KR101574840B1 - 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 photo-curable monomer and (B) a monomer of formula (1) or an oligomer thereof, a barrier layer comprising the same, and an encapsulated device comprising the same.

Description

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

The present invention relates to a photocurable composition, a barrier layer comprising the same, and an encapsulated device comprising the same.

An organic light emitting diode (OLED) is a structure in which a functional organic layer is interposed between an anode and a cathode. The hole injected into the anode and the electrons injected into the anode recombine to form an exciton 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.

Related prior arts include Korean Patent Publication No. 2005-0021054 entitled " Organic electroluminescent device and its manufacturing method ".

It is an object of the present invention to provide a photocurable composition capable of realizing a layer in which the moisture permeability and the outgassing amount after curing are remarkably low, the degree of curing is high, and the shift due to curing shrinkage stress does not occur.

Another object of the present invention is to provide a photocurable composition capable of realizing a layer capable of prolonging the lifetime of a device member when encapsulating a member for a device.

It is another object of the present invention to provide a barrier layer comprising a cured product of said photocurable composition and an encapsulated device comprising the same.

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

≪ Formula 1 >

(Wherein Y is one of the following formulas (2) to (4)

(2)

(3)

≪ Formula 4 >

Z is the following formula (5).

≪ Formula 5 >

)

)

Another aspect of the present invention is an encapsulated device comprising a device member and a barrier stack formed on the device member and including an inorganic barrier layer and an organic barrier layer, wherein the organic barrier layer has an outgassing amount of less than 2000 ppm .

An encapsulated device, which is another aspect of the present invention, comprises a member for a device, and a barrier stack formed on the device for the device and including an inorganic barrier layer and an organic barrier layer, wherein the organic barrier layer has a thickness The moisture permeability measured at 37.8 DEG C, 100% relative humidity, and 24 hours with respect to 5 mu m can be 4.0 g / m < ² >

The present invention provides a photo-curing composition capable of realizing a layer having a significantly low moisture-permeability and outgassing amount after curing and capable of preventing deterioration of the performance of the device during device sealing and prolonging its service life. Also, the present invention provides a photocurable composition capable of realizing a layer in which no shift occurs during sealing of a device due to its high degree of curing.

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

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

One aspect of the present invention is a photocurable composition comprising (A) a photocurable monomer and (B) a monomer represented by the following formula (1) or an oligomer thereof.

(A) Photocurable Monomer

The photocurable monomer may include a heterocyclic or non-epoxy monomer containing no heterocycle or epoxy group.

In embodiments, the photo-curable monomer may be selected from the group consisting of non-oxirane systems that do not contain an oxirane group, non-oxetane systems that do not include an oxetane group, or non-oxycane systems that do not contain an epoxycycloalkyl group Alkyl-based monomer.

In one embodiment, the photocurable monomer may not comprise one of the following formulas (2) to (4):

(2)

(Where * is the connecting site of the element,

X ₁ and X ₂ are the same or different and are O, S, NR, or a substituted or unsubstituted R'-CR "(R, R ', R" is hydrogen, or a substituted or unsubstituted alkyl group having 1-5 carbon atoms Lt; / RTI >

At least one of X < _{1 >} and X < ₂ > is O, S,

R ₁ represents a substituted or unsubstituted alkylene group having 1-30 carbon atoms, a substituted or unsubstituted alkyl ether group having 1-30 carbon atoms, a substituted or unsubstituted alkyleneoxy group having 1-30 carbon atoms, a substituted or unsubstituted carbon number A substituted or unsubstituted alkylthio group having 1 to 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, or a substituted Or an unsubstituted alkoxysilane group having 1-20 carbon atoms)

(3)

(Where * is the connecting site of the element,

X ₃ , X ₄ and X ₅ are the same or different and are O, S, NR, substituted or unsubstituted R'-CR "(R, R ', R"Lt; / RTI >

At least one of X ₃ , X ₄ , and X ₅ is O, S, or NR,

R < ₁ > is as defined above,

R ₂ represents hydrogen, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkyl ether group having 1 to 30 carbon atoms, a substituted or unsubstituted alkylamine group having 1 to 30 carbon atoms or a dialkylamine group, A substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted arylalkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted aryl group having 1 to 20 carbon atoms Alkoxy group)

≪ Formula 4 >

(Where * is the connecting site of the element,

X ₆ is O, S, NR (R is hydrogen or a substituted or unsubstituted alkyl group having 1-5 carbon atoms)

R ₁ and R ₂ are as defined above,

n is an integer of 1 to 5, and m is an integer of 0 to n + 1.

