WO2017039228A1 - Composition for encapsulating organic light emitting device, and organic light emitting device display apparatus manufactured therefrom - Google Patents

Abstract

The present invention provides: a composition for encapsulating an organic light emitting device, comprising silicone-based particles having an average diameter of approximately 0.7-10.0 μm, one or more curable compounds, and an initiator; and an organic light emitting device display apparatus comprising an organic film formed therefrom. The composition for encapsulating an organic light emitting device, of the present invention, implements an organic film, which increases a color shift reduction rate on the lateral side, compared to the front side, and increases luminance.

Description

A composition for encapsulating an organic light emitting device and an organic light emitting display device manufactured therefrom

The present invention relates to a composition for encapsulating an organic light emitting device and an organic light emitting display device manufactured therefrom.

The organic light emitting diode display is a display that emits light by using an electroluminescence phenomenon and includes an organic light emitting diode. In the organic light emitting device, since the light emitter is an organic material, a shortening of the life due to deterioration may be a problem. Shortening the lifespan of the organic light emitting device can be solved by using a micro cavity structure.

The microcavity structure resonates light of a specific wavelength to emit light, thereby increasing light intensity and decreasing the width of the light emitting wavelength, thereby reducing power consumption and improving color purity. That is, the distance between the anode and the cathode of the organic light emitting device is designed to match the representative wavelengths of red (R), green (G), and blue (B), so that only light corresponding to the corresponding wavelength is resonated, It emits light and weakens light other than the wavelength. As a result, the intensity of light emitted outside the organic light emitting element becomes sharper and sharper, thereby increasing luminance and color purity.

Even if the organic light emitting diode display includes the microcavity structure, when the organic light emitting diode is viewed from the side rather than the front side, the path length of the light at the side is different from the path length of the light at the front side. This results in the same effect as the thickness of the organic light emitting layer is different, causing the wavelength to be amplified is different. That is, as the viewing angle of the organic light emitting diode is from the front to the side, the shortest wavelength shows the maximum resonant wavelength, and color shift occurs toward the short wavelength. Therefore, the front of the organic light emitting device appears to be white, but the blue shift toward the side occurs (blue shift) occurs to see the screen in blue color.

In order to suppress such color change, an optical film for reducing color change may be introduced into an organic light emitting display device as in Korean Patent Publication No. 2014-0137954. However, separately introducing an optical film for reducing color change cannot reduce the thickness of the organic light emitting display device.

On the other hand, since the organic light emitting device is damaged by external moisture and / or oxygen, it should be sealed by the thin film encapsulation structure of the organic film and the inorganic film.

Background art of the present invention is disclosed in Korea Patent Publication No. 2012-0115841.

An object of the present invention is to provide a composition for encapsulating an organic light emitting device that can implement an organic film that increases the color shift reduction rate in the front contrast side and increases the brightness.

Another object of the present invention is to provide a composition for encapsulating an organic light emitting device capable of realizing an organic film which increases the reduction rate of color change in the short wavelength side and increases the luminance in terms of the aspect.

Still another object of the present invention is to provide a composition for encapsulating an organic light emitting device, which can implement an organic film that suppresses color shift from white to blue and increases brightness.

Still another object of the present invention is to provide a composition for encapsulating an organic light emitting device that can implement an organic film having a high light transmittance.

Still another object of the present invention is to provide a composition for encapsulating an organic light emitting device capable of realizing an organic film having a color improving effect having an appropriate light scattering property.

The present invention is to provide a composition for encapsulating an organic light emitting device that can block the penetration of moisture and / or oxygen from the outside to increase the reliability of the organic light emitting device, and to implement an organic film having a low plasma etching rate.

Still another object of the present invention is to provide an organic light emitting display device including the organic layer.

The composition for encapsulating an organic light emitting device of the present invention may include silicon-based particles, one or more curable compounds, and an initiator having an average particle diameter of about 0.70 μm to about 10.0 μm.

The organic light emitting diode display device of the present invention includes an organic light emitting diode and a thin film encapsulation layer formed on the organic light emitting diode and including at least one inorganic film and at least one organic film, wherein the organic film is used for encapsulating the organic light emitting diode of the present invention. It can be formed into a composition.

The present invention provides a composition for encapsulating an organic light emitting device that can implement an organic film that increases the color change reduction rate in terms of front side and increases luminance.

The present invention provides a composition for encapsulating an organic light emitting device that can implement an organic film that increases the color change reduction rate of the short wavelength side and increases the brightness in terms of the aspect.

The present invention provides a composition for encapsulating an organic light emitting device that can implement an organic film to suppress the color change from white to blue in the aspect and to increase the brightness.

The present invention provides a composition for encapsulating an organic light emitting device that can implement an organic film having a high light transmittance.

The present invention provides a composition for encapsulating an organic light emitting device that can implement an organic film having a color improving effect having a suitable light scattering property.

The present invention provides a composition for encapsulating an organic light emitting device that can implement an organic film, which improves reliability of the organic light emitting device by blocking penetration of external moisture and / or oxygen, and has a low plasma etching rate.

The present invention provides an organic light emitting display device including the organic film.

1 is a cross-sectional view of an organic light emitting diode display according to an exemplary embodiment of the present invention.

2 is a cross-sectional view of an organic light emitting diode display according to another exemplary embodiment of the present invention.

DETAILED DESCRIPTION Hereinafter, exemplary embodiments will be described in detail with reference to the accompanying drawings so that those skilled in the art may easily implement the present invention. As those skilled in the art would realize, the described embodiments may be modified in various different ways, all without departing from the spirit or scope of the present invention. The drawings and description are to be regarded as illustrative in nature and not restrictive. Like reference numerals designate like elements throughout the specification.

In the present specification, "(meth) acryl" means acrylic and / or methacryl.

In this specification, "substituted" means, unless otherwise defined, that at least one hydrogen atom of the functional group is halogen (eg, F, Cl, Br or I), hydroxy group, nitro group, cyano group, imino group (= NH , = NR, R is C1 to C10 alkyl group), amino group (-NH ₂ , -NH (R '), -N (R ") (R"'), said R ', R ", R"' are respectively Independently C1 to C10 alkyl group), amidino group, hydrazine group, hydrazone group, carboxylic acid group, C1 to C20 alkyl group, C6 to C30 aryl group, C3 to C30 cycloalkyl group, C3 to C30 heteroaryl group, Or it is substituted with a heterocycloalkyl group of C2 to C30.

As used herein, "aryl group" means a functional group in which all elements of a cyclic substituent have a p-orbital, and these p-orbitals form conjugation. Aryl groups include monocyclic, non-fused polycyclic or fused polycyclic functional groups. In this case, fusion means a ring form in which carbon atoms divide adjacent pairs. The aryl group also includes a biphenyl group, terphenyl group, or quarterphenyl group in which two or more aryl groups are linked via a sigma bond. An aryl group may mean a phenyl group, naphthyl group, anthracenyl group, phenanthrenyl group (phenanthrenyl), pyrenyl group, or chrysenyl group.

As used herein, "heteroaryl group" means a functional group containing 1 to 3 heteroatoms selected from the group consisting of N, O, S, P, and Si in the aryl group, and the rest being carbon. Heteroaryl groups include those in which two or more heteroaryl groups are directly connected through a sigma bond. Heteroaryl groups include those in which two or more heteroaryl groups are fused to each other. When the heteroaryl group is fused, each ring may contain 1 to 3 heteroatoms. The heteroaryl group may mean, for example, a pyridinyl group, a pyrimidinyl group, a pyrazinyl group, a pyridazinyl group, a triazinyl group, a quinolinyl group, an isoquinolinyl group, and the like.

