TWI613247B - Photocurable composition, barrier layer including the same, and encapsulated apparatus including the same - Google Patents

Abstract

The present invention discloses a photocurable composition comprising (A) a photocurable monomer and (B) a ruthenium containing monomer or an oligomer thereof, wherein the ruthenium containing monomer is represented by Formula 1. Also disclosed in the present invention is a barrier layer comprising the photocurable composition, and a packaging device comprising the barrier layer.

Description

Photocurable composition, barrier layer comprising the same, and packaging device comprising the same Field of invention

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

Background of the invention

An organic light emitting diode (OLED) refers to a structure of a functional organic material layer interposed between an anode and a cathode, wherein a high energy can be generated by recombination of a hole injected into the cathode and electrons injected into the anode. Excitons. The generated excitons can transition in the ground state to emit light in a specific wavelength band. Organic light-emitting diodes have various advantages such as self-illumination, fast response, wide viewing angle, ultra-thin, high definition and durability.

However, the organic light-emitting diode has a problem in that due to moisture or oxygen flowing in from the outside or outgas (outgas) generated inside or outside the light-emitting diode, organic material and/or electrode, although sealed. The material will be oxidized, causing deterioration in its performance and life. In order to overcome such problems, methods have been proposed, such as coating a photocurable sealant, attaching a transparent or opaque moisture absorbent, or a base on which an organic light-emitting portion is formed. The board provides frit.

Summary of invention

According to an aspect of the invention, the photocurable composition may comprise: (A) a photocurable monomer and (B) a ruthenium containing monomer or an oligomer thereof, wherein the oxime-containing system is represented by Formula 1:

Wherein X ₁ and X ₂ are the same or different and are O, S, NH or N-R';R' is a substituted or unsubstituted C1-C20 alkyl group; R ₁ and R ₂ are the same or different and are A single bond, a substituted or unsubstituted C1-C20 alkylene group, a substituted or unsubstituted C1-C30 alkyl ether group, a substituted or unsubstituted C1-C30 alkylamine group, a substituted or unsubstituted C1- a C30 alkyl sulfide group, a substituted or unsubstituted C6-C30 extended aryl group, a substituted or unsubstituted C7-C30 arylalkylene group, or a substituted or unsubstituted C1-C20 alkyleneoxy group; and Y ₁ , Y ₂ , Y ₃ , Y ₄ , Y ₅ and Y ₆ are the same or different and are hydrogen, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C1-C30 alkyl ether group, substituted Or an unsubstituted C1-C30 dialkylamine group, a substituted or unsubstituted C1-C30 alkyl sulfide group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C7-C30 aralkyl a substituted, unsubstituted or unsubstituted C1-C30 alkylene group, a substituted or unsubstituted C1-C30 alkyleneoxy group, or a compound represented by Formula 2 or Formula 3: [Formula 2]

Wherein * represents a binding site of Si in Formula 1; R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are the same or different and are hydrogen, substituted or unsubstituted C1-C30 alkyl, substituted Or an unsubstituted C1-C30 alkyl ether group, a substituted or unsubstituted C1-C30 dialkylamine group, a substituted or unsubstituted C1-C30 alkyl sulfide group, a substituted or unsubstituted C6- a C30 aryl group, or a substituted or unsubstituted C7-C30 arylalkyl group; X ₃ is O, S, NH, or N-R';R' is a substituted or unsubstituted C1-C20 alkyl group; and Z ₁ And Z ₂ are the same or different, and are compounds represented by Formula 4:

Wherein * represents a binding site of R ₁ or R ₂ in Formula 1, R ₉ is hydrogen, or a substituted or unsubstituted C1-C30 alkyl group; and n is an integer of about 0 to 30 or an average value of n is about 0. To the extent of 30.

According to another aspect of the present invention, a packaging device may include a member of a device and a barrier stack formed on a member of the device and including an inorganic barrier layer and an organic barrier layer, wherein the organic barrier layer has The amount of outgassing (degassing) produced below about 2000 ppm.

According to a further aspect of the invention, a packaging device may comprise a member for a device and a barrier laminate formed on a component of the device and comprising an inorganic barrier layer and an organic barrier layer, wherein the organic barrier layer has a thickness of about 4.0 g/m ² . The water vapor transmission (transmission) rate (WVTR) below 24 hours, as measured at a layer thickness of 5 μm in the organic barrier layer and at 24 ° C at 37.8 ° C and 100% relative humidity (RH).

10‧‧‧Substrate

20‧‧‧ components of the device

30‧‧‧Block stack

31‧‧‧Inorganic barrier

32‧‧‧Organic barrier

40‧‧‧Internal space

100,200‧‧‧Package

1 is a cross-sectional view of a packaging device in accordance with an embodiment of the present invention.

