KR101687058B1 - Photocurable composition and encapsulated apparatus prepared from using the same - Google Patents

Abstract

The present invention relates to a photocurable composition comprising (A) a bifunctional photo-curable monomer containing a urethane bond, (B) a non-urethane-based photo-curable monomer, and (C) And an encapsulated device made using the same.

Description

FIELD OF THE INVENTION [0001] The present invention relates to a photocurable composition and an encapsulated device using the same,

The present invention relates to a photocurable composition and an encapsulated device made using the same.

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

The organic electroluminescence portion is oxidized by moisture or oxygen introduced from the outside or outgas generated from the outside or inside even if the organic electroluminescence portion is sealed, and the performance and lifetime of the organic electroluminescence portion are lowered. 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 having high adhesion to the inorganic barrier layer after curing.

Another object of the present invention is to provide a photocurable composition capable of realizing a layer in which a shift due to hardening shrinkage stress due to a high photo-curing rate is not generated.

It is a further object of the present invention to provide a photocurable composition which enables the encapsulation of a member for a device with high reliability.

It is still another object of the present invention to provide a photocurable composition which can prolong the life of a device member for sealing a member for a device.

The photocurable composition of the present invention comprises (A) a bifunctional photo-curable monomer containing a urethane bond, (B) a non-urethane-based photo-curable monomer, and (C) Can be displayed:

≪ Formula 1 >

(Wherein R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are as defined in the detailed description below).

The composition for encapsulating an organic luminescent element of the present invention may comprise the photocurable composition.

The encapsulated device of the present invention comprises a member for the device; And a barrier stack formed on the device for the device, the barrier stack comprising an inorganic barrier layer and an organic barrier layer formed of the photocurable composition.

The present invention provides a photocurable composition having good adhesion to an inorganic barrier layer after curing.

The present invention provides a photocurable composition capable of realizing a layer in which a shift due to hardening shrinkage stress due to a high photo-curing rate is not generated.

The present invention provides a photocurable composition that enables sealing of a member for a device with high reliability.

The present invention provides a photocurable composition capable of prolonging the lifetime of a device member when sealing a member for a device.

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, the term "substituted" means that the hydrogen atom of the functional group of the present invention is a halogen (F, Cl, Br or I), a hydroxy group, a nitro group, a cyano group, (Wherein R is an alkyl group having from 1 to 10 carbon atoms), an amino group (-NH ₂ , -NH (R '), -N (R ") (R"'), R ', R " A substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C1- 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, '*' means a connecting site of an element, '(meth) Means acrylate and / or methacrylate.

The photocurable composition of the present invention may comprise (A) a bifunctional photo-curable monomer containing a urethane bond, (B) a non-urethane-based photo-curable monomer, and (C) an initiator.

(A) Including urethane bond Bifunctionality Photocurable Monomer

The photocurable monomer (A) contains two urethane bonds (-NH-C (= O) O-) and two photocurable functional groups (e.g., (meth) acrylate groups) It is possible to increase the adhesion of the composition to the inorganic barrier layer after curing and increase the curing rate. In embodiments, the photocurable monomer (A) may be represented by the following formula (1): < EMI ID =

≪ Formula 1 >

(Wherein R ₁ and R ₂ are each independently hydrogen or a methyl group,

R ₃ is a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms or a substituted or unsubstituted arylene group having 6 to 30 carbon atoms,

R ₄ represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a substituted or unsubstituted arylalkyl group having 7 to 20 carbon atoms, 3,

(2)

(Wherein R < ₆ > is a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, R < ₇ > and R < ₈ > each independently represent hydrogen, a substituted or unsubstituted C1- To 10 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms)

(3)

Wherein R ₉ is a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms or a substituted or unsubstituted arylene group having 6 to 10 carbon atoms, R ₁₀ , R ₁₁ , R ₁₂ each independently represents hydrogen, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, or a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, R ₁₀ , R ₁₁ , and R ₁₂ is a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms,

R ₅ is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a substituted or unsubstituted arylalkyl group having 7 to 20 carbon atoms, )

R ₃ is specifically an alkylene group having 1 to 10 carbon atoms, more specifically an alkylene group having 1 to 5 carbon atoms, and R ₄ is specifically hydrogen, an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, Or R ₆ is an alkylene group having 2 to 5 carbon atoms and R ₇ and R ₈ are an alkyl group having 1 to 5 carbon atoms, and R ₅ is specifically an aryl group having 6 to 10 carbon atoms, or R ₆ is a carbon number 2 to 5, and R ₇ and R ₈ are each an alkyl group having 1 to 5 carbon atoms.