More specifically, the C6 to C30 aryl group and / or C3 to C30 heteroaryl group, substituted or unsubstituted phenyl group, substituted or unsubstituted naphthyl group, substituted or unsubstituted anthracenyl group, substituted or unsubstituted phenanthryl Groups, substituted or unsubstituted naphthacenyl groups, substituted or unsubstituted pyrenyl groups, substituted or unsubstituted biphenyl groups, substituted or unsubstituted p-terphenyl groups, substituted or unsubstituted m-terphenyl groups, substituted or unsubstituted groups A substituted crysenyl group, a substituted or unsubstituted triphenylenyl group, a substituted or unsubstituted peryleneyl group, a substituted or unsubstituted indenyl group, a substituted or unsubstituted furanyl group, a substituted or unsubstituted thiophenyl group, a substitution Or unsubstituted pyrrolyl group, substituted or unsubstituted pyrazolyl group, substituted or unsubstituted imidazolyl group, substituted or unsubstituted triazolyl group, substituted or unsubstituted oxazolyl group, substituted or unsubstituted An azoleyl group, a substituted or unsubstituted oxadiazolyl group, a substituted or unsubstituted thiadiazolyl group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted pyrimidinyl group, a substituted or unsubstituted pyrazinyl group, a substitution Or unsubstituted triazinyl group, substituted or unsubstituted benzofuranyl group, substituted or unsubstituted benzothiophenyl group, substituted or unsubstituted benzimidazolyl group, substituted or unsubstituted indolyl group, substituted or unsubstituted qui Nolinyl group, substituted or unsubstituted isoquinolinyl group, substituted or unsubstituted quinazolinyl group, substituted or unsubstituted quinoxalinyl group, substituted or unsubstituted naphthyridinyl group, substituted or unsubstituted benzoxazinyl group, Substituted or unsubstituted benzthiazinyl group, substituted or unsubstituted acridinyl group, substituted or unsubstituted phenazineyl group, substituted or unsubstituted phenthiazineyl group, substituted or unsubstituted phenoxa It may be a true group, a substituted or unsubstituted dibenzofuranyl group, or a substituted or unsubstituted dibenzothiophenyl group, or a combination thereof, but is not limited thereto.

In the present specification, "organic light emitting device encapsulation composition" may be simply referred to as "encapsulation composition".

Hereinafter, a composition for encapsulating an organic light emitting device according to an embodiment of the present invention.

The composition for encapsulating an organic light emitting device according to an embodiment of the present invention may include silicon-based particles having an average particle diameter of about 0.70 μm to about 10.0 μm, one or more curable compounds, and an initiator. For example, the composition for encapsulating an organic light emitting device of the present embodiment includes silicon particles having an average particle diameter of about 0.70 μm to about 10.0 μm, specifically about 1 μm to about 5 μm, and thus have light scattering properties, Both the luminance can be increased, and an organic film having a high light transmittance can be formed. In particular, the composition for encapsulating the organic light emitting device of the present embodiment can form an organic film capable of increasing the reduction rate of color change in the blue wavelength, especially in the short wavelength side. In this case, the “short wavelength” may mean a wavelength of 380 nm to 490 nm. The higher the color change reduction rate, the lower the color change in terms of front contrast of the organic light emitting device. In addition, the composition for encapsulating the organic light emitting device according to the present embodiment may include at least one curable compound and an initiator described below, thereby preventing external moisture and / or oxygen from penetrating and forming an organic film having a low plasma etch rate. In addition, in the composition for encapsulating the organic light emitting device of the present embodiment, by providing light scattering property to the organic film encapsulating the organic light emitting device, it is not necessary to use an optical film for reducing color change, and the organic light emitting display device can be thinned. .

Hereinafter, silicon-based particle | grains are demonstrated.

The silicon-based particles may be included in the composition for encapsulating the organic light emitting diode, and may have light scattering properties to increase the color change reduction rate, thereby suppressing the color change and increasing the luminance. The silicon-based particles may have an average particle diameter of about 0.70 μm to about 10.0 μm. In the above range, it is possible to implement an organic film that suppresses color change and increases luminance. Specifically, the silicon-based particles may have an average particle diameter of about 1 μm to about 5 μm. The “average particle diameter” may mean a value corresponding to D50 when measured by a particle size analyzer.

Silicon-based particles may have a large difference in refractive index relative to the refractive index of the matrix of the organic layer formed of the at least one curable compound and the initiator. As the refractive index difference increases, an organic film that can suppress color change and increase luminance can be formed. Silicon-based particles are impregnated into the matrix of the organic film. The refractive index difference (the refractive index of the matrix of the organic film or the refractive index of one or more curable compounds and the initiator as a whole-the refractive index of the silicon-based particles) may be about 0.07 or more, specifically about 0.078 to about 0.2. In this range, the color change can be suppressed and the luminance can be increased.

The silicon-based particles may have a refractive index of less than about 1.5, specifically about 1.3 to about 1.49, more specifically about 1.3 to about 1.45, about 1.35 to about 1.45, about 1.40 to about 1.45. Within this range, an organic film having high light efficiency and excellent surface flatness can be realized. The silicon-based particles are not limited in shape, but may have a spherical bead, an amorphous shape, or the like.

The silicon-based particles are particles containing silicon and may include silicon-based organic particles. Specifically, the silicon-based organic particles may include polysilsesquioxane organic particles. Polysilsesquioxane particles may implement an organic film having a relatively excellent surface flatness. Specifically, the silicon-based particles may comprise a polysilsesquioxane particles having a (RSiO _3/2) n units. In this case, R may be an alkyl group of C1 to C5, specifically, a methyl group. These may be included alone or in combination of two or more. Specifically, the silicon-based particles may include polymethylsilsesquioxane (PMSQ) particles.

The silicon-based particles may be about 0.1% to about 20% by weight, specifically about 1% to about 10% by weight, more specifically about 1% of the total of the at least one curable compound, the silicon-based particles, and the initiator in the composition for encapsulating the organic light emitting device. Weight percent to about 5 weight percent. In the above range, the color change reduction rate may be high, the luminance may be increased, and an organic film capable of suppressing penetration of external moisture and / or oxygen may be implemented.

Hereinafter, one or more curable compounds and initiators will be described.

One or more curable compounds and initiators may be cured to form a matrix of organic films. Curing may include one or more of light curing, thermal curing. The curable compound may include one or more of a photocurable compound and a thermosetting compound.

Hereinafter, a composition for a matrix of an organic film including at least one curable compound and an initiator according to an embodiment of the present invention will be described.

Composition for the matrix of the organic film according to an embodiment of the present invention is a (A) non-silicone di (meth) acrylate, (B) silicon-based di (meth) acrylate, (C) mono (meth) Mixtures of acrylates and (D) initiators. The refractive index of the matrix composition of the organic layer may be about 1.45 or more, specifically about 1.49 to about 1.65, specifically about 1.49 to about 1.60, about 1.49 to about 1.55, and about 1.49 to about 1.50. In addition, in one embodiment of the present invention, the refractive index of the matrix composition of the organic film may be about 1.55 or more, specifically about 1.60 or more, about 1.60 to about 1.70, in the above range, when the refractive index difference is large compared to the silicon-based particles, the luminance It can increase.

