3.7 3.2 4.2 4.4 4.6 6.9 7.5 9.9 14.1 Outgassing Amount (ppm) 170 130 120 210 120 70 250 190 180 220 180 110 1290 1540 2980 1620 Light curing rate (%) 91.8 92.6 92.3 91 89.3 88.6 93.7 95.7 96.2 91.4 90.3 92.7 82 88 89 82.1 Die share strength (kgf / (mm) ² )
GLS / GLS 14.6 17.3 21.2 12.6 13.3 18.2 9.3 11.3 13.4 13.6 14.4 16.8 5.8 6.3 6.1 5.8 Die share strength (kgf / (mm) ² )
SiNx / SiNx 7.1 8.2 10.3 6.2 6.8 9.1 4.2 5.6 6.8 6.9 7.1 8.2 2.3 2.8 2.8 2.4

As shown in Table 2, the coating film formed of the photo-curable composition containing the spiroflavluorene-based compound of the present invention had low moisture permeability, markedly low outgass evaluation amount at the outgass evaluation, high light curing rate, Respectively.

On the other hand, the coating film prepared from the composition of Comparative Example 1-3, which did not contain a spirobifluorene compound, had a high moisture permeability, an outgassing evaluation value remarkably high when outgassing was evaluated, a low light curing rate, And the effects of the present invention can not be realized.

Also, the coating film prepared from the composition of Comparative Example 4 containing a fluorene-based compound having no biphenyls was brittle and had a low degree of curing and a large amount of outgassing.

It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (19)

A spirobifluorene compound represented by the following formula (1-1): < EMI ID =
&Lt; Formula 1-1 &gt;

(Wherein R ₁ and R ₃ are the same or different and each represents a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a substituted or unsubstituted 3-carbon group A substituted or unsubstituted arylalkyl group having 7 to 20 carbon atoms, a hydroxy group, a halogen, or a group represented by the following formula (2)
At least one of R &lt; ₁ &gt; and R &lt; ₃ &gt;
(2)

(Wherein, * is a linking group to the aromatic carbon of the formula (1-1)
Y is O, S, NH, or NR (wherein R is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms)
R ₅ is a substituted or unsubstituted aliphatic hydrocarbon having 1 to 30 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon having 6 to 30 carbon atoms, or a substituted or unsubstituted alicyclic hydrocarbon having 3 to 20 carbon atoms,
X ₁ and X ₂ are the same or different and independently of one another O, S, NH, or NR (wherein R is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms Lt; / RTI >
Z ₁ and Z ₂ are the same or different and represent hydrogen, the following formula 3 or the following formula 4,
(3)

(Wherein, * is a linking group to X ₁ or a linking group to X ₂ ,
And R &lt; ₆ &gt; is hydrogen or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms)
&Lt; Formula 4 &gt;

(Wherein, * is a linking group to X ₁ or a linking group to X ₂ ,
R ₇ represents a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkylene group having 5 to 20 carbon atoms, a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, An arylalkylene group having 7 to 20 carbon atoms,
R ₈ is hydrogen or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms,
X ₃ is O, S, NH, or NR (wherein R is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms)
At least one of Z ₁ and Z ₂ is the above-described formula (3) or (4)
n ₁ and n ₂ are integers of 0 to 4, at least one of n ₁ and n ₂ is an integer of 1 to 4,
In the substituted or unsubstituted heterocyclic group, at least one hydrogen atom of the functional group is substituted by halogen (F, Cl, Br or I), a hydroxy group, a nitro group, a cyano group, an imino group (R '), R', R "and R '' each independently represent an alkyl group having 1 to 10 carbon atoms Alkyl group, an amidino group, a hydrazine or hydrazone group, a carboxy group, an unsubstituted alkyl group having 1-20 carbon atoms, an unsubstituted aryl group having 6-30 carbon atoms, an unsubstituted cycloalkyl group having 3-30 carbon atoms, A heteroaryl group having 3-30 carbon atoms, or an unsubstituted heterocycloalkyl group having 2-30 carbon atoms). delete The spirobifluorene compound according to claim 1, wherein the spirobifluorene compound is represented by any one of the following formulas (5) to (8)
&Lt; Formula 5 >

(6)

&Lt; Formula 7 >

(8)

.
A copolymer of a monomer mixture comprising the spirobifluorene compound of claim 1.
The composition according to claim 4, wherein the monomer mixture is a (meth) acrylic monomer having an alkyl group having 1 to 10 carbon atoms, a (meth) acrylic monomer having an alkyl group having 1 to 10 carbon atoms and a hydroxyl group, , A (meth) acrylic monomer having a hetero-alicyclic group, and a (meth) acrylic monomer having a carboxylic acid group.
(A) the spirobifluorene compound of claim 1;
(B) a non-spirobifluorene photocurable monomer; And
(C) an initiator.
7. The photocurable composition according to claim 6, wherein the spirobifluorene compound is represented by any one of the following formulas (5) to (8)
&Lt; Formula 5 >

(6)

&Lt; Formula 7 >

(8)

.
7. The photocurable composition according to claim 6, wherein the spirobifluorene compound is contained in an amount of 5 to 90% by weight based on the solid content of the composition.
The photocurable monomer according to claim 6, 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.
7. The photocurable composition of claim 6, wherein the initiator comprises a photopolymerization initiator.
The photocurable composition according to claim 6, wherein the composition comprises 5 to 90% by weight of the component (A), 5 to 90% by weight of the component (B), and 0.1 to 10% by weight of the component (C) on a solid basis.
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 comprises a cured product of the photocurable composition of any one of claims 6 to 11.
13. The encapsulated device of claim 12, wherein the organic barrier layer has a moisture permeability of less than 4.9 g / m &lt; ² &gt; .24 hr measured at 37.8 DEG C and 100% relative humidity for a coating thickness of 5 mu m for 24 hours.
13. The encapsulated device of claim 12, wherein the organic barrier layer has an adhesion to the inorganic barrier layer of at least 4 kgf / (mm) ² .
13. The method of claim 12, wherein the inorganic barrier layer is selected from the group consisting of metals, intermetallic compounds or alloys, oxides of metals or mixed metals, fluorides of metals or mixed metals, nitrides of metals or mixed metals, metal carbides, (Al), selenium (Se), zinc (Zn), zinc (Zn), zinc (Zn), and combinations thereof, At least one of zinc (Zn), antimony (Sb), indium (In), germanium (Ge), tin (Sn), bismuth (Bi), transition metals and lanthanide metals.
13. The encapsulated device of claim 12, wherein the organic barrier layer and the inorganic barrier layer are alternately formed.
13. The encapsulated device of claim 12, wherein the barrier stack is stacked with less than a total of ten layers of the organic barrier layer and the inorganic barrier layer.
13. The encapsulated device of claim 12, 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.
13. The device of claim 12, 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.

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