2 is a cross-sectional view of a packaging device in accordance with another embodiment of the present invention.

detailed description

The term "substituted" as used herein, unless otherwise indicated, means that at least one hydrogen atom in the functional group of the present invention is substituted by a halogen (F, Cl, Br or I). , hydroxy, nitro, cyano, imino (=NH, =NR, wherein R is C1-C10 alkyl), amine [-NH2, -NH(R'), -N(R")(R "'), wherein R', R" and R''' are each independently a C1-C10 alkyl], fluorenyl, hydrazine or hydrazine group, a carboxylic acid group, a substituted or unsubstituted C1-C20 alkyl group a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted C3-C30 heteroaryl group, or a substituted or unsubstituted C2-C30 heterocycloalkyl group.

As used herein, the term "hetero" refers to a carbon atom substituted with an atom selected from the group consisting of N, O, S, and P.

As used herein, the symbol "*" is the joint of an element.

One aspect of the present invention relates to a photocurable composition comprising (A) a photocurable monomer, and (B) a ruthenium containing monomer or an oligomer thereof.

(A) Photocuring monomer

The photocurable monomer may refer to a non-fluorene-type photocurable monomer that does not contain hydrazine and has one or more photocurable functional groups, for example, (meth) acrylate groups, vinyl groups, and the like.

The photocurable monomer may comprise a mixture of a monofunctional monomer, a polyfunctional monomer, and the like, which may have one or more photocurable functional groups, such as an unsaturated group. The photocurable monomer may comprise a monomer having from about 1 to 30, preferably from about 1 to 20, more preferably from about 1 to 5 photocurable functional groups. The photocurable functional group may include a substituted or unsubstituted vinyl group, an acrylate group, or a methacrylate group.

The photocurable monomer may include a mixture of a monofunctional monomer and a polyfunctional monomer. In the mixture, the monofunctional monomer:polyfunctional monomer may be present in a weight ratio of from about 1:0.1 to about 1:10, preferably from about 1:0.5 to about 1:3.5.

Examples of the photocurable monomer may include a C6-C20 aromatic compound having a substituted or unsubstituted vinyl group; an unsaturated carboxylic acid ester having one or more C1-C20 alkyl groups, a C3-C20 cycloalkyl group, C6- a C20 aromatic group, or a hydroxyl group and a C1-C20 alkyl group; an unsaturated carboxylic acid ester having a C1-C20 aminoalkyl group; a vinyl ester of a C1-C20 saturated or unsaturated carboxylic acid; a C1-C20 unsaturated carboxylic acid Acid glycidyl ester; vinyl cyanide; unsaturated decylamine compound; monofunctional or polyfunctional (meth) acrylate of monohydric or polyhydric alcohol, and the like. 'Polyol' means an alcohol as follows: it has two or more, about 2 to 20, preferably about 2 Up to 10, more preferably about 2 to 6 hydroxyl groups.

In some embodiments, examples of the photocurable monomer may include, but are not limited to, a C6-C20 aromatic compound having an alkenyl group (including a vinyl group) such as styrene, α-methylstyrene, vinyltoluene, vinylbenzyl chloride. Ether ether, vinylbenzyl methyl ether, etc.; unsaturated carboxylic acid esters such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, (meth)acrylic acid-2- Hydroxyethyl ester, 2-hydroxybutyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, decyl (meth)acrylate, decyl (meth)acrylate, (A) Ethyl undecyl acrylate, dodecyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, etc.; unsaturated Aminoalkyl carboxylates such as 2-aminoethyl (meth)acrylate, 2-dimethylaminoethyl (meth)acrylate, etc.; saturated or unsaturated carboxylic acid vinyl esters such as Vinyl acetate, vinyl benzoate, etc.; C1-C20 unsaturated glycidyl carboxylate such as glycidyl (meth)acrylate; vinyl cyanide compound such as (meth)acrylonitrile An unsaturated decylamine compound such as (meth) acrylamide or the like; a monofunctional or polyfunctional (meth) acrylate of a monohydric or polyhydric alcohol, such as ethylene glycol di(meth)acrylate, triethylene glycol II (Meth) acrylate, trimethylolpropane tri(meth) acrylate, 1,4-butanediol di(meth) acrylate, 1,6-hexanediol di(meth) acrylate, Octanediol di(meth)acrylate, decanediol di(meth)acrylate, decanediol di(meth)acrylate, undecanediol di(meth)acrylate, dodecane two Alcohol di(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol Di(meth)acrylate, dipentaerythritol Tris(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, bisphenol A di(meth)acrylate, phenolic Epoxy (meth) acrylate, diethylene glycol di (meth) acrylate, tri (propylene glycol) di (meth) acrylate, poly (propylene glycol) di (meth) acrylate, and the like.

Preferably, the photocurable monomer may include at least one of the following: a mono(meth)acrylate having a C1-C20 alkyl group, a di(meth)acrylate of a C2-C20 diol, and a C3-C20 Tri(meth) acrylate of triol, and tetra (meth) acrylate of C4-C20 tetraol.

The photocurable monomer may be present in an amount of from about 1 to 99 parts by weight in terms of solid content and based on 100 parts by weight of (A) + (B). Preferably, the photocurable monomer is present in an amount of from about 20 to 95 parts by weight, more preferably from about 30 to 95 parts by weight, still more preferably from about 30 to 65 parts by weight. Within this range, the photocurable composition can exhibit strong resistance to plasma, thereby reducing or preventing outgassing (degassing) generation or reduction of water vapor transmission from the plasma in the manufacture of the thin encapsulation layer ( Through) rate.