Specifically, the composition for the matrix of the organic film is about 10% to about 70% of (A) non-silicone di (meth) acrylate based on the total weight of (A), (B), (C) and (D) % By weight specifically about 10% to about 50% or about 35% to about 48% by weight, (B) about 20% to about 70% by weight of silicone-based di (meth) acrylate, specifically about 25% by weight About 45% by weight, about 5% to about 40% by weight (C) mono (meth) acrylate, specifically about 5% to about 30% by weight. In the above range, the light curing rate of the composition for encapsulation may be improved, and an organic film having a high light transmittance and a low plasma etching rate may be realized. The thin film encapsulation structure includes an inorganic film and an organic film, and the inorganic film is formed by plasma. As the organic layer is etched by the plasma, the penetration of external moisture and / or oxygen may be facilitated. The composition for the matrix of the organic film is about 1% to about 10% by weight of the initiator (D), specifically about 2% by weight based on the total weight of (A), (B), (C) and (D) About 5% by weight. In the above range, the composition for encapsulation may sufficiently occur photopolymerization upon exposure. In addition, it is possible to reduce the unreacted initiator remaining after the photopolymerization and to further improve the light transmittance of the organic film. The (B) silicon-based di (meth) acrylate may be represented by the following formula (1):

<Formula 1>

(In Formula 1, R ₁ , R ₂ , R ₃ , R ₄ , X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ , and n will be described later).

In the above range, the composition is organically excellent in the light curing rate, excellent light transmittance, low etching rate by the plasma, the display device from the effects of the environment including moisture and gas, and excellent in reliability over time to the device A film can be implemented.

In the present specification, (A) non-silicone-based di (meth) acrylate, (B) silicon-based di (meth) acrylate, (C) mono (meth) acrylate and (D) initiator are each different compounds. These may be included alone or two or more kinds.

(A) Non-silicone system Di (meth) acrylate

The (A) non-silicone di (meth) acrylate is a photocurable monomer which does not contain silicone (Si) and has two (meth) acrylate groups. Through this, the composition for encapsulation can be improved in the light curing rate, it is possible to increase the light transmittance after curing. In addition, the (A) non-silicone di (meth) acrylate has a low viscosity of 25 ° C., which can lower the viscosity of the composition for sealing. Through this, the composition for encapsulation may be such that the organic film is easily formed on the organic light emitting device or the inorganic film encapsulating the organic light emitting device by a method such as inkjet.

The (A) non-silicone di (meth) acrylate is a non-aromatic system not containing an aromatic group and may include a non-silicone di (meth) acrylate including a substituted or unsubstituted long chain alkylene group. .

Specifically, the (A) non-silicone di (meth) acrylate may be a di (meth) acrylate having a substituted or unsubstituted C1 to C20 alkylene group. More specifically, the (A) non-silicone di (meth) acrylate may include a di (meth) acrylate having a C1 to C15 alkylene group unsubstituted between the (meth) acrylate groups. At this time, the carbon number of the alkylene group means only the carbon number in the alkylene group itself except for the carbon in the di (meth) acrylate group. In one embodiment, the (A) non-silicone di (meth) acrylate may be represented by the formula (2):

<Formula 2>

(In Formula 2, R ₃ , R ₄ are each independently hydrogen or a methyl group, R ₅ is a substituted or unsubstituted C1 to C20 alkylene group). For example, in Formula 2, R ₅ may be an unsubstituted C8 to C12 alkylene group. More specifically, the (A) non-silicone di (meth) acrylate is octanediol di (meth) acrylate, nonanediol di (meth) acrylate, decanediol di (meth) acrylate, undecanediol di (meth) It may include one or more of acrylate, dodecanediol di (meth) acrylate.

The (A) non-silicone di (meth) acrylate is from about 10% to about 70% by weight, specifically based on the total weight of the silicone particles, (A), (B), (C) and (D) About 10% to about 60%, specifically about 25% to about 50%, for example about 25%, about 26%, about 27%, about 28%, about 29%, About 30%, about 31%, about 32%, about 33%, about 34%, about 35%, about 36%, about 37%, about 38%, about 39%, About 40%, about 41%, about 42%, about 43%, about 44%, about 45%, about 46%, about 47%, about 48%, about 49%, About 50% by weight. In the above range, there may be an effect that the photocuring rate of the composition for encapsulating the organic light emitting device is significantly improved.

(B) silicone Di (meth) acrylate

The (B) silicon-based di (meth) acrylate includes at least one or more substituted or unsubstituted C6 to C30 aryl groups linked to silicon atoms. (B) silicon-based di (meth) acrylate may be represented by the formula (1):

<Formula 1>

(In Formula 1, R ₁ , R ₂ are independently of each other, a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C1 to C30 alkylene ether group, * -N (R ')-(R ")-* (* is a linking site of an element, R' is hydrogen or a substituted or unsubstituted C1 to C30 alkyl group, R" is a substituted or unsubstituted C1 to C20 alkylene group), A substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted C7 to C30 arylalkylene group, or *-(R ')-O-** (where * is a linkage to O in Formula 1) , ** is a linking site for Si in Formula 1, R 'is a substituted or unsubstituted C1 to C30 alkylene group),

X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ are each independently hydrogen, hydroxyl, halogen, cyano group, substituted or unsubstituted C1 to C30 alkyl group, substituted or unsubstituted C1 to C30 A heterocycloalkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C1 to C30 alkyl ether group, * -N (R ') (R ") (* is an elemental linking site, R 'And R' are each independently hydrogen or substituted or unsubstituted C1 to C30 alkyl group), substituted or unsubstituted C1 to C30 alkylsulphide group, substituted or unsubstituted C6 to C30 aryl group, substituted Or an unsubstituted C2 to C30 heteroaryl group, or a substituted or unsubstituted C7 to C30 arylalkyl group,

At least one of X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ is a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C2 to C30 heteroaryl group,

R ₃ and R ₄ are each independently hydrogen or a methyl group,

n is 0 To An integer of 30 or an average value of n is 0 to 30).

The "single bond" means that Si and O in Formula 1 is directly connected (Si-O).

Specifically, in Chemical Formula 1, R ₁ and R ₂ may be each independently a single bond, a substituted or unsubstituted C1 to C20 alkylene group, or a substituted or unsubstituted C1 to C30 alkylene ether group. . Specifically, in Chemical Formula 1, X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ are each independently hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, substituted or unsubstituted C1 to C30 alkylether group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C2 to C30 heteroaryl group, or substituted or unsubstituted C7 To C30 is an arylalkyl group, and at least one of X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , and X ₆ may be a substituted or unsubstituted C6 to C30 aryl group.

More specifically, in Formula 1, R ₁ , R ₂ may be each independently a single bond or a substituted or unsubstituted C1 to C20 alkylene group. In this case, the plasma etch rate may be further lowered.

More specifically, in Formula 1, X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ are each independently a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C10 It is an aryl group, and one or more of X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ may be a substituted or unsubstituted C6 to C10 aryl group. More specifically, X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ may each independently be a methyl group, ethyl group, propyl group, butyl group, pentyl group, phenyl group, biphenyl group, or naphthyl group And one, two, three or six of X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ may be a phenyl group or a naphthyl group. In this case, the plasma etch rate may be further lowered.

More specifically, n can be an integer from 1 to 5. In this case, the plasma etch rate may be further lowered.

More specifically, (B) silicon-based di (meth) acrylate may be represented by any one of the following formula 1-1 to formula 1-6:

<Formula 1-1>

<Formula 1-2>

<Formula 1-3>

<Formula 1-4>

<Formula 1-5>

<Formula 1-6>

(B) Silicone type di (meth) acrylate can be manufactured by a conventional method. For example, (B) silicone-based di (meth) acrylate is a carbon chain and a siloxane compound in which a substituted or unsubstituted C6 to C30 aryl group or a substituted or unsubstituted C2 to C30 heteroaryl group is connected with at least one silicon atom. It may be prepared by reacting a compound (e.g. allyl alcohol) that extends, followed by reacting (meth) acryloyl chloride, but is not limited thereto. Or (B) silicone-based di (meth) acrylate is a siloxane compound and (meth) acrylic having a substituted or unsubstituted C6 to C30 aryl group or a substituted or unsubstituted C2 to C30 heteroaryl group connected with at least one silicon atom. It may be prepared by reacting monochloride, but is not limited thereto.