The photocurable monomer may include a monofunctional monomer having an unsaturated group, a polyfunctional monomer, or a mixture thereof. In embodiments, the photo-curable monomer may comprise monomers having 1-30, preferably 1-20, and more preferably 1-5 photo-curable functional groups. The photo-curable functional group may include a substituted or unsubstituted vinyl group, an acrylate group, or a methacrylate group.

The photocurable monomer may comprise a mixture of a monofunctional monomer and a multifunctional monomer. The monofunctional monomer: polyfunctional monomer in the mixture may be contained in a weight ratio of 1: 0.1 to 1: 4, preferably 1: 1 to 1: 4, more preferably 1: 2 to 1: 4.

The photocurable monomer may be an aromatic hydrocarbon compound having 6-20 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; Vinyl cyanide compounds; Unsaturated amide compounds; A mono-alcohol or a polyfunctional (meth) acrylate of a polyhydric alcohol, and the like. The 'polyhydric alcohol' may be an alcohol having two or more hydroxyl groups and having 2 to 20, preferably 2 to 10, more preferably 2 to 6 alcohols.

In an embodiment, the photocurable monomer is an aromatic hydrocarbon 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 including (meth) acrylic 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; 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 an amount of 1-99 parts by weight, preferably 50-90 parts by weight, based on 100 parts by weight of (A) + (B) of the composition on a solid basis. In the above range, low outgassing and moisture permeability can be realized with a higher light curing effect.

(B) Monomer  Or his Oligomer

The monomer or oligomer thereof of Formula 1 may be a photo-curable monomer having photo-curable functional groups or an oligomer thereof. The photo-curable functional group may include a substituted or unsubstituted vinyl group, an acrylate group, or a methacrylate group.

In an embodiment, the monomer of Formula 1 may be represented by Formula 1:

≪ Formula 1 >

(Wherein Y is one of the following formulas (2) to (4)

(2)

(Wherein * is the connecting site of -O- of Z in formula (1)

X ₁ and X ₂ are the same or different and are O, S, NR, or a substituted or unsubstituted R'-CR "(R, R ', R" is hydrogen, or a substituted or unsubstituted alkyl group having 1-5 carbon atoms Lt; / RTI >

At least one of X < _{1 >} and X < ₂ > is O, S,

R ₁ represents a substituted or unsubstituted alkylene group having 1-30 carbon atoms, a substituted or unsubstituted alkyl ether group having 1-30 carbon atoms, a substituted or unsubstituted alkyleneoxy group having 1-30 carbon atoms, a substituted or unsubstituted carbon number A substituted or unsubstituted alkylthio group having 1 to 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, or a substituted Or an unsubstituted alkoxysilane group having 1-20 carbon atoms)

(3)

(Wherein * is a connecting site of -O- of Z in formula (1)

X ₃ , X ₄ and X ₅ are the same or different and are O, S, NR, substituted or unsubstituted R'-CR "(R, R ', R"Lt; / RTI >

At least one of X ₃ , X ₄ , and X ₅ is O, S, or NR,

R < ₁ > is as defined above,

R ₂ represents hydrogen, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkyl ether group having 1 to 30 carbon atoms, a substituted or unsubstituted alkylamine group having 1 to 30 carbon atoms or a dialkylamine group, A substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted arylalkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted aryl group having 1 to 20 carbon atoms Alkoxy group)

≪ Formula 4 >

(Wherein * is the connecting site of -O- of Z in formula (1)

X ₆ is O, S, NR (R is hydrogen or a substituted or unsubstituted alkyl group having 1-5 carbon atoms)

R ₁ and R ₂ are as defined above,

n is an integer of 1 to 5, and m is an integer of 0 to n + 1)

Z is the following formula (5).