(B) cerium-containing monomer or oligomer thereof

The ruthenium containing monomer or oligomer thereof may be a ruthenium type photocurable monomer or an oligomer thereof, which contains ruthenium (Si) and photocurable functional groups at both ends. The photocurable functional group may include a substituted or unsubstituted vinyl group, an acrylate group, or a methacrylate group.

The monomer or oligomer thereof may include a double-end curable monomer or an oligomer thereof.

In one embodiment, the ruthenium containing monomer can be represented by Formula 1:

Wherein X ₁ and X ₂ are the same or different and are O, S, NH or N-R';R' is a substituted or unsubstituted C1-C20 alkyl group; R ₁ and R ₂ are the same or different and Is a single bond, a substituted or unsubstituted C1-C20 alkylene group, a substituted or unsubstituted C1-C30 alkyl ether group, a substituted or unsubstituted C1-C30 alkylamine group, a substituted or unsubstituted C1 a C30 alkyl sulfide group, a substituted or unsubstituted C6-C30 extended aryl group, a substituted or unsubstituted C7-C30 arylalkylene group, or a substituted or unsubstituted C1-C20 alkyleneoxy group; ₁ , Y ₂ , Y ₃ , Y ₄ , Y ₅ and Y ₆ are the same or different and are hydrogen, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C1-C30 alkyl ether groups , substituted or unsubstituted C1-C30 dialkylamine group, substituted or unsubstituted C1-C30 alkyl sulfide group, substituted or unsubstituted C6-C30 aryl group, substituted or unsubstituted C7-C30 An aralkyl group, a substituted or unsubstituted C1-C30 alkylene group, a substituted or unsubstituted C1-C30 alkyleneoxy group, or a compound represented by Formula 2 or Formula 3:

Wherein * represents a binding site of Si in Formula 1; R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are the same or different and are hydrogen, substituted or unsubstituted C1-C30 alkyl, a substituted or unsubstituted C1-C30 alkyl ether group, a substituted or unsubstituted C1-C30 dialkylamine group, a substituted or unsubstituted C1-C30 alkyl sulfide group, a substituted or unsubstituted C6 group a C30 aryl group, or a substituted or unsubstituted C7-C30 arylalkyl group; X ₃ is O, S, NH, or N-R';R' is a substituted or unsubstituted C1-C20 alkyl group; ₁ and Z ₂ are the same or different and are a compound represented by Formula 4:

Wherein * represents a binding site of R ₁ or R ₂ in Formula 1, R ₉ is hydrogen, or a substituted or unsubstituted C1-C30 alkyl group; and n is an integer of about 0 to 30 or an average value of n is about 0. To 30.

Within this range, the water vapor transmission rate and the amount of outgassing (degassing) generated after the composition is cured can be lowered, and the photocuring rate can be increased. Preferably, n may be from about 0 to 15, more preferably from about 0 to 10.

R ₁ and R ₂ may be preferably C1-C10 alkylene, more preferably C1-C6 alkylene group.

Y ₁ , Y ₂ , Y ₃ , Y ₄ , Y ₅ and Y ₆ may preferably be a C1-C10 alkyl group, a C6-C14 aryl group, or a compound represented by Formula 2 or Formula 3, wherein R ₃ and R ₄ And R ₅ , R ₆ , R ₇ and R ₈ are a C1-C10 alkyl group. More preferably, Y ₁ , Y ₂ , Y ₃ , Y ₄ , Y ₅ and Y ₆ may be a C1-C6 alkyl group, or a compound represented by Formula 2 or Formula 3, wherein R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are C1-C6 alkyl groups.

Z ₁ and Z ₂ may be a compound represented by Formula 4, wherein R ₉ is hydrogen or a C1-C5 alkyl group.

In one embodiment, the ruthenium containing monomer may include at least one of the following: 1,3-bis(3-(methyl)acryloxypropyl)tetramethyldioxane, 1,3 - bis(3-(methyl)propenyloxypropyl)tetrakis(trimethyldecyloxy)dioxane and a monomer of formula 5:

Wherein Z ₁ , Z ₂ , R ₁ , R ₂ and n are as defined in formula 1.

The ruthenium-containing monomer or oligomer thereof included in the photocurable composition together with the photocurable monomer can provide a layer, and after curing, its water vapor transmission (transmission) rate and outgassing amount are remarkably lowered, thereby increasing photocuring. rate.

In addition, due to the presence of germanium, the germanium-containing monomer or oligomer thereof included in the organic barrier layer can minimize damage to the device from the plasma, wherein the plasma is used in an existing package structure (which is inorganic An inorganic barrier layer is deposited in the barrier layer and the organic barrier layer.

The ruthenium containing monomer or oligomer thereof may be present in an amount of from about 1 to 99 parts by weight, based on 100 parts by weight of the composition of (A) + (B). Preferably, the ruthenium containing monomer or oligomer thereof is present in an amount of from about 5 to 80 parts by weight, more preferably from about 5 to 70 parts by weight, still more preferably from about 35 to 70 parts by weight. Within this range, the photocurable composition can exhibit strong resistance to plasma, thereby reducing or preventing outgassing from the plasma or reducing the rate of water vapor transmission (transmission) in the preparation of the thin encapsulation layer.