(B) silicon-based di (meth) acrylate is from about 20% to about 70% by weight, specifically about 25, based on the total weight of the silicon-based particles, (A), (B), (C) and (D) % To about 45%, for example about 25%, about 26%, about 27%, about 28%, about 29%, about 30%, about 31%, about 32% , About 33%, about 34%, about 35%, about 36%, about 37%, about 38%, about 39%, about 40%, about 41%, about 42% , About 43%, about 44%, about 45% by weight. In the above range, the transmittance of the organic layer may be increased, and the plasma etching rate may be decreased.

(C) mono (meth) acrylate

(C) Mono (meth) acrylate is contained in the composition for sealing an organic light emitting element, and can increase the photocuring rate of the composition for sealing. In addition, the (C) mono (meth) acrylate may increase the light transmittance of the organic film and at the same time reduce the plasma etch rate. The (C) mono (meth) acrylate may comprise a non-silicone mono (meth) acrylate, which does not contain silicone. The (C) mono (meth) acrylate may comprise at least one of aromatic mono (meth) acrylates having aromatic groups and non-aromatic mono (meth) acrylates having no aromatic groups.

In one embodiment, the (C) mono (meth) acrylate may comprise a mono (meth) acrylate having an aromatic group. Both the mono (meth) acrylate having an aromatic group and the aforementioned (B) silicone di (meth) acrylate have an aromatic group, and when used together, the compatibility in the composition for encapsulating an organic light emitting device is particularly excellent. Thereby, (C) mono (meth) acrylate can further improve the miscibility with the above-mentioned (B) silicone type di (meth) acrylate. In this case, the composition for encapsulation may be more excellent in significantly lowering the plasma etch rate of the organic layer.

The aromatic mono (meth) acrylate may include mono (meth) acrylate having a substituted or unsubstituted aromatic group. In this case, the "aromatic group" means a polycyclic aromatic group including a monocyclic or fused form, or the like, or a form in which a single ring is connected by a sigma bond. For example, the aromatic group is substituted or unsubstituted C6 to C50 aryl group, substituted or unsubstituted C7 to C50 arylalkyl group, substituted or unsubstituted C3 to C50 heteroaryl group, substituted or unsubstituted C3 to It may mean one or more of the heteroarylalkyl group of C50. More specifically, the aromatic group is phenyl, biphenyl, terphenyl, quarterphenyl, naphthyl, anthracenyl, phenanthrenyl, chrysenyl, triphenylenyl, tetrasenyl, pyrenyl, benzopyrenyl, pentaxenyl, coronyl , Ovalenyl, coranulenyl, benzyl, pyridinyl, pyrazinyl, pyrimidinyl, pyridazinyl, triazinyl, quinolinyl, isoquinolinyl, quinoxalinyl, acridinyl, quinazolinyl, shin Norinyl, phthalazinyl, thiazolyl, benzothiazolyl, isoxazolyl, benzisoxazolyl, oxazolyl, benzoxazolyl, pyrazolyl, indazolyl, imidazolyl, benzimidazolyl, purinyl, thiophenyl, It may be one or more of benzothiophenyl, furanyl, benzofuranyl, isobenzopranyl.

For example, the aromatic mono (meth) acrylate may be represented by the following Chemical Formula 3:

<Formula 3>

(In Formula 3, R ₃ is hydrogen or methyl group, s is an integer of 0 to 10, R ₆ is substituted or unsubstituted C6 to C50 aryl group or substituted or unsubstituted C6 to C50 aryloxy group to be).

For example, R ₆ is a phenylphenoxyethyl group, phenoxyethyl group, benzyl group, phenyl group, phenylphenoxy group, phenoxy group, phenylethyl group, phenylpropyl group, phenylbutyl group, methylphenylethyl group, propylphenylethyl group, methoxyphenylethyl group , Cyclohexylphenylethyl group, chlorophenylethyl group, bromophenylethyl group, methylphenyl group, methylethylphenyl group, methoxyphenyl group, propylphenyl group, cyclohexylphenyl group, chlorophenyl group, bromophenyl group, phenylphenyl group, biphenyl group, terphenyl (terphenyl ), Quaterphenyl, anthracenyl, naphthalenyl, triphenylenyl, methylphenoxy, ethylphenoxy, methylethylphenoxy, methoxyphenyloxy, propylphenoxy and cyclohexyl Phenoxy group, chlorophenoxy group, bromophenoxy group, biphenyloxy group, terphenyloxy group, quaterphenyloxy group, anthracenyloxy group, naphthalenyloxy (naphthaleneyloxy group) It may be a phthalenyloxy group, triphenylenyloxy group. Specifically, the aromatic mono (meth) acrylate is 2-phenylphenoxyethyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenyl (meth) acrylate, phenoxy (meth) acrylate, 2- Ethylphenoxy (meth) acrylate, benzyl (meth) acrylate, 2-phenylethyl (meth) acrylate, 3-phenylpropyl (meth) acrylate, 4-phenylbutyl (meth) acrylate, 2- (2 -Methylphenyl) ethyl (meth) acrylate, 2- (3-methylphenyl) ethyl (meth) acrylate, 2- (4-methylphenyl) ethyl (meth) acrylate, 2- (4-propylphenyl) ethyl (meth) Acrylate, 2- (4- (1-methylethyl) phenyl) ethyl (meth) acrylate, 2- (4-methoxyphenyl) ethyl (meth) acrylate, 2- (4-cyclohexylphenyl) ethyl ( Meth) acrylate, 2- (2-chlorophenyl) ethyl (meth) acrylate, 2- (3-chlorophenyl) ethyl (meth) acrylate, 2- (4-chlorophenyl) ethyl (meth) acrylate 2- (4-bromophenyl) ethyl (meth) acrylate, 2- (3-phenylphenyl) ethyl (meth) acrylate, 4- (biphenyl-2-yloxy) butyl (meth) acrylate, 3- (biphenyl-2-yloxy) butyl (meth) acrylate, 2- (biphenyl-2-yloxy) butyl (meth) acrylate, 1- (biphenyl-2-yloxy) butyl (meth ) Acrylate, 4- (biphenyl-2-yloxy) propyl (meth) acrylate, 3- (biphenyl-2-yloxy) propyl (meth) acrylate, 2- (biphenyl-2-yloxy ) Propyl (meth) acrylate, 1- (biphenyl-2-yloxy) propyl (meth) acrylate, 4- (biphenyl-2-yloxy) ethyl (meth) acrylate, 3- (biphenyl- 2-yloxy) ethyl (meth) acrylate, 2- (biphenyl-2-yloxy) ethyl (meth) acrylate, 1- (biphenyl-2-yloxy) ethyl (meth) acrylate, 2- (4-benzylphenyl) ethyl (meth) acrylate, 1- (4-benzylphenyl) ethyl (meth) acrylate or structural isomers thereof But, without being limited thereto. That is, the (meth) acrylates mentioned in the present invention are not limited to the examples, but the present invention further includes all the acrylates in the structural isomer relationship. For example, although only 2-phenylethyl (meth) acrylate is mentioned as an example of the present invention, the present invention includes both 3-phenylethyl (meth) acrylate and 4-phenyl (meth) acrylate.

Specifically, in Formula 3, s is an integer of 1 to 5, R ₆ is substituted or unsubstituted phenylphenoxy group, substituted or unsubstituted phenylphenylthiol group, substituted or unsubstituted biphenylphenoxy group, substituted or Unsubstituted terphenylphenoxy group, substituted or unsubstituted substituent is deuterium, C1-10 alkyl group, C1 ~ C10 alkoxy group, C6-18 aryl group, C3-18 heteroaryl group, or thiol It can be a machine.