≪ Formula 5 >

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

R ₃ is hydrogen, or a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms)

Preferably, X ₁ is O and X ₂ is -CH ₂ -.

Preferably, X ₄ is O, and X ₃ and X ₅ are -CH ₂ -.

Preferably, R ₁ is an alkylene group having ₁ to 10 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms.

Preferably, R ₂ is hydrogen or an alkyl group having 1 to 6 carbon atoms and 1 to 6 carbon atoms.

Preferably, n is an integer of 1-2.

In one embodiment, the monomer of Formula 1 is selected from the group consisting of glycidyl (meth) acrylate, (3-ethyl-3-oxetanyl) methyl (meth) acrylate, 3,4-epoxycyclohexylmethyl ≪ / RTI >

The monomer of Formula 1 or its oligomer may be included in the photocurable composition together with the photocurable monomer to provide a layer having a significantly lowered moisture permeability and outgassing amount after curing, and the degree of curing can be increased. In addition, when the monomer of Formula 1 is included in the organic barrier layer, the damage to the device member from the plasma used for deposition of the inorganic barrier layer can be minimized.

The monomer or oligomer of Formula 1 may be contained in an amount of 1 to 99 parts by weight, preferably 10 to 50 parts by weight, based on 100 parts by weight of (A) + (B) based on the solid content. Within this range, low outgassing and moisture permeability can be realized with a higher light curing effect.

The composition may further comprise an initiator.

(C) Initiator

The initiator may include at least one of a photopolymerization initiator and a photo acid generator.

The photopolymerization 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 photopolymerization initiator is used in an amount of 0.1 to 20 parts by weight, preferably 1 to 10 parts by weight, more preferably 2 to 8 parts by weight, based on 100 parts by weight of (A) + (B) 2-5 parts by weight. In the above range, photopolymerization can sufficiently take place at the time of exposure, and the transmittance can be prevented from being lowered due to the unreacted initiator remaining after the photopolymerization.

The photoacid generator may generate an acid at the same time as the radical polymerization reaction by the photopolymerization initiator to cure the epoxy group, thereby enhancing the photo-curing effect.

The photoacid generator may include, without limitation, conventional photoacid generators. For example, the photoacid generator may be a carbazole system, a diketone system, a sulfonium system, an iodonium system, a diazo system, a nonimidazole system or a mixture thereof.

The photoacid generator may be added in an amount of 0.001-10 parts by weight, preferably 0.01-5 parts by weight, more preferably 0.1-2 parts by weight based on 100 parts by weight of (A) + (B) based on the solid content in the composition. In the above range, photopolymerization can sufficiently take place at the time of exposure, and the transmittance can be prevented from being lowered due to the unreacted photoacid generator remaining after the photopolymerization.

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

The photocurable composition can be formed by mixing the photocurable monomer, the monomer of Formula 1 or an oligomer thereof, or by further mixing an initiator. Preferably, it may be formed into a solventless type solventless type.

The photocurable composition may have a degree of cure of 90% or more, preferably 90-99%, more preferably 92.5-98.5%. In the above range, since the hardening shrinkage stress after curing is low and the shift is not generated, the layer can be used for sealing the device.

Devices for devices, in particular devices for display devices, can degrade or become defective due to the permeation of gases or liquids in the surrounding environment, such as oxygen and / or moisture in the atmosphere and / or water vapor and chemicals used in processing into electronics have. To this end, the member for the device needs to be encapsulated or encapsulated.

Such a device member may be an organic light emitting device (OLED), a lighting device, a flexible organic light emitting device, a metal sensor pad, a micro disk 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 of the present invention may form an organic barrier layer for use in the encapsulation or encapsulation of a member for the device, particularly an organic light emitting device or a flexible organic light emitting device.