The composition may further comprise an initiator.

(C) initiator

As the initiator, any conventional photopolymerization initiator can be used without being limited as long as the initiator can be photocured. For example, the photopolymerization initiator may include a starter based on triazine, acetophenone, benzophenone, thioxanthone, benzoin, phosphorus, ruthenium, and the like.

Examples of the triazine initiator may include 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-di(trichloromethyl)-s-triazine, 2-(3' , 4'-dimethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4'-methoxynaphthyl)-4,6-di(III Chloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-di(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6- Bis(trichloromethyl)-s-triazine, 2-biphenyl-4,6-di(trichloromethyl)-s-triazine, di(trichloromethyl)-6-styryl- S-triazine, 2-(naphthoquinone-1-yl)-4,6-di(trichloromethyl)-s-triazine (2-(naphtho-1-yl)-4,6-bis ( Trichloromethyl)-s-triazine), 2-(4-methoxynaphthoquinone-1-yl)-4,6-bis(trichloromethyl)-s-triazine (2-(4-methoxynaphtho-1) -yl)-4,6-bis(trichloromethyl)-s-triazine), 2,4-trichloromethyl (piperonyl)-6-triazine, 2,4-(trichloromethyl (4) '-Methoxystyryl)-6-triazine, and mixtures thereof.

啉代丙-1-酮、2-苄基-2-二甲基胺基-1-(4-

啉代苯基)-丁-1-酮、以及其等之混合物。 Examples of the acetophenone starter may include 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylpropiophenone, and p-tert-butyl Trichloroacetophenone, p-tert-butyldichloroacetophenone, 4-chloroacetophenone, 2,2'-dichloro-4-phenoxyacetophenone, 2-methyl-1-(4) -(methylthio)phenyl)-2-

Phenylpropan-1-one, 2-benzyl-2-dimethylamino-1-(4-

Orthophenylene)-butan-1-one, and mixtures thereof.

Examples of the benzophenone initiator may include benzophenone, benzamidine benzoic acid, benzamidine benzoic acid methyl ester, 4-phenyl benzophenone, hydroxybenzophenone, acrylated benzophenone, 4 , 4'-bis(dimethylamino)benzophenone, 4,4'-dichlorobenzophenone, 3,3'-dimethyl-2-methoxybenzophenone, and mixtures thereof .

Examples of the thioxanthone starter may include thioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthene Ketones, 2-chlorothioxanthone, and mixtures thereof.

Examples of the benzoin starter may include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyldimethyl group. Ketones, and mixtures thereof.

Examples of the phosphorus initiator may include benzhydrin phenylphosphine oxide, benzamidine diphenylphosphine oxide, and the like.

Examples of the hydrazine initiator may include 2-(o-benzamide)-1-[4-(phenylthio)phenyl]-1,2-octanedione, 1-(o-ethylindenyl)- 1-[9-Ethyl-6-(2-methylbenzhydrazin)-9H-indazol-3-yl]ethanone, and mixtures thereof.

The initiator may be present in an amount of from about 0.1 to 20 parts by weight, based on the solid content and based on 100 parts by weight of (A) + (B) in the photocurable composition. Within this range, photopolymerization can be sufficiently exhibited under exposure to light and a decrease in the transfer of remaining unreacted starter after photopolymerization can be prevented. Preferably, the initiator is present in an amount of from about 0.5 to 10 parts by weight, more preferably from about 1 to 8 parts by weight.

The photocurable composition can be produced by mixing a photocurable monomer, a ruthenium containing monomer or an oligomer thereof, or an additional initiator. Preferably, the composition can be produced as a solventless composition which does not require the use of a solvent.

The photocurable composition can exhibit a photocuring rate of about 90% or more. Within this range, after curing the photocurable composition, the curing shrinkage stress is low, thereby forming a layer that does not cause any change, enabling use in sealing applications. Preferably, the photocuring rate may be from about 90 to 99%, more preferably from about 92 to 98.5%.

Due to the gas or liquid in the surrounding environment, for example, oxygen and/or moisture and/or steam in the atmosphere, and due to the penetration of chemicals used to treat electronic products, the components of the device, especially the components of the display, suffer Degradation or deterioration of quality. To avoid this problem, the components of the device must be sealed or packaged.

Such components of the device may include, but are not limited to, an organic light emitting diode (OLED), a lighting device, a flexible organic light emitting diode display, a metal sensing pad, a microdisk laser, an electrochromic device (device) , Photochromic devices (devices), MEMS, solar cells, integrated circuits, charge coupled devices, luminescent polymers, light-emitting diodes, and the like.

The photocurable composition can be used to form an organic barrier layer for sealing or encapsulation of a flexible display.