Non-aromatic mono (meth) acrylates may be mono (meth) acrylates having substituted or unsubstituted C1 to C20 alkyl groups. Specifically, the non-aromatic mono (meth) acrylate is a mono (meth) acrylate having an unsubstituted linear C1 to C20 alkyl group, more specifically an unsubstituted straight C10 to C20 alkyl group. It can be a mono (meth) acrylate having. For example, non-aromatic mono (meth) acrylates include decyl (meth) acrylate, undecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth ) Acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, octadecyl (meth) acrylate, nonadecyl (meth) acrylate, arachidyl (meth) acrylic It may include, but is not limited to, one or more of the rates.

(C) mono (meth) acrylate is from about 5% to about 40% by weight, specifically about 5% by weight, based on the total weight of the silicone-based particles, (A), (B), (C) and (D) % To about 30%, more specifically about 10% to about 25%, for example about 10%, about 11%, about 12%, about 13%, about 14%, about 15 Weight%, about 16%, about 17%, about 18%, about 19%, about 20%, about 21%, about 22%, about 23%, about 24%, about 25 It may be included in weight percent. In the above range, the photocuring rate of the composition for sealing can be increased.

(D) Initiator

(D) The initiator is to cure the curable compound to form an organic film, and may include a conventional photopolymerization initiator without limitation.

(D) The initiator may include, but is not limited to, one or more of a triazine initiator, an acetophenone initiator, a benzophenone initiator, a thioxanthone initiator, a benzoin initiator, a phosphorus initiator, an oxime initiator. For example, as the phosphorus initiator, diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide, benzyl (diphenyl) phosphine oxide, bis (2,6-dimethoxybenzoyl) (2,4, 4-trimethylpentyl) phosphine oxide or mixtures thereof. For example, the use of phosphorus-based initiators may exhibit better onset performance at long wavelength UV in the compositions of the present invention. These may be included alone or in combination of two or more.

(D) the initiator is about 1% to about 10% by weight, specifically about 2% to about 5% by weight based on the total weight of the silicone-based particles, (A), (B), (C) and (D) May be included as a%. In the above range, photopolymerization may sufficiently occur during exposure of the composition for encapsulation.

Hereinafter, a composition for a matrix of an organic film including at least one curable compound and an initiator according to another embodiment of the present invention will be described.

The composition for the matrix of the organic film according to another embodiment of the present invention may include (E) (meth) acrylic compound of formula 4 and (D) initiator as one or more curable compounds:

<Formula 4>

, *-NH-*, *-S-*,

,

, *-SO-*, *-SO₂-*, ,

,

, 또는

(In Formula 4, X is * -CH _2- *, * -O- *,

, * -NH- *, * -S- *,

,

, * -SO- *, * -SO _2- *, ,

,

, or

(X ₁ is O or S, X ₂ is H, an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 20 carbon atoms, m is an integer of 1 to 10, n is an integer of 1 to 5),

Y is a single bond, * -CH _2- *, * -O- *, * -S- *, * -NH- *, * -SO- *, * -SO _2- * or, A ₁ and A ₂ Two hydrogens each bonded (where * represents a bond),

A ₁ and A ₂ are each independently aromatic having 6 to 20 carbon atoms or heteroaromatic having 3 to 20 carbon atoms,

,

Z ₁ and Z ₂ are each independently hydrogen,

,

(R is Z ₁ and Z ₂ each independently represent an alkylene group having 1 to 5, n is Z ₁ and Z ₂ each independently represent an integer of 1 to 10, R 'is hydrogen or a methyl group, and * represents a binding site )ego,

Unless both Z ₁ and Z ₂ are hydrogen).

For example, the composition for a matrix of the organic film of the present invention is (E) specific examples of the (meth) acrylic compound of formula (E) as one or more curable compounds, (meth) acrylate containing a dibenzothiophene structure, It may include one or more of the (meth) acrylates containing a dibenzofuran structure.

The refractive index of the matrix composition of the organic film may be about 1.55 or more, specifically about 1.55 to about 1.65. In this case, the difference in refractive index is greater than that of the silicon-based particles, and thus the luminance may be further increased.

When Y is “two hydrogens respectively bonded to A ₁ and A ₂ ”, as in Formula 4b, A ₁ and A ₂ are not connected, and Y is hydrogen.

Specifically, the (meth) acrylic compound represented by Formula 4 may be any one of Formulas 4a to 4f:

<Formula 4a>

<Formula 4b>

<Formula 4c>

<Formula 4d>

<Formula 4e>

<Formula 4f>

(In Formulas 4a to 4f, X, Y, Z ₁ and Z ₂ are the same as those of Formula 4, and Q ₁ and Q ₂ are each independently -S-, -NH-, or -O-).

이고, R은 메틸렌기이고, n은 1일 수 있다.(Meth) acrylic compound represented by the formula (4) is at least one of Z ₁ and Z ₂

, R is a methylene group, n may be 1.

The (meth) acrylic compound of formula 4 may be included alone or in mixture of two or more thereof. In an embodiment, the mixture of the (meth) acrylic compound of Formula 4 may be a mixture of the mono (meth) acrylic compound of Formula 4 that is monofunctional and the di (meth) acrylic compound of Formula 4 that is bifunctional. By including the mixture, the refractive index and the viscosity can be balanced, and the brightness and the moldability of the organic film can be good.

In one embodiment of the invention, the composition for the matrix of the organic film comprises a dibenzofuran moiety, a dibenzothiophene moiety, an azadibenzofuran moiety or an azadibenzothiophene moiety as one or more curable compounds. (Meth) acrylate.

The mixture of the (meth) acrylic compounds of formula 4 may have a refractive index of about 1.58 to about 1.70, specifically about 1.59 to about 1.68, more specifically about 1.60 to about 1.68. Within the above range, the refractive index is high, so that the luminance can be increased and the color change can be suppressed.

The (meth) acrylic compound of Formula 4 may be prepared by a conventional method, specifically, by a method of chloromethylation, but is not necessarily limited thereto. Chloromethylation utilizes a mechanism for introducing chloromethyl groups into aromatic compounds, and introduces chloromethyl groups into aromatic compounds with (para) formaldehyde and hydrochloric acid. At this time, the chloromethyl group can be introduced at all positions such as ortho, meta, or para of the aromatic compound. The above monofunctional or bifunctional compound can be prepared simultaneously by adding sodium acrylate to the product into which the chloromethyl group is introduced. The preparation method by chloromethylation has an advantage of simultaneously preparing a mixture of a monofunctional (meth) acrylic compound of Formula 4 and a bifunctional (meth) acrylic compound of Formula 4.

Compound (E) may be included in about 75.0% to about 98.0%, specifically about 90.0% to about 98.0% by weight based on the total weight of the silicon-based particles, (E) and (D). Further, about 92.0 wt% to about 97.0 wt%, for example about 75 wt%, about 76 wt%, about 77 wt%, about 78 wt%, about 79 wt%, about 80 wt%, about 81 wt% , About 82%, about 83%, about 84%, about 85%, about 86%, about 87%, about 88%, about 89%, about 90%, about 91% , About 92%, about 93%, about 94%, about 95% by weight. In the above range, there may be a color improving effect.

Compound (E) may be included in about 90% to about 99% by weight, specifically about 95% to about 98% by weight based on the total weight of (E) and (D). It may also be included from about 92.0% to about 98.0% by weight. In the above range, there may be a color improving effect.

(D) Initiator is the same as described in the composition for organic film matrix according to an embodiment of the present invention.

(D) the initiator may be included in about 1% to about 10% by weight, specifically about 2% to about 5% by weight based on the total weight of the silicon-based particles, (E) and (D). In the above range, photopolymerization may sufficiently occur during exposure of the composition for encapsulation.

(D) The initiator may be included in about 1% to about 10% by weight, specifically about 2% to about 5% by weight based on the total weight of (E) and (D). In the above range, photopolymerization may sufficiently occur during exposure of the composition for encapsulation.