The barrier layer further aspect of the present invention (barrier layer) is the moisture permeability measured at 37.8 ℃ film for thickness 5㎛, 100% relative humidity, and a 24-hour condition as an organic barrier layer (moisture permeability) is 4.0g / m ² and 24 hours or less. Within this range, it can be used for sealing members for devices. Preferably, the moisture permeability may be 1.0-4.0 g / m ² .24 hr, more preferably 1.2-3.6 g / m ² 24 hr.

The barrier layer, which is another aspect of the present invention, may be an organic barrier layer and may have an outgassing amount of 2000 ppm or less. In the above range, there is little influence when applied to the member for the apparatus, and the life of the member for the apparatus can be maintained for a long time. Preferably, the outgas generation amount may be 10-1000 ppm.

The barrier layer may comprise a cured product of the photocurable composition.

In an embodiment, the barrier layer may be formed by photocuring the photocurable composition. But are not limited to, the photocurable composition is coated with a 0.1㎛-20㎛, preferably 1㎛-10㎛ thickness, it can be cured by irradiation in 10-500mW / cm ² for one second to -50 seconds.

The barrier layer has the above-described moisture permeability and outgassing amount, and can be used as an encapsulation of device members by forming a barrier stack together with the following inorganic barrier layer.

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

Since the inorganic barrier layer is different from the organic barrier layer in constitutional component, 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, the inorganic barrier layer may be formed of 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, Or borides of mixed metals, oxygen borides of metals or mixed metals, silicides of metals or mixed metals, or mixtures thereof.

In an embodiment, the metal is selected from the group consisting of Si, Al, Selenium, Zn, Sb, In, Ge, Sn, Bi, ), A transition metal, a lanthanide metal, and the like.

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 organic barrier layer can secure the above-described moisture permeability and outgassing amount. 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 may comprise a cured product of the photocurable composition.

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

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 of the device member.

Preferably, the organic barrier layer and the inorganic barrier layer may be formed in two or more layers alternately, and the total number of the organic barrier layer and the inorganic barrier layer may be 10 or less (e.g., 2-10), preferably 7 or less (e.g., 2-7) As shown in FIG.

In the barrier stack, the thickness of one organic barrier layer may be 0.1 占 퐉 to 20 占 퐉, preferably 1 占 퐉 to 10 占 퐉, and the thickness of one inorganic barrier layer may be 5 nm to 500 nm, preferably 5 nm to 50 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.

The inorganic 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.

The organic barrier layer may be deposited by the same method as the inorganic barrier layer or by coating and curing the photocurable composition.

 An encapsulated device, which is another aspect of the present invention, may include a member for the device, and a barrier stack formed over the device for the device and including an inorganic barrier layer and an organic barrier layer.

In an embodiment, the organic barrier layer may have a moisture permeability of 4.0 g / m < ² > .24 hr or less measured at 37.8 DEG C, 100% relative humidity, and 24 hours for a film thickness of 5 mu m.

 In another embodiment, the organic barrier layer may have an outgassing amount of 2000 ppm or less.

The organic barrier layer may comprise a cured product of the photocurable composition.

The organic barrier layer may mean a sealing layer for protecting a member for an apparatus including an organic electroluminescent portion, an organic solar cell, and the like. The organic barrier layer may prevent the member for the device from being decomposed or oxidized by the external environment for moisture, oxygen, and the like. Further, the organic barrier layer has a remarkably small amount of outgassing even under high humidity or high temperature and high humidity, thereby minimizing the outgas effect on the device member, thereby preventing the performance of the device member from deteriorating and shortening the service life.

The organic barrier layer may be formed on or under the inorganic barrier layer.

The inorganic barrier layer may mean a sealing layer for protecting a member for an apparatus including an organic electroluminescent portion, an organic solar cell, and the like. The inorganic barrier layer may seal the element by contacting the element for the device, or may seal the internal space in which the element for the device is accommodated without contacting the element for the device. The inorganic barrier layer can prevent the element for the device from being disassembled or damaged by blocking the contact of the element with oxygen or moisture outside.