In one embodiment of the present invention, the bifunctional photo-curing monomer (A) having a urethane bond is represented by the following formula (1) wherein R ₁ and R ₂ are each independently hydrogen or a methyl group, and R ₃ is a substituted or unsubstituted C1- and to the 30 alkylene group, R ₄ is hydrogen, a substituted or unsubstituted C1 to 30 alkyl group, or the following formula 2 in the ring, R ₅ is a substituted or unsubstituted carbon atoms of 6 to 20 aryl group, a substituted or unsubstituted ring An arylalkyl group having 7 to 20 carbon atoms, and the formula (2) or (3).

The monomers of formula (1) can be prepared by conventional methods. For example, the monomer of the formula (1) is obtained by reacting a compound containing an epoxy group (e.g., oxirane, glycidol) with (meth) acrylic acid. The reaction for obtaining the product 1 can be carried out in the absence of a solvent or in an organic solvent, and may be carried out by further adding a base (for example, triethylamine). The reaction time may be 10 to 20 hours, and the reaction temperature may be 25 to 100 占 폚. The monomer of formula (1) can be prepared by reacting the resulting product (1) with an isocyanate-containing compound containing a (meth) acrylate group such as isocyanatoalkyl (meth) acrylate to form a urethane bond. The reaction for obtaining the monomer of the formula (1) can be carried out in the absence of a solvent or under an organic solvent and can be carried out in the presence of a catalyst (for example dibutyltin dilaurate) in order to increase the reaction yield. The reaction may be carried out at 0 to 25 ° C and the reaction time may be 1 to 10 hours. Further, it may further include a step of further reacting the vinyl group-containing compound (for example, diethyl vinylphosphonate) before reacting the (meth) acrylate-containing isocyanate-containing compound to the product 1.

(A) the photo-curable monomer may be contained in an amount of 1 to 90% by weight, specifically 10 to 50% by weight, based on the solid basis photo-curable composition. Within this range, the resistance to plasma is strong and the outgas generated from the plasma generated during the production of the sealing layer can be lowered.

(B) the photo-curable monomer may include a non-urethane based photo-curable monomer that does not contain a urethane bond and contains a photo-curable functional group such as a (meth) acrylate group.

(B) photo-curable monomers may comprise a mixture of monofunctional monomers and polyfunctional monomers, wherein the monofunctional monomer: polyfunctional monomer in the mixture is present in a weight ratio of 1: 0.1 to 1: 4, for example 1: 1: 4, such as 1: 2 to 1: 4.

(B) the photo-curable monomer is an alkyl group of 1-20 carbon atoms, a cycloalkyl group of 3-20 carbon atoms, or an unsaturated carboxylic acid ester having a hydroxy group and an alkyl group of 1-20 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; Monoalcohol or polyhydric alcohol monofunctional or polyfunctional (meth) acrylate, and the like. The 'polyhydric alcohol' may be an alcohol having two or more hydroxyl groups and having 2 to 20, for example, 2 to 10, such as 2 to 6, alcohols.

In an embodiment, the photocurable monomer (B) is selected from the group consisting of methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2- hydroxyethyl (meth) acrylate, 2- (Meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decanyl Unsaturated carboxylic acid esters including (meth) acrylic acid esters such as hexyl (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, etc .; 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 ) Acrylate, octanediol di (meth) acrylate, nonanediol di (meth) acrylate, decanediol di (meth) acrylate, undecanediol di , Neopentyl glycol di (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol di (Meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) (Propyleneglycol) di (meth) acrylate including diethyleneglycol di (meth) acrylate, tri (propyleneglycol) di (meth) acrylate, tetraethyleneglycol di A monofunctional or polyfunctional (meth) acrylate of an alcohol or a polyhydric alcohol, and the like, but is not limited thereto. (Meth) acrylate having an alkyl group of 1-20 carbon atoms, di (meth) acrylate of a diol having 2-20 carbon atoms, tri (meth) acrylate of a triol having 3-20 carbon atoms, Acrylate, tetra (meth) acrylate of tetraol having 4-20 carbon atoms, polyalkylene glycol di (meth) acrylate, and polyalkylene glycol di (meth) acrylate may have one or more of carbon number Di (meth) acrylates having 2-5 linear or branched alkylene glycol units.