The composition for encapsulating the organic light emitting device of the present invention may further include a heat stabilizer. As a result, the viscosity change in normal temperature of the composition for sealing can be suppressed. The heat stabilizer is included in the composition for encapsulation to suppress the change in viscosity at room temperature of the encapsulation composition, and a conventional heat stabilizer can be used without limitation, but the heat stabilizer uses a sterically hindered phenolic heat stabilizer. Can be. Specifically, the heat stabilizer is pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], stearyl-3- (3,5-di-t- Butyl-4-hydroxyphenyl) propionate, 1,3,5-tris (2,6-dimethyl-3-hydroxy-4-t-butylbenzyl) isocyanurate, 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (2-hydroxyethyl) isocyanurate, pentaerythritol tetrakis [3- ( 3,5-di-t-butylhydroxyphenyl) propionate], tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, but This is not restrictive. The heat stabilizer is about 2000 ppm or less, specifically about 0.01 ppm to about 2000 ppm, more specifically, based on the total weight of (A), (B), (C), and (D) or the total weight of (E) and (D) It may be included as about 100ppm to about 800ppm. The heat stabilizer in the above range can further improve the storage stability and fairness of the liquid state of the composition for sealing.

The composition for encapsulating the organic light emitting device of the present invention may be a solvent-free type containing no solvent.

The composition for encapsulating an organic light emitting device of the present invention has a viscosity of about 0 cps to about 200 cps, specifically about 100 cps or less, more specifically about 5 cps to about 50 cps, about 5 cps to about 25 ° C. ± 2 ° C. (23 ° C. to 27 ° C.). 40 cps or about 5 cps to about 30 cps. The composition for encapsulating the organic light emitting device in the above range can facilitate the formation of an organic film. In addition, in the above range, it may be advantageous to perform a method such as deposition, inkjet at the time of forming the organic film.

The composition for encapsulating an organic light emitting device of the present invention is a photocurable composition, which may be cured by irradiation for about 1 second to about 100 seconds at about 10 mJ / cm ² to about 1000 mJ / cm ² at a UV wavelength, but is not limited thereto. . Curing may be repeated one or more times. UV is not particularly limited but may be irradiated with a UV LED lamp.

The composition for encapsulating an organic light emitting device of the present invention can be used to encapsulate an organic light emitting device. Specifically, the organic film may be formed from a multilayer encapsulation film in which an inorganic film and an organic film are sequentially formed. For example, the composition for encapsulating an organic light emitting device may form an organic layer by a method such as deposition, inkjet, gravure coating, die coating, lip coating, spin coating, spin coating, but is not limited thereto.

Hereinafter, an organic light emitting display device of the present invention will be described.

The organic light emitting diode display device of the present invention may include an organic film formed of the composition for encapsulating the organic light emitting diode according to the embodiment of the present invention. Specifically, the organic light emitting diode display device includes an organic light emitting diode and a thin film encapsulation layer formed on the organic light emitting diode and including at least one inorganic film and at least one organic film, wherein the organic film is an organic light emitting diode encapsulation composition of an embodiment of the present invention. It can be formed as. As a result, the organic light emitting display device can suppress color change on the side surface and have high luminance. In particular, it is possible to suppress the color shift (blue shift) from the white side to the blue side and increase the luminance.

The thin film encapsulation layer may include a structure in which inorganic layers and organic layers are alternately formed. The total number of inorganic films and organic films may be 10 or less, for example, 2 to 7 layers. Specifically, a three-layer structure of an inorganic film, an organic film, and an inorganic film, a four-layer structure of an inorganic film, an organic film, an inorganic film, and an organic film, or a five-layer structure of an inorganic film, an organic film, an inorganic film, an organic film, and an inorganic film may be formed. Can be.

The inorganic film differs from the organic film in its components, thereby making it possible to compensate for the effects of the organic film. The inorganic film may be formed of an inorganic material having excellent light transmittance and excellent moisture and / or oxygen barrier properties. For example, the inorganic film may be a metal, a nonmetal, an intermetallic compound or alloy, a nonmetal intermetallic compound or alloy, an oxide of a metal or a nonmetal, a fluoride of a metal or a nonmetal, a nitride of a metal or a nonmetal, a carbide of a metal or a nonmetal, a carbide of a metal or a nonmetal, Oxynitride, borides of metals or nonmetals, oxygen borides of metals or nonmetals, silicides of metals or nonmetals, or mixtures thereof. Metals or nonmetals include silicon (Si), aluminum (Al), selenium (Se), zinc (Zn), antimony (Sb), indium (In), germanium (Ge), tin (Sn), bismuth (Bi), transitions Metal, lanthanide metal, and the like, but is not limited thereto. Specifically, the inorganic layer may include AlOx, In ₂ O ₃ , SnO ₂ , including silicon oxide (SiOx), silicon nitride (SiNx), silicon oxygen nitride (SiOxNy), ZnSe, ZnO, Sb ₂ O ₃ , Al ₂ O ₃ , and the like. Can be The inorganic film can be deposited by a plasma process, 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 thickness of one inorganic film is not particularly limited but may be about 100 kPa to about 2000 kPa. In the above range, excellent light transmittance, there may be a sealing effect excellent in moisture or oxygen barrier properties. The inorganic film may further include at least one of the silicon-based particles, alumina oxide, titanium oxide, and zirconium oxide in order to enhance the light scattering effect.

The refractive index of one organic layer may be about 1.45 or more, specifically about 1.47 to about 1.65. In the above range, there may be an effect of increasing the front brightness. The thickness of one organic layer may be about 5 μm to about 35 μm. In the above range, there may be a color improving effect.

Hereinafter, an organic light emitting diode display according to an exemplary embodiment of the present invention will be described with reference to FIG. 1. 1 is a cross-sectional view of an organic light emitting diode display according to an exemplary embodiment of the present invention.

Referring to FIG. 1, the organic light emitting diode display 100 may include a substrate 18; A driving transistor portion T2 formed on the substrate 18 and including a source electrode 30, a gate electrode 28, and a drain electrode 32; An organic light emitting element L1 formed on the driving transistor unit T2 and including a first pixel electrode 22, an organic light emitting layer 24, and a second pixel electrode 26 connected to the drain electrode 32; An overcoat 27 formed on the second pixel electrode 26; The thin film encapsulation layer 20 is formed on the overcoat 27, and the thin film encapsulation layer includes inorganic films 201 and 203 and organic films 202 that are alternately stacked. It may be formed of a composition for encapsulating an organic light emitting device of the present invention. The inorganic film 201 and the inorganic film 203 may have different compositions or thicknesses. However, the case where the inorganic film 201 and the inorganic film 203 are the same may also be included in the scope of the present invention.

Hereinafter, an organic light emitting diode display according to another exemplary embodiment of the present invention will be described with reference to FIG. 2. 2 is a cross-sectional view of an organic light emitting diode display according to another exemplary embodiment of the present invention.

Referring to FIG. 2, the organic light emitting diode display 100 ′ may include a substrate 18; A driving transistor portion T2 formed on the substrate 18 and including a source electrode 30, a gate electrode 28, and a drain electrode 32; An organic light emitting element L1 formed on the driving transistor unit T2 and including a first pixel electrode 22, an organic light emitting layer 24, and a second pixel electrode 26 connected to the drain electrode 32; An overcoat 27 formed on the second pixel electrode 26; A thin film encapsulation layer 20 'formed on the overcoat 27, and the thin film encapsulation layer 20' includes an inorganic film 201,203 and an organic film 202,204 that are alternately stacked. The organic layers 202 and 204 may be formed of the composition for encapsulating the organic light emitting device of the present invention. Except that the organic layer 204 is further formed, the organic light emitting diode display is substantially the same as the organic light emitting display device according to the exemplary embodiment.