The inorganic barrier layer may be formed on the device member, on top of the organic barrier layer, or on the bottom of the organic barrier layer.

The encapsulated device is encapsulated by an inorganic barrier layer and an organic barrier layer, which are barrier layers having different properties. At least one of the inorganic barrier layer and the organic barrier layer may be bonded to the substrate for device encapsulation.

The inorganic barrier layer and the organic barrier layer may be included in the device more than once or more times. In one embodiment, the inorganic barrier layer and the organic barrier layer may be alternately deposited, such as an inorganic barrier layer / organic barrier layer / inorganic barrier layer / organic barrier layer. Preferably, the inorganic barrier layer and the organic barrier layer may be included in total not more than 10 times (e.g., 2 to 10 times), more preferably not more than 7 times (e.g., 2 to 7 times).

Details of the organic barrier layer and the inorganic barrier layer are as described above.

A substrate may be included depending on the type of member for the apparatus.

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, the substrate may be made of a material such as transparent glass, a plastic sheet, a silicon or metal substrate, or the like.

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

1, an encapsulated device 100 is formed on a substrate 10, a device member 20 and a device member 20 formed on the substrate 10, and the inorganic barrier layer 31 and organic And the barrier layer 30 including the barrier layer 32. The inorganic barrier layer 31 is in contact with the device member 20.

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

 2, an encapsulated device 200 is formed on a substrate 10, a device member 20 and a device member 20 formed on the substrate 10, and the inorganic barrier layer 31 and organic And the inorganic barrier layer 31 is capable of sealing the internal space 40 in which the device member 20 is accommodated.

 1 and 2 show a structure in which the inorganic barrier layer and the organic barrier layer are formed as a single layer, respectively. However, the inorganic barrier layer and the organic barrier layer may be formed a plurality of times. Further, a sealant and / or a substrate may be further formed on the side and / or the top of the composite barrier layer composed of the inorganic barrier layer and the organic barrier layer (not shown in FIGS. 1 and 2).

 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 photocurable composition may be applied in a thickness of 1-5 占 퐉 by spin coating, slit coating, or the like, and light may be applied to form an organic barrier layer. The formation process of the inorganic barrier layer and the organic barrier layer may be repeated (preferably, 10 times or less).

In an embodiment, the encapsulated device may be an organic electroluminescent display device including an organic electroluminescent portion, a display device including a liquid crystal display device, a solar cell, and the like, but is not limited thereto.

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) 3-Ethyl-3-oxetanyl) methyl Acrylate OXE-10 (available from Osaka Yuki Co., Ltd., formula 3) ), (B3) 7-Oxabicyclo [4,1,0] hept-3-ylmethyl methacrylate, Cyclomer M100 (Daicel, Including Formula 4)

(C) initiator: (C1) photopolymerization initiator Darocur TPO (BASF), (C2) photo acid generator: Irgacure PAG 121 (BASF)

Examples Comparative Example

(B) a monomer represented by the formula (1) 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 the mixture was stirred 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 1 below.

Property evaluation method

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 of Organic Barrier Layer: 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 (width x length x thickness) organic Barrier layer specimens are obtained. For the specimen, use a GC / MS instrument (Perkin Elmer Clarus 600). As GC / MS, a helium gas (flow rate: 1.0 mL / min, average velocity = 32 cm / s) was used as a mobile phase using a DB-5MS column (length: 30 m, diameter: 0.25 mm, ), The split ratio is 20: 1, the temperature condition is kept at 40 ° C for 3 minutes, then the temperature is raised at a rate of 10 ° C / minute, and then the temperature is maintained at 320 ° C for 6 minutes. The adsorbent was Tenax GR (5% phenylmethylpolysiloxane), and the adsorbent was N2 purge at a flow rate of 300 mL / min. . As a standard solution, a calibration curve is prepared at 150 ppm, 400 ppm, and 800 ppm of a toluene solution in n-hexane, and R2 value is obtained as 0.9987. The above conditions are summarized in Table 1 below.

division
Detail Collection conditions





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


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



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

3. hardening: with respect to the photocurable composition of FT-IR (NICOLET 4700, Thermo Co.) for use in the vicinity of 1635cm ^-1 (C = C), 1720cm ^-1 measured intensity of the absorption peak in the vicinity of the (C = O) do. A photocurable composition is applied on a glass substrate by spraying and irradiated at 100 mW / 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). 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 degree of cure is calculated according to the following formula (1).