Another aspect of the invention relates to a barrier layer which is an organic barrier layer and has a outgassing amount of about 2000 ppm or less. Within this range, the barrier layer has a negligible effect when applied to the components of the device and ensures a very long life of the components of the device. Preferably, the outgas production amount may be from about 10 to 2000 ppm, more preferably from about 570 to 1720 ppm.

A further aspect of the invention relates to a barrier layer which is an organic barrier layer and has a thickness of about 4.0 g/m ² . The water vapor transmission (permeation) rate below 24 hours, as measured at a layer thickness of 5 μm at 37.8 ° C and 100% RH for 24 hours. Within this range, a barrier layer can be used to seal the components of the device. Preferably, the water vapor transmission rate may be from about 1.0 to 4.0 g/m ² . 24 hours, more preferably about 1.9 to 3.5 g/m ² . 24 hours.

The barrier layer can include a cured product of the photocurable composition.

In one embodiment, the barrier layer can be formed by photocuring the photocurable composition. The photocurable composition may be applied to a thickness of about 0.1 μm to 20 μm, preferably about 1 μm to 10 μm, and then cured by irradiation light of about 10 to 500 mW/cm ² for about 1 second to about 50 seconds.

The barrier layer can have the above-described water vapor transmission (transmission) rate and outgassing amount to form a barrier laminate along with the inorganic barrier layer, which can be used for encapsulation of components of the device.

Yet another aspect of the invention relates to a barrier laminate comprising an organic barrier layer and an inorganic barrier layer.

The inorganic barrier layer may be different from the organic barrier layer and may enhance the action of the organic barrier layer.

The inorganic barrier layer is not particularly limited as long as the barrier layer exhibits good light transmittance and good moisture and/or oxygen barrier properties.

For example, the inorganic barrier layer may be composed of a metal, an intermetallic compound or 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, a metal or Mixed metal oxynitride (nitrogen oxide), metal or mixed metal boride, metal or mixed metal oxyborate (boron oxide), metal or mixed metal telluride, and mixtures thereof.

The metal may include, but is not limited to, bismuth (Si), aluminum (Al), selenium (Se), zinc (Zn), antimony (Sb), indium (In), germanium (Ge), tin (Sn), antimony (Bi). , transition metals, lanthanide metals, etc.

Specifically, the inorganic barrier layer may include hafnium oxide, tantalum nitride, hafnium oxynitride (niobium oxynitride), ZnSe, ZnO, Sb ₂ O ₃ , Al ₂ O ₃ , In ₂ O ₃ , or SnO ₂ .

The organic barrier layer has the above properties. Therefore, when the organic barrier layer and the inorganic barrier layer are alternately deposited, the smooth performance of the organic barrier layer can be ensured. In addition, the organic barrier layer can prevent defects in the inorganic barrier layer from diffusing to other inorganic barrier layers.

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

The barrier stack can include an organic barrier layer and an inorganic barrier layer. Here, the number of barrier laminates is not limited. The combination of barrier laminates can be modified depending on the degree of resistance to oxygen and/or moisture and/or vapor and/or chemical permeation.

In the barrier stack, the organic barrier layer and the inorganic barrier layer may be alternately deposited. This is because such deposition can provide a beneficial effect on the organic barrier layer (due to the physical properties of the composition). To this end, the organic barrier layer and the inorganic barrier layer can complement or enhance the encapsulation effect on the device.

The organic barrier layer and the inorganic barrier layer may be alternately deposited. In some embodiments, a total of 10 or less (eg, about 2 to 10), preferably 7 or less (eg, about 2 to 7 layers) organic barrier layers and inorganic barrier layers are alternately deposited.

In the barrier stack, the organic barrier layer may have a thickness of about 0.1 μm to 20 μm, preferably about 1 μm to 10 μm. The inorganic barrier layer can have about 5 The thickness of nm to 500 nm is preferably about 5 nm to 50 nm.

The barrier stack can be a thin-film encapsulator of the components of the device and can have a thickness of about 5 μm or less, preferably about 1.5 μm to 5 μm.

The inorganic barrier layer may be deposited by a vacuum method, for example, by sputtering, chemical vapor deposition, plasma chemical vapor deposition, evaporation, sublimation, electrocyclone resonance-plasma vapor deposition, or The combination of them.

The organic barrier layer may be deposited by a method similar to the inorganic barrier layer, or the organic barrier layer may be formed by coating and curing the photocurable composition.

Yet another aspect of the invention relates to a packaging device comprising a member of the device, and a barrier laminate formed on the member of the device and comprising an inorganic barrier layer and an organic barrier layer.

In one embodiment, the organic barrier layer can have a thickness of about 4.0 g/m ² . The water vapor transmission (permeation) rate below 24 hours, as measured at a layer thickness of 5 μm at 37.8 ° C and 100% relative humidity for 24 hours.

In another embodiment, the organic barrier layer can have a outgassing amount of less than about 2000 ppm.

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

The organic barrier layer may refer to an encapsulation layer for protecting a member of the device, including an organic light emitting diode, an organic solar cell, and the like. The organic barrier layer can prevent components of the device from being degraded or oxidized by external environments such as moisture, oxygen, and the like. In addition, in high humidity conditions or high temperature and high humidity conditions, the organic barrier layer rarely produces outgassing, thus the maximum limit The outgassing of the components of the device is reduced, which in turn prevents degradation of the performance of the components of the device and shortens the life.