2 illustrates a case where both the organic film 202 and the organic film 204 are formed of the organic light emitting device encapsulation composition of the present invention. However, any one of the organic film 202 and the organic film 204 does not contain a conventional organic light emitting element encapsulation composition, for example, the silicon-based particles, or zirconium oxide, titanium oxide, or oxide instead of the silicon-based particles. It may include one or more of the alumina, or may include silicon-based particles outside the average particle diameter.

Hereinafter, the configuration and operation of the present invention through the preferred embodiment of the present invention will be described in more detail. However, this is presented as a preferred example of the present invention and in no sense can be construed as limiting the present invention.

Production Example  1: silicone Of di (meth) acrylate  Produce

300 ml of ethyl acetate was added to a 1000 ml flask equipped with a cooling tube and a stirrer, and 25 g of 3-phenyl-1,1,3,5,5-pentamethyltrisiloxane (Gelest) and 43 g of allyl alcohol (purified) The mixture containing gold) was purged with nitrogen for 30 minutes. Thereafter, after adding 72 ppm of Pt on carbon black powder (Aldrich) to the mixture, the temperature in the flask was raised to 80 ° C. and stirred for 4 hours. The residual solvent was removed by distillation to give a compound. 71.5 g of the obtained compound was placed in 300 ml of dichloromethane, 39 g of triethylamine was added, and 34.3 g of acryloyl chloride was slowly added while stirring at 0 ° C. The residual solvent was removed by distillation to give a monomer of the following Chemical Formula 1-1 (molecular weight: 522.85 g / mol) in an HPLC purity of 97%. (1H NMR: δ7.61, m, 3H; δ7.12, m, 2H; δ6.25, d, 2H; δ6.02, dd, 2H; δ5.82, t, 1H; δ 5.59, d, 2H; δ3.87, m, 4H; δ1.54, m, 4H; δ0.58, m, 4H; δ0.02, m, 15H)

<Formula 1-1>

Production Example  2: Dibenzothiophene  Having structure Acrylate  Produce

(1) Preparation of the compound represented by formula (4-1a) or (4-1b)

9.84 g (53.4 mmol) of dibenzothiophene, 24.6 g of acetic acid, 2.82 g of paraformaldehyde (93.9 mmol) and 9.51 g of hydrochloric acid were added to a round bottom flask, followed by stirring. 15.7 g of sulfuric acid was slowly added dropwise thereto, the temperature was raised to 60 ° C., stirred for 5 hours, and the reaction was terminated. After the reaction was cooled to room temperature, the mixture was extracted with toluene, washed with water and 10% aqueous sodium hydroxide solution, and dried. The dried compound is a white solid (10.2 g), and includes the following Chemical Formulas 4-1a and 4-1b, which are produced by mono chloromethylation / dichloromethylation = 75/25 (by NMR). Confirmed.

[Formula 4-1a]

[Formula 4-1b]

(2) a compound represented by the formula (4-2a) or the formula (4-2b) Dibenzothiophene acryl Production rate)

Prepared Compounds of Formulas 4-1a and 4-2b (9.0 g), 10 mg of 2,6-ditertbutyl-4-methylphenol, sodium acrylate 14,1 g, tetrabutylammonium bromide (20 mg) was added to a round bottom flask, and 80 g of toluene was added thereto, and the temperature was raised to 105 ° C. and stirred for 12 hours. At the end of the reaction, the reactant was cooled to room temperature and the precipitate formed was removed through a filter. The filtrate was washed with 10% hydrochloric acid and 10% sodium hydroxide and dried. The dried compound was a colorless liquid (11.2 g), including the following formulas 4-2a and 4-2b, it was confirmed to maintain the ratio of monochloromethylation / dichloromethylation = 75/25.

[Formula 4-2a]

[Formula 4-2b]

Specific specifications of the components used in the following Examples and Comparative Examples are as follows.

(A) Non-silicone di (meth) acrylate: 1,12- dodecanediol dimethacrylate (Sartomer company)

(B) Silicone Di (meth) acrylate: Monomer of Preparation Example 1

(C) mono (meth) acrylate: M1142 (Miwon Specialty)

(D) Initiator: Darocur TPO (BASF)

(E) Mixture of (meth) acrylic compounds of Formula 4: Mixture of Preparation Example 2

Example  One

45.0 parts by weight of (A), 28.5 parts by weight of (B), 19.0 parts by weight of (C) and 2.9 parts by weight of (D) were mixed to prepare 95.0 parts by weight of the matrix composition for organic films. 5 weight part of polymethylsilsesquioxane particle | grains (SL-100M, Samsung SDI, average particle diameter: 1 micrometer) were mixed with the prepared matrix composition for organic films. A predetermined amount of zirconia beads (particle diameter: 0.5 mm) was added to the obtained mixture, stirred to be uniform, and the zirconia beads were removed to prepare a composition for encapsulating an organic light emitting device.

Example  2

(E) 96 parts by weight and (D) 3 parts by weight were mixed to prepare a 99 parts by weight matrix composition for organic films. 1 weight part of polymethylsilsesquioxane particle | grains (SL-030M, Samsung SDI, average particle diameter: 1 micrometer) were mixed with the prepared matrix composition for organic films. A predetermined amount of zirconia beads (particle diameter: 0.5 mm) was added to the obtained mixture, stirred to be uniform, and the zirconia beads were removed to prepare a composition for encapsulating an organic light emitting device.

Example  3

94.1 parts by weight of (E) and 2.9 parts by weight of (D) were mixed to prepare 97 parts by weight of the matrix composition for organic films. 3 weight part of polymethylsilsesquioxane particle | grains (SL-030M, Samsung SDI, average particle diameter: 1 micrometer) were mixed with the prepared matrix composition for organic films. A predetermined amount of zirconia beads (particle diameter: 0.5 mm) was added to the obtained mixture, followed by stirring to be uniform, and the zirconia beads were removed to prepare a composition for encapsulating an organic light emitting device.

Example  4 and Example  5

Except for changing the average particle diameter of the polymethylsilsesquioxane particles in Example 3, as shown in Table 1, the organic light emitting device sealing composition was prepared in the same manner. SL-300M (Samsung SDI) was used as a polymethylsilsesquioxane particle with an average particle diameter of 3 micrometers, and SL-500M (Samsung SDI) was used as a polymethylsilsesquioxane particle with an average particle diameter of 5 micrometers.

Comparative example  One

49.0 weight part of (A), 29.7 weight part of (B), 19.8 weight part of (C), and 3.0 weight part of (D) were mixed, and 99.0 weight part of matrix compositions for organic membranes were produced. 1 weight part of aluminum oxide particle | grains (SG-AL01P5S, a grain diameter AT company, an average particle diameter: 0.3 micrometer) were mixed with the manufactured matrix composition for organic films. A predetermined amount of zirconia beads (particle diameter: 0.5 mm) was added to the obtained mixture, stirred to be uniform, and zirconia beads were removed to prepare a composition for encapsulating an organic light emitting device.

Comparative example  2 to Comparative example  6

The same method as in Comparative Example 1 except that the content of (A), (B), (C), (D) and / or aluminum oxide particles and / or the average particle diameter of the aluminum oxide particles were changed as shown in Table 2 below. Thus, a composition for encapsulating an organic light emitting device was prepared.

Comparative example  7

(A) 46.9 weight part, (B) 29.9 weight part, (C) 19.9 weight part, and (D) 3.0 weight part were mixed, and 99.7 weight part of matrix compositions for organic membranes were produced. Titanium oxide particles (SG-AL01P5S, P.K., AT., Average particle size: 0.3 μm 0.3 parts by weight were mixed with the prepared organic film matrix composition. The zirconia beads were removed to prepare an organic light emitting device encapsulation composition.