The photocurable monomer (B) may be contained in an amount of 1 to 90% by weight, for example, 50 to 80% by weight, based on the solids-based photo-curable composition. In the above range, the reliability of the sealing for the device member may not be deteriorated.

 The initiator (C) 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- (4'-methoxystyryl) -6-triazine, or a mixture thereof. Examples of the acetophenone-based compounds include 2, 2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylpropyl 2-methyl-1- (4- (methylthio) phenoxy) acetophenone, 2,2'-dichloro-4-phenoxyacetophenone, Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, or a mixture thereof. Examples of the phenone-based compounds include benzophenone, benzoylbenzoic acid, methyl benzoyl benzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4,4'-bis (dimethylamino) benzophenone, 4,4'-dichlorobenzophenone , 3,3'-dimethyl-2-methoxybenzophenone, or a mixture thereof. The thioxanthone series includes thioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-di Ethylthioxanthone, 2,4-diisopropylthioxanthone, 2-chlorothioxanthone, or a mixture thereof. The benzoin group includes benzoin, benzoin methyl ether, benzoin Ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal or mixtures thereof. The phosphorous can be diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide or a mixture 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.

(C) initiator may be included in the solid-based photocurable composition in an amount of 0.1 to 10% by weight, for example, 1 to 5% 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 photo-curable composition can be formed by mixing (A) a bifunctional photo-curable monomer having a urethane bond, (B) a photo-curable monomer, and (C) an initiator. Preferably, it may be formed into a solventless type solventless type.

The photo-curable composition may have a photo-curing rate of 85% or more, for example, 87 to 99%. 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.

The device member may be an organic light emitting diode (OLED), a lighting device, a flexible organic light emitting device, a metal sensor pad, a microdisk laser, an electrochromic device, a photochromic device, a microelectromechanical system, a solar cell, Bonding devices, light emitting polymers, light emitting diodes, and the like.

The photocurable composition can form an organic barrier layer for encapsulation or encapsulation of a device member, particularly an organic light emitting device or a flexible organic light emitting device. In an embodiment, the composition for encapsulating an organic light emitting device is a light curable composition . ≪ / RTI >

The organic barrier layer of the present invention may be formed from the photocurable composition. In embodiments, the organic barrier layer can be formed by photo-curing the photocurable composition. The photocurable composition can be prepared by coating the photocurable composition to a thickness of 0.1 占 퐉 to 20 占 퐉, specifically 1 占 퐉 to 10 占 퐉, and curing by irradiation at 10-500 mW / cm ² for 1 second to 50 seconds.

The organic barrier layer is low in moisture permeability and outgassing amount and high in adhesion to the inorganic barrier layer, and can be used as an encapsulation of device members by forming a barrier stack together with the inorganic barrier layer below. In one embodiment, the organic barrier layer has a water vapor transmission rate of 20.0 g / m < ² > 24hr or less measured at 37.8 DEG C, 100% . Within this range, it can be used for sealing members for devices. For example, the moisture permeability may be 1.0 to 10.0 g / m ² .24 hr. In one embodiment, the organic barrier layer can have an outgassing amount of 2000 ng / cm ³ 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. Specifically, the outgas generation amount may be 10 to 1000 ng / cm < ³ >. In one embodiment, the organic barrier layer may have an adhesion to the inorganic barrier layer of 20 kgf or more, for example 25 to 50 kgf. Within this range, the reliability of the encapsulated device can be increased. The organic barrier layer may have a light transmittance of 90% or more, specifically 90 to 99% at a wavelength of 550 nm. Within this range, it can be used as the organic barrier layer of the member for the device.

The barrier stack of the present invention may comprise an organic barrier layer and an inorganic barrier layer. The inorganic barrier layer is 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, the inorganic barrier layer may comprise a metal; nonmetal; Oxides of metals, non-metals or mixtures thereof; Fluorides of metals, nonmetals, or mixtures thereof; Nitrides of metals, nonmetals or mixtures thereof; Carbides of metals, non-metals or mixtures thereof; Oxygen nitrides of metals, nonmetals or mixtures thereof; Borides of metals, non-metals or mixtures thereof; Silicides of metals, nonmetals or mixtures thereof; An alloy of two or more metals; The metal may include at least one of a metal and an alloy of a nonmetal, and the metal may be, but is not limited to, a metal, a metalloid, a transition metal, a lanthanide metal, or the like after the transition. For example, the metal may be silicon, aluminum, iron, nickel, or the like, the inorganic barrier layer is silicon oxide, silicon nitride, silicon oxygen nitride, ZnSe, ZnO, Sb ₂ O _3, Al ₂ O _3, In ₂ O ₃ , and SnO ₂ .