The organic barrier layer may be formed on the upper or lower portion of the inorganic barrier layer.

The inorganic barrier layer may refer to a sealing layer for protecting a member of the device, the member including an organic light emitting diode, an organic solar cell, or the like. The inorganic barrier layer can be sealed by contacting the member of the device with the inorganic barrier layer, or by sealing the internal space of the member in which the device is placed without contacting the member of the device. The inorganic barrier layer can prevent the device from contacting external oxygen or moisture, thereby preventing degradation or damage to the components of the device.

The inorganic barrier layer may be formed on the upper portion of the member of the device or formed on the upper or lower portion of the organic barrier layer.

The packaging device has a structure in which an inorganic barrier layer and an organic barrier layer having different properties are used. At least one of an inorganic barrier layer and an organic barrier layer is coupled to the substrate for sealing the components of the device.

Multiple pairs (e.g., two or more pairs) of inorganic barrier layers and organic barrier layers can be included in the device. In one embodiment, the inorganic barrier layer and the organic barrier layer are deposited alternately (eg, in the order of an inorganic barrier layer/organic barrier layer/inorganic barrier layer/organic barrier layer). Preferably, the inorganic barrier layer/organic barrier layer is deposited a total of 10 times or less (for example, about 2 to 10 times), more preferably 7 times or less (for example, about 2 to 7 times).

Details of the organic barrier layer and the inorganic barrier layer have been described above.

A substrate may be included depending on the kind of components of the device.

It is not particularly limited to the substrate as long as it can cause the components of the device to be stacked thereon. Examples of the substrate may include transparent glass, plastic sheets, enamel or Metal substrate, etc.

1 shows a cross-sectional view of a package device in accordance with an embodiment of the present invention.

Referring to FIG. 1, a package apparatus 100 may include a substrate 10, a member 20 of the device on the substrate 10, and a barrier laminate 30 formed on the member 20 of the device and including an inorganic barrier layer 31 and an organic barrier layer 32, wherein inorganic The barrier layer 31 contacts the member 20 of the device 20.

2 shows a cross-sectional view of a package device in accordance with another embodiment of the present invention.

Referring to FIG. 2, the packaging device 200 includes a substrate 10, a member 20 of the device formed on the substrate 10, and a barrier laminate 32 formed on the member 20 of the device and including an inorganic barrier layer 31 and an organic barrier layer 32, wherein inorganic The barrier layer 31 can seal the interior space 40 of the component in which the device is housed.

1 and 2 illustrate a structure in which a single inorganic barrier layer and a single organic barrier layer are formed. However, the inorganic barrier layer and the organic barrier layer may be deposited multiple times. Additionally, a sealant and/or substrate (not shown in Figures 1 and 2) may be further formed on the sides and/or the upper portion of the composite barrier layer comprised of an inorganic barrier layer and an organic barrier layer.

The device can be produced by any typical method. A device is deposited on the substrate and an inorganic barrier layer is then formed thereon. The photocurable composition is applied to a thickness of about 1 μm to 5 μm by spin coating, slit coating, or the like, and light is irradiated thereon to form an organic barrier layer. The procedure of forming the inorganic barrier layer and the organic barrier layer (preferably 10 or less) may be repeated.

In an embodiment, examples of the packaging device may include organic hair Optical displays, including but not limited to organic light emitting diodes, liquid crystal displays, solar cells, and the like.

Next, the present invention will be described in more detail with reference to some embodiments. These examples are for illustrative purposes only and are not to be considered as limiting the invention in any way.

The details of the components used in the examples and comparative examples are as follows:

(A) Photocurable monomer: (A1) hexyl acrylate, (A2) hexanediol diacrylate, (A3) pentaerythritol tetraacrylate, (A4) tris(propylene glycol) diacrylate (Aldrich)

(B) ruthenium containing monomer: (B1) 1,3-bis(3-methylpropenyloxypropyl)tetramethyldioxane, (B2) 1,3-bis(3-methylpropene) Methoxypropyl)tetrakis(trimethyldecyloxy)dioxane (Gelest), (B3)X-22-164A (Shinetsu) (monomer represented by formula 5), wherein R ₁ and R ₂ are Propyl propyl (-CH ₂ CH ₂ CH ₂ -), Z ₁ and Z ₂ are methacrylate groups, and the average value of n is 6:

(C) Starter: Darocur TPO (BASF AG)

Examples and comparative examples

(A) photocurable monomer, (B) ruthenium containing monomer and (C) starter were placed in a 125 ml brown polypropylene bottle in an amount (unit: parts by weight) as listed in Table 2, followed by vibration The shaker was mixed for 3 hours to prepare a composition.

Experimental example

The physical properties of the compositions produced in the examples and comparative examples were evaluated. The results are shown in Table 2.