Comparative example  8 to Comparative example  12

In Comparative Example 7 except that the content of (A), (B), (C), (D) and / or titanium oxide particles and / or the average particle diameter of titanium oxide were changed as shown in Table 3 below. , To prepare a composition for encapsulating an organic light emitting device.

Comparative example  13

47 parts by weight of (A), 30 parts by weight of (B), 20 parts by weight of (C) and 3 parts by weight of (D) were mixed and 100 parts by weight were mixed to prepare a matrix composition for an organic film.

Example One 2 3 4 5 (A) (part by weight) 44.6 - - - - (B) (part by weight) 28.5 - - - - (C) (part by weight) 19.0 - - - - (D) (part by weight) 2.9 3 2.9 2.9 2.9 (E) (part by weight) - 96 94.1 94.1 94.1 Total of (A), (B), (C) and (D) (parts by weight) 95.0 - - - - Sum of (D), (E) (parts by weight) - 99 97 97 97 Content of Silicon Particles (parts by weight) 5 One 3 3 3 Refractive index of the sum of (A), (B), (C) and (D) 1.498 - - - - Refractive index of the sum of (D) and (E) - 1.604 1.604 1.604 1.604 Refractive Index of Silicon-Based Particles 1.420 1.420 1.420 1.420 1.420 Average particle size of the silicon particles (㎛) One One One 3 5

Comparative example One 2 3 4 5 6 (A) (part by weight) 46.5 45.6 44.6 46.5 45.6 44.6 (B) (part by weight) 29.7 29.1 28.5 29.7 29.1 28.5 (C) (part by weight) 19.8 19.4 19.0 19.8 19.4 19.0 (D) (part by weight) 3.0 2.9 2.90 3.0 2.9 2.9 Total (parts by weight) of (A), (B), (C) and (D) 99.0 97.0 95.0 99.0 97.0 95.0 Content of aluminum oxide particles (parts by weight) One 3 5 One 3 5 Refractive index of the sum of (A), (B), (C) and (D) 1.498 1.498 1.498 1.498 1.498 1.498 Refractive Index of Aluminum Oxide Particles 1.768 1.768 1.768 1.768 1.768 1.768 Average particle size of aluminum oxide particles (µm) 0.3 0.3 0.3 2.6 2.6 2.6

Comparative example 7 8 9 10 11 12 13 (A) (part by weight) 46.9 46.8 46.5 46.9 46.8 46.9 47 (B) (part by weight) 29.9 29.9 29.7 29.9 29.9 29.7 30 (C) (part by weight) 19.9 19.9 19.8 19.9 19.9 19.8 20 (D) (part by weight) 3.0 2.9 3.0 3.0 2.9 3.0 3.0 Total (parts by weight) of (A), (B), (C) and (D) 99.7 99.5 99.0 99.7 99.5 99.0 100 Content of titanium oxide particles (parts by weight) 0.3 0.5 One 0.3 0.5 One - Refractive index of the sum of (A), (B), (C) and (D) 1.498 1.498 1.498 1.498 1.498 1.498 1.498 Refractive Index of Titanium Oxide Particles 2.488 2.488 2.488 2.488 2.488 2.488 - Average particle size of titanium oxide particles (µm) 0.3 0.3 0.3 2.6 2.6 2.6 -

The physical properties of the following Tables 4 and 5 were evaluated for the composition for encapsulating the organic light emitting device according to Examples and Comparative Examples.

Example One 2 3 4 5 Color change rate 0.018 0.019 0.014 0.012 0.015 Color change rate reduction rate (%) 38 34 52 59 48 Relative brightness (%) 90 93 80 87 89 Haze (%) 20.8 42.7 69.7 40.2 30.6 Light transmittance (%) 88.3 85.6 85.8 86.3 85.0

Comparative example One 2 3 4 5 6 7 8 9 10 11 12 13 Color change rate 0.026 0.021 0.020 0.023 0.017 0.015 0.018 0.014 0.006 0.023 0.010 0.011 0.029 Color change rate reduction rate (%) 10 28 31 21 41 48 38 52 79 21 66 62 0 Relative brightness (%) 93 81 74 92 78 67 74 57 41 83 74 59 100 Haze (%) 11.3 29 44.5 18.5 43.9 65.9 33.7 54.1 79.3 24.1 34.2 59.8 1.6 Light transmittance (%) 88.4 84.1 80.6 89.2 86.4 82.1 75.5 66.9 55.3 87.1 80.2 67.0 90.6

In the organic light-emitting device encapsulation composition, the WAD improvement effect can be visually confirmed when the color change rate is reduced by 30% or more, and the higher the relative luminance, the better the value, or at least 80% or more, which corresponds to the specification that can be used in the OLED display device. do.

In this regard, as shown in Table 4, the composition for encapsulating the organic light emitting device of the present invention has a high light transmittance of 85% or more, and a color change rate reduction rate of 30% or more, which corresponds to a specification that can be used in an OLED display device. Organic films with high relative luminance of 80% or more can be realized.

On the other hand, as shown in Table 5, the comparative example including the aluminum oxide particles or titanium oxide particles has a high rate of color change reduction but low relative luminance, or high relative brightness but low rate of color change reduction.

<Property evaluation method>

(1) color shift (column shift): The composition for encapsulating the organic light-emitting device of Example and Comparative Example was coated on a plastic film, and cured twice at 180mJ / cm ² at a wavelength of 390nm using a Belt type LED lamp to have a thickness of 30 An organic film of μm was prepared. An organic film was attached to the panel on which the organic light emitting element was formed. The front of the panel is 0 ° and the left and right ends are 90 ° with respect to the front, and EZcontrast (Eldim) uses 0 ° to 60 ° in 1 ° increments in luminance and color coordinates (u'v '). The value was obtained. The difference between the value at 0 ° and the value at 1 ° intervals from 0 ° to 60 ° was calculated as the color change rate (Δu'v '). A medium color change rate was taken from 0 ° to 60 °.

(2) Color change rate reduction rate: The color change rate was obtained by the method of (1). The color change rate obtained by the color change rate of the comparative example 13 in A, the said Example, or the comparative example was called B. The rate of color change reduction was calculated as | (A-B) / A | x 100. The higher the color change rate reduction rate, the more the color change in the front facing side is suppressed. When the rate of color change decreases to 30% or more, it can be said that the color change rate decreases.

(3) Relative luminance: An organic film was produced by the method of (1). An organic film was attached to the panel on which the organic light emitting element was formed. The front side of the panel was made 0 degree, and the luminance value was obtained at 0 degree using EZcontrast (Eldim). C and the luminance value obtained by the said Example or the comparative example were made into the luminance value of the comparative example 13. Relative luminance was calculated as | (C-D) / C | x 100. The higher the relative luminance, the higher the luminance in the front. It can be said that the luminance is high when the relative luminance is more than 80%.

(4) Haze and light transmittance: An organic film was prepared in the same manner as in (1). The haze and light transmittance of the organic film were measured at a wavelength of 589 nm using NDH5000W (NIPPON DENSHOKU) in accordance with ASTM D1003.

Simple modifications or changes of the present invention can be easily carried out by those skilled in the art, and all such modifications or changes can be seen to be included in the scope of the present invention.

Claims (15)

A composition for encapsulating an organic light emitting device, comprising silicon particles having an average particle diameter of about 0.70 μm to about 10.0 μm, at least one curable compound, and an initiator. The composition of claim 1, wherein a difference between the refractive indices of the at least one curable compound and the entire initiator and the silicon-based particles is about 0.07 or more. The composition of claim 1, wherein the silicon-based particles include polysilsesquioxane organic particles. The composition of claim 3, wherein the silicon-based particles include polymethylsilsesquioxane particles. The composition of claim 1, wherein the silicon-based particles are included in about 0.1% by weight to about 