The organic barrier layer can secure the aforementioned moisture permeability, outgassing amount, and adhesion. As a result, when the organic barrier layer is deposited alternately with the inorganic barrier layer, the smoothing property of the inorganic barrier layer can be secured. In addition, the organic barrier layer can prevent the defects of the inorganic barrier layer from propagating to another inorganic barrier layer.

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

The organic barrier layer and the inorganic barrier layer may 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. For example, the organic barrier layer and the inorganic barrier layer may be alternately formed in two or more layers, and a total of 10 layers or less (for example, 2-10 layers), preferably 7 layers or less (for example, 2-7 layers) As shown in FIG.

In the barrier stack, the thickness of one of the organic barrier layers may be from 0.1 占 퐉 to 20 占 퐉, for example, from 1 占 퐉 to 10 占 퐉, and the thickness of one inorganic barrier layer may be from 5 nm to 500 nm, for example, from 5 nm to 50 nm. The barrier stack may be a thin film encapsulant and have a thickness of 5 탆 or less, for example, 1.5 탆 to 5 탆. Within this range, it can be used as an encapsulation of a member for an apparatus.

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.

The encapsulated device of the present invention comprises a member for the device, and an inorganic barrier layer and an organic barrier layer formed on the device member, and the organic barrier layer may be formed of the photo-curable composition.

The organic barrier layer may be formed on or under the inorganic barrier layer, and 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. As described above, the encapsulated device is sealed by the inorganic barrier layer, which is a barrier layer having different properties, and the organic barrier layer, so that the organic barrier layer and the inorganic barrier layer complement or improve the sealing effect of the device member. Can be strengthened.

The inorganic barrier layer and the organic barrier layer may be included in the encapsulated device in two or more layers, respectively. 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 comprised of not more than 10 layers in total (for example, 2 to 10 layers), more preferably not more than 7 layers (for example, 2 to 7 layers).

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

At least one of the inorganic barrier layer and the organic barrier layer may be bonded to the substrate for sealing the device, and the substrate may be included depending on the type of the member for the device. 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 an apparatus member 20 formed on the substrate 10, and the inorganic barrier layer 31 and organic Includes a barrier stack (30) comprising a barrier layer (32), wherein 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 a barrier layer 32 including a barrier layer 32 and the inorganic barrier layer 31 may seal the internal space 40 in which the device member 20 is received.

FIGS. 1 and 2 show a structure in which the inorganic barrier layer and the organic barrier layer are formed as a single layer, respectively, but the inorganic barrier layer and the organic barrier layer may be formed of a plurality of layers, respectively. 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 photo-curable composition can be coated to a thickness of 1 占 퐉 to 5 占 퐉 by spin coating, slit coating, or the like, and light can be irradiated to form an organic barrier layer. The formation process of the inorganic barrier layer and the organic barrier layer may be repeated (preferably, a total of 10 layers 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.

Manufacturing example  1: Monomeric  Produce

60 g of 2-phenyloxirane (TCI), 79 g of acrylic acid and 350 g of triethylamine were stirred at 25 DEG C, and the temperature was raised to 80 DEG C, followed by stirring for 12 hours. After completion of the reaction, 73 g of the product was extracted with dichloromethane. 100 mg of dibutyltin dilaurate was slowly added to 53.61 g of 2-isocyanatoethyl acrylate at 0 ° C to obtain a monomer (yield: 78%) of the following formula 4: ), And confirmed by 1 H NMR data (1 H NMR:? 7.73, m, 5H;? 7.12, s, 1H;? 6.25, d, 2H;? 6.02, dd, 2H; t, 1H;? 5.59, d, 2H;? 4.73, m, 2H;? 4.55, m, 2H;

≪ Formula 4 >

Manufacturing example  2: Monomeric  Produce

In the same manner as in Preparation Example 1 except that 2-methyl-3-phenyloxirane was used instead of 2-phenyloxirane in Production Example 1, a monomer represented by the following Formula 5 was obtained and confirmed by 1H NMR data (1H NMR, δ 7.39, m, 5H; 隆 7.02, s, 1H; 隆 6.25, d, 2H; 隆 6.05, dd, 2H; 隆 5.82, t, 1H; m, 2H;? 4.55, m, 2H;? 3.12, m, 2H, 1.54, d, 3H).