Evaluation of physical properties

1. Water vapor transmission (permeation) rate: A water vapor transmission (permeation) rate tester (PERMATRAN-W 3/33, manufactured by MOCON) was used. The photocurable composition was sprayed Al sample holder and subjected to a UV-curable, in which by 100 mW / cm ² under UV irradiation for 10 seconds to produce a layer thickness of 5 μm in a cured sample. Water vapor transmission (permeation) rate was measured using a water vapor transmission (permeation) rate tester (PERMATRAN-W 3/33, manufactured by MOCON) at a layer thickness of 5 μm for 24 hours at 37.8 ° C and 100% RH. .

2. Outgassing amount of the organic barrier layer: The photocurable composition was sprayed on a glass substrate and subjected to UV curing by UV irradiation at 100 mW/cm ² for 10 seconds to produce a size of 20 cm x 20 cm x 3 μm ( Organic barrier sample of width x length x thickness). Outgassing generation was measured using a GC/MS tester (Perkin Elmer Clarus 600). GC/MS uses DB-5MS column (length: 30 m, diameter: 0.25 mm, thickness of stationary phase: 0.25 μm) as the column, and helium (flow: 1.0 mL/min, average flow rate = 32 cm/s) ) as a mobile phase. Further, the split ratio was 20:1 and the temperature conditions were set such that the temperature was maintained at 40 ° C for 3 minutes, heated at a rate of 10 ° C / minute, and then held at 320 ° C for 6 minutes. The outgas was collected at a glass size of 20 cm x 20 cm. The collection container was a Tedlar bag. The collection temperature was 90 ° C, the collection time was 30 minutes, N ₂ cleaning was performed at a flow rate of 300 mL/min, and the adsorbent was Tenax. GR (5% phenylmethyl polyoxane). A calibration curve was prepared using a toluene solution having a concentration of 150 ppm, 400 ppm, and 800 ppm in n-hexane as a standard solution, wherein the R2 value obtained was 0.9987. The above conditions can be summarized in Table 1.

Table 1

3. Photocuring rate: The intensity of the absorption peak of the photocurable composition was measured by FT-IR (NICOLET 4700, Thermo) and in the vicinity of 1635 cm ^-1 (C=C) and 1720 cm ^-1 (C=O). First, a photocurable composition was sprayed on a glass substrate and subjected to UV curing by UV irradiation at 100 mW/cm ² for 10 seconds to produce a sample having a size of 20 cm x 20 cm x 3 μm (width x length x thickness). The cured film was cut into a sample which was in turn used to measure the intensity of the absorption peak near 1635 cm ^-1 (C=C) and 1720 cm ^-1 (C=O) using FT-IR (NICOLET 4700, by Thermo Manufacturing). Calculate the photocuring rate by Equation 1: Photocuring rate (%) = | 1-(A/B)| x 100

Wherein, A is the cured film strength at 1635 cm ^-1 and an absorption peak in the vicinity of the intensity ratio of absorption peaks near 1720 cm ^-1, and B is the absorption near 1635cm ^-1 in the photocurable composition The ratio of the intensity of the peak to the intensity of the absorption peak around 1720 cm ^-1 .

As shown in Table 2, the layers prepared from the photocurable composition of the present invention exhibited a low water vapor transmission (permeation) rate and a significantly reduced outgassing as compared to the comparative examples. In addition, the photocurable composition of the present invention exhibited a significantly high photocuring ratio as compared with the comparative examples.

It is apparent to those skilled in the art that the present invention is not limited to the above-described embodiments and the drawings, and various modifications, changes, and substitutions may be made without departing from the spirit and scope of the invention. Therefore, these implementations are only for The purpose of the description is not to be construed as limiting the invention in any way.

10‧‧‧Substrate

20‧‧‧ components

30‧‧‧Block stack

31‧‧‧Inorganic barrier

32‧‧‧Organic barrier

100‧‧‧Package

Claims (16)