<Formula 1>

Hardening degree (%) = | 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 at about 1635 cm ^-1 to the intensity of the absorption peak at about 1720 cm ^-1 for the photo-curable composition.

Example Comparative Example One 2 3 4 5 6 One 2 (A) (A1) 20 20 20 - - - 50 30 (A2) 60 60 60 40 40 40 40 60 (A3) 10 10 10 10 10 10 10 10 (B) (B1) 10 - - 50 - - - - (B2) - 10 - - 50 - - - (B3) - - 10 - - 50 - - (C) (C1) 5 5 5 5 5 5 5 - (C2) One One One One One One One 6 Moisture permeability
(g / m ² ㆍ 24 hr) 3.6 3.2 2.2 2.3 2.1 1.2 12.5 7.9 Outgassing Amount (ppm)  830 880 320 630 540 180 8540 2450 Hardness (%) 92.5 94 93 95 98 94 83 88

As shown in Table 2, the coating film formed from the photocurable composition of the present invention had a low moisture permeability, markedly low outgassing, and a markedly high degree of curing.

On the other hand, the coating film formed of the photocurable composition of Comparative Example 1, which does not include the monomer of Formula 1, had a significantly higher moisture permeability than that of the present invention, a higher amount of outgassing, and a lower degree of curing than the present invention. Also, the coating film formed of the composition of Comparative Example 2, which does not include the monomer of Formula 1 and the photopolymerization initiator, was also significantly higher in moisture permeability than the present invention, had a higher outgassing amount, and had a lower degree of curing than the present invention.

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 (19)

(A) a photocurable monomer and (B) a monomer or oligomer thereof represented by the following formula (1):
&Lt; Formula 1 >

(Wherein Y is one of the following formulas (2) to (4)
(2)

(Wherein * is a connecting site to Z in formula (1)
X ₁ and X ₂ are the same or different and are O, S, NR, or a substituted or unsubstituted R'-CR "(R, R ', R" is hydrogen, or a substituted or unsubstituted alkyl group having 1-5 carbon atoms Lt; / RTI &gt;
At least one of X &lt; _{1 &gt;} and X &lt; ₂ &gt; is O, S,
R ₁ represents a substituted or unsubstituted alkylene group having 1-30 carbon atoms, a substituted or unsubstituted alkyl ether group having 1-30 carbon atoms, a substituted or unsubstituted alkyleneoxy group having 1-30 carbon atoms, a substituted or unsubstituted carbon number A substituted or unsubstituted alkylthio group having 1 to 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, or a substituted Or an unsubstituted alkoxysilane group having 1-20 carbon atoms)
(3)

(Wherein * is the connecting site for Z in formula (1)
X ₃ , X ₄ and X ₅ are the same or different and are O, S, NR, substituted or unsubstituted R'-CR "(R, R ', R"Lt; / RTI >
At least one of X ₃ , X ₄ , and X ₅ is O, S, or NR,
R < ₁ > is as defined above,
R ₂ represents hydrogen, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkyl ether group having 1 to 30 carbon atoms, a substituted or unsubstituted alkylamine group having 1 to 30 carbon atoms or a dialkylamine group, A substituted or unsubstituted alkyl group having 1-30 carbon atoms, a substituted or unsubstituted aryl group having 6-30 carbon atoms, a substituted or unsubstituted arylalkyl group having 7-30 carbon atoms, Lt; / RTI &gt;
&Lt; Formula 4 &gt;

(Wherein * is a connecting site to Z in formula (1)
X ₆ is O, S, NR (R is hydrogen or a substituted or unsubstituted alkyl group having 1-5 carbon atoms)
R ₁ and R ₂ are as defined above,
n is an integer of 1 to 5, and m is an integer of 0 to n + 1)
Z is the following formula (5).
&Lt; Formula 5 &gt;

In the above, * is the connecting site of carbon of R ₁ ,
And R ₃ is hydrogen or a substituted or unsubstituted alkyl group having 1-30 carbon atoms).
The method of claim 1, wherein the monomer of Formula 1 is selected from the group consisting of glycidyl (meth) acrylate, (3-ethyl-3-oxetanyl) methyl (meth) acrylate, 3,4-epoxycyclohexylmethyl Acrylate &lt; / RTI &gt;
The photocurable composition according to claim 1, wherein the photocurable monomer (A) comprises a monomer having 1-30 substituted or unsubstituted vinyl groups, acrylate groups, or methacrylate groups.
(Meth) acrylate having an alkyl group of 1 to 20 carbon atoms, a di (meth) acrylate of a diol having a carbon number of 2 to 20, a triol having a carbon number of 3 to 20 Tri (meth) acrylate, and tetra (meth) acrylate of tetraol having 4-20 carbon atoms.
The composition according to claim 1, wherein the composition comprises 1-99 parts by weight of the component (A), 100-99 parts by weight of the component (A) and component (B) in 100 parts by weight of the sum of the components (A) By weight based on the total weight of the photocurable composition.
The photocurable composition of claim 1, wherein the composition further comprises (C) an initiator.
The photocurable composition according to claim 6, wherein the initiator (C) comprises at least one of a photopolymerization initiator and a photoacid generator.
The composition according to claim 6, wherein the composition comprises 1-99 parts by weight of the above (A), 100-99 parts by weight of said (B) 1-99 parts by weight of said component (A) And (C) 0.1 to 20 parts by weight based on 100 parts by weight of (A) + (B).
The photocurable composition according to claim 7, wherein the photopolymerization initiator is contained in an amount of 0.05 to 19 parts by weight based on 100 parts by weight of the sum (A) + (B) of the components (A) and (B).
The photocurable composition according to claim 7, wherein the photoacid generator is contained in an amount of 0.001-10 parts by weight based on 100 parts by weight of the sum (A) + (B) of the components (A) and (B).
A member for a device encapsulated using the photocurable composition of any one of claims 1 to 10.
Member for apparatus, and
And a barrier stack formed on the member for the device, the barrier stack comprising an inorganic barrier layer and an organic barrier layer,
Wherein the organic barrier layer comprises a cured product of the photocurable composition of claim 1 and the outgassing amount is 2000 ppm or less.
Member for apparatus, and
And a barrier stack formed on the member for the device, the barrier stack comprising an inorganic barrier layer and an organic barrier layer,
Wherein the organic barrier layer comprises a cured product of the photocurable composition of claim 1 and has a moisture permeability of 4.0 g / m &lt; ² &gt; for a film thickness of 5 mu m measured at 37.8 DEG C, 100% An encapsulated device of 24 hours or less.
14. The method of claim 12 or 13, wherein the inorganic barrier layer comprises a metal, a metal oxide, a metal nitride, a metal carbide, a metal oxynitride, a metal oxygen boride, or a mixture thereof, At least one of Al, Al, Se, Zn, Sb, In, Ge, Sn, Bi, And an encapsulated device.
14. The encapsulated device of claim 12 or 13, wherein the organic barrier layer and the inorganic barrier layer in the barrier stack are alternately formed.
14. The encapsulated device of claim 12 or 13, wherein the inorganic barrier layer and the organic barrier layer in the barrier stack are formed less than 10 times in total.
The encapsulated device according to claim 12 or 13, wherein the thickness of one of the organic barrier layers is 0.1 占 퐉 to 20 占 퐉 and the thickness of one of the inorganic barrier layers is 5 nm to 500 nm.
14. The device of claim 12 or 13, 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 solar cell, an integrated circuit, a charge coupled device, a light emitting polymer or a light emitting diode.
delete

Images