≪ Formula 5 >

Manufacturing example  3: Monomeric  Produce

22.57 g of glicydol (TCI) and 50 g of diethyl vinylphosphonate were added to a 1000 ml flask equipped with a cooling tube and a stirrer, and 19.85 g of cesium carbonate was added thereto, followed by stirring at 50 ° C for 12 hours Respectively. The monomer of Formula 6 was obtained in the same manner as in Preparation Example 1 except that the reaction product was filtered and used in place of 2-phenyloxirane in Production Example 1, and it was confirmed by ¹ H NMR data ( ¹ H NMR: 1H M, 4H, 4.15, q, d, 2H, d, 2H, M, 4H;? 1.95, t, 2H, 1.32, t, 6H).

(6)

Manufacturing example  4: Monomeric  Produce

After the reaction product was filtered using a 2-phenyl-oxirane instead of glycidol in the reaction product prepared in Production Example 3, to manufacture them by the same manner as in Production Example 3 was obtained after the reaction was filtered, the monomer of formula 7, ¹ H was confirmed by NMR data ^{(1H NMR: 1 H NMR:} 7.42, m, 5H; δ6.95, s, 1H; δ6.25, d, 2H; δ6.05, dd, 2H; δ5.79, d, 1H ; 4.88, m, 1H, 4.43, m, 4H, 4.15, q, 4H, .delta.3.71, m, 2H, .delta.3.25, m, 4H, .delta.1.95, t, 2H, 1.32, t, 6H).

≪ Formula 7 >

(A2) the monomer of Production Example 2, (A3) the monomer of Production Example 3, (A4) the monomer of Production Example 4 (A3)

(B1) tetraethylene glycol diacrylate, (B2) decanediol diacrylate, (B3) pentaerythritol tetraacrylate (available from Aldrich)

(C) Initiator: Diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide (Darocure TPO, BASF) as a photopolymerization initiator.

Example  1 to 8 and Comparative Example  1 to 3

Without photo-solvent, photo-curing monomer and initiator were placed in a 125 ml brown polypropylene bottle in the content (unit: parts by weight) shown in the following Table 1 and mixed for 3 hours using a shaker to prepare a photo-curable composition.

The following properties were evaluated for the compositions prepared in Examples and Comparative Examples, and the results are shown in Table 1 below.

Property evaluation method

1. Adhesion (kgf): The adhesive force was measured by the same method as that for measuring the die shear strength as a method for measuring the adhesion between silicon nitride (SiNx,) and glass. The adhesive strength meter dage series 4000PXY was used to measure the force exerted by pushing the upper glass from the side with a force of 200 kgf at 25 캜. The size of the lower glass was 2 cm x 2 cm x 1 mm (width x length x thickness), and the size of the upper glass was 1.5 cm x 1.5 cm x 1 mm (width x length x thickness) Respectively.

By ± 10㎛ the composition on the glass substrate was washed and then coated with a UV curing 2㎛ outside (100mW / cm ² x 10 seconds) film (thickness:: 9㎛ ± 2㎛) 2. The light transmittance (%) was prepared. The visible light transmittance of the prepared film was measured at a wavelength of 550 nm with a Lambda 950 (Perkin Elmer) instrument.

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 < 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 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 and B is the intensity at about 1720 cm ^-1 for the photo- The ratio of the intensity of the absorption peak at around 1635 cm &lt; ^-1 &gt;

Example Comparative Example One 2 3 4 5 6 7 8 One 2 3 B B1 20 20 20 20 20 20 20 20 20 20 20 B2 55 55 55 55 50 50 50 50 75 70 65 B3 - - - - 5 5 5 5 - 5 10 A A1 20 - - - 20 - - - - - - A2 - 20 - - - 20 - - - - - A3 - - 20 - - - 20 - - - - A4 - - - 20 - - - 20 - - - C 5 5 5 5 5 5 5 5 5 5 5 Adhesion (kgf) 26.8 24.5 41.5 42.5 27.2 25.3. 45.2 46.3 11 13.5 15 Light transmittance (%) 96.4 95.8 95.2 95.1 96.8 95.3 94.7 95.5 96.3 95.3 95.1 Light curing rate (%) 87.5 88.4 88.2 87.6 87.9 89.8 91.1 90.3 83 87.5 89.8