A photocurable composition comprising: (A) a non-fluorene-type photocurable monomer and (B) a fluorene-containing monomer or an oligomer thereof, wherein the hydrazine-containing mono-system is represented by Formula 1: Wherein X ₁ and X ₂ are the same or different and are O, S, NH or N-R';R' is a substituted or unsubstituted C1-C20 alkyl group; R ₁ and R ₂ are the same or different, And is a single bond, a substituted or unsubstituted C1-C20 alkylene group, a substituted or unsubstituted C1-C30 alkyl ether group, a substituted or unsubstituted C1-C30 alkylamine group, a substituted or unsubstituted a C1-C30 alkyl sulfide group, a substituted or unsubstituted C6-C30 extended aryl group, a substituted or unsubstituted C7-C30 arylalkylene group, or a substituted or unsubstituted C1-C20 alkyleneoxy group; Y ₁ , Y ₂ , Y ₃ , Y ₄ , Y ₅ and Y ₆ are the same or different and are hydrogen, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C1-C30 alkyl ether group a substituted, unsubstituted or unsubstituted C1-C30 dialkylamine group, a substituted or unsubstituted C1-C30 alkyl sulfide group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C7- a C30 aralkyl group, a substituted or unsubstituted C1-C30 alkylene group, a substituted or unsubstituted C1-C30 alkyleneoxy group, or a compound represented by Formula 2 or Formula 3: Wherein * represents a binding site of Si in Formula 1; R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are the same or different and are hydrogen, substituted or unsubstituted C1-C30 alkyl, a substituted or unsubstituted C1-C30 alkyl ether group, a substituted or unsubstituted C1-C30 dialkylamine group, a substituted or unsubstituted C1-C30 alkyl sulfide group, a substituted or unsubstituted C6 group a C30 aryl group, or a substituted or unsubstituted C7-C30 aralkyl group; X ₃ is O, S, NH, or N-R';R' is a substituted or unsubstituted C1-C20 alkyl group; and Z ₁ And Z ₂ are the same or different and are compounds represented by Formula 4: Wherein * represents a binding site of R ₁ or R ₂ in Formula 1, R ₉ is hydrogen, or a substituted or unsubstituted C1-C30 alkyl group; and n is an integer of 0 to 30 or an average value of n is about 0 to In the range of 30; and wherein the (A) non-fluorene-type photocurable monomer comprises a mixture of one or more monofunctional monomers and one or more polyfunctional monomers, the monofunctional monomer: the polyfunctional monomer is A weight ratio from 1:0.1 to 1:10 exists. The photocurable composition of claim 1, wherein the cerium-containing monomer comprises at least one of the following: 1,3-bis(3-(methyl)acryloxypropyl)tetra Methyldioxane, 1,3-bis(3-(methyl)propenyloxypropyl)tetrakis(trimethyldecyloxy)dioxane, and a monomer represented by Formula 5: Wherein Z ₁ , Z ₂ , R ₁ , R ₂ and n are as defined in formula 1. The photocurable composition of claim 1, wherein the (A) photocurable monomer comprises a monomer having from about 1 to 30 substituted or unsubstituted vinyl, substituted or unsubstituted An acrylate group, or a substituted or unsubstituted methacrylate group. The photocurable composition of claim 1, wherein the (A) photocurable monomer comprises at least one of the following: a mono(meth)acrylate having a C1-C20 alkyl group, C2- A di(meth) acrylate of C20 diol, a tri(meth) acrylate of C3-C20 triol, and a tetra(meth) acrylate of C4-C20 tetraol. The photocurable composition of claim 1, wherein the (A) photocurable monomer is contained in an amount of from about 1 to 99 parts by weight based on 100 parts by weight of (A) + (B) in terms of solid content and About 1 to 99 parts by weight of the (B) ruthenium-containing monomer or oligomer thereof. The photocurable composition of claim 1, further comprising; (C) an initiator. The photocurable composition of claim 6, wherein the (C) starter comprises a photopolymerization initiator. A photocurable composition according to claim 6 of the patent application, comprising from about 1 to 99 parts by weight of the (A) photocurable monomer and based on 100 parts by weight of (A) + (B) in terms of solid content About 1 to 99 parts by weight of the (B) ruthenium-containing monomer or oligomer thereof, and in terms of solid content and based on 100 parts by weight of (A) + (B), comprising from about 0.1 to 20 parts by weight The (C) initiator. A member for use in a device packaged by a photocurable composition according to any one of claims 1 to 8. A packaging device comprising a member for the device and a barrier stack formed on the member of the device, and comprising an inorganic barrier layer and an organic barrier layer, wherein the organic barrier layer has a release of less than about 2000 ppm The outgas is produced in an amount and contains the cured product of the photocurable composition as in the first aspect of the patent application. A packaging device comprising a member for the device and a barrier laminate formed on the member of the device, the barrier laminate comprising an inorganic barrier layer and an organic barrier layer, wherein the organic barrier layer has about 4.0g/m ² . a water vapor transmission rate of 24 hours or less, as measured at a layer thickness of 5 μm in the thickness direction and 24 hours at 37.8 ° C and 100% RH, and the organic barrier layer is included in the first patent application scope A cured product of the photocurable composition. The encapsulating device of claim 10 or 11, wherein the inorganic barrier layer comprises at least one of the following: a metal, a metal oxide, a metal nitride, a metal carbide, a metal oxynitride, a metal oxygen a mixture of a boride, and the like, and wherein the metal is bismuth (Si), aluminum (Al), selenium (Se), zinc (Zn), antimony (Sb), indium (In), germanium (Ge), Tin (Sn), Bismuth (Bi), transition metal, or steel metal. The packaging device of claim 10 or 11, wherein the organic barrier layer and the inorganic barrier layer are alternately deposited in the barrier laminate. The packaging device of claim 10 or 11, wherein the organic barrier layer and the inorganic barrier layer are deposited in the barrier stack a total of 10 times or less. The packaging device of claim 10 or 11, wherein the organic barrier layer has a thickness of about 0.1 μm to 20 μm and the inorganic barrier layer has a thickness of about 5 nm to 500 nm. The package device of claim 10 or 11, wherein the member for the device comprises a flexible organic light emitting diode, an organic light emitting diode, a lighting device, a metal sensing pad, and a microdisk. Lasers, electrochromic devices, photochromic devices, microelectromechanical systems, solar cells, integrated circuits, charge coupled devices, luminescent polymers or light emitting diodes.