As shown in Table 1, it was confirmed that the photocurable composition of the present invention has high adhesion to an inorganic barrier layer such as silicon nitride, an organic barrier layer having a high light transmittance, and a high photo-curability. On the other hand, it was confirmed that Comparative Examples 1 to 3, which did not contain the bifunctional photo-curable monomer containing the urethane bond of the present invention, can realize a barrier layer having a lower adhesive force than the photocurable composition of the present invention.

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.

100, 200: encapsulated device,
10: substrate, 20: member for device, 30: barrier stack, 40: inner space
31: inorganic barrier layer, 32: organic barrier layer

Claims (9)

(A) a bifunctional photo-curable monomer containing a urethane bond, (B) a non-urethane based photo-curable monomer and (C) an initiator, wherein the bifunctional photo- Photocurable composition:
&Lt; Formula 1 >

(Wherein R ₁ and R ₂ are each independently hydrogen or a methyl group,
R ₃ is a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms or a substituted or unsubstituted arylene group having 6 to 30 carbon atoms,
R ₄ represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a substituted or unsubstituted arylalkyl group having 7 to 20 carbon atoms, 3,
(2)

(Wherein R < ₆ > is a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, R < ₇ > and R &lt; ₈ &gt; each independently represent hydrogen or a substituted or unsubstituted C1- To 10 carbon atoms, or a substituted or unsubstituted C6-C12 aryl group)
(3)

Wherein R ₉ is a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms or a substituted or unsubstituted arylene group having 6 to 12 carbon atoms, R ₁₀ , R ₁₁ , R ₁₂ each independently represents hydrogen, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, or a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, R ₁₀ , R ₁₁ , and R ₁₂ is a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms,
R ₅ is a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a substituted or unsubstituted arylalkyl group having 7 to 20 carbon atoms, the formula 2, or the formula 3. The bifunctional photocurable monomer composition according to claim 1, wherein the (A) urethane bond-containing bifunctional photo-
In formula (1), R ₁ and R ₂ are each independently hydrogen or a methyl group,
R ₃ is a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms,
And R ₄ is hydrogen, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, or a group represented by the formula (2). The photocurable composition according to claim 1, wherein the photocurable monomer (A) is represented by any one of the following formulas (4) to (7):
&Lt; Formula 4 >

&Lt; Formula 5 >

(6)

&Lt; Formula 7 >

. (Meth) acrylate having an alkyl group of 1-20 carbon atoms, a di (meth) acrylate of a diol having 2-20 carbon atoms, a triol of a triol having 3-20 carbon atoms (Meth) acrylate, tetra (meth) acrylate of tetraol of 4-20 carbon atoms, and polyalkylene glycol di (meth) acrylate. The photocurable composition of claim 1, wherein the photocurable composition comprises 1 to 90% by weight of the photocurable monomer (A), 1 to 90% by weight of the photocurable monomer (B), and 0.1 to 10% / RTI &gt; A composition for encapsulating an organic luminescent element comprising the photo-curable composition according to any one of claims 1 to 5. A member for a device; And
And a barrier stack formed over the member for the device, the barrier stack comprising an inorganic barrier layer and an organic barrier layer formed from the photocurable composition of any one of claims 1 to 5. 8. The method of claim 7, wherein the inorganic barrier layer comprises a metal; nonmetal; Oxides of metals, non-metals or mixtures thereof; Fluorides of metals, nonmetals, or mixtures thereof; Nitrides of metals, nonmetals or mixtures thereof; Carbides of metals, non-metals or mixtures thereof; Oxygen nitrides of metals, nonmetals or mixtures thereof; Borides of metals, non-metals or mixtures thereof; Silicides of metals, nonmetals or mixtures thereof; An alloy of two or more metals; A barrier layer formed of any one of a metal and a nonmetal alloy, wherein the metal is a transition metal, a metalloid, a transition metal, or a lanthanide metal. 8. The device of claim 7, wherein the device member is selected from the group consisting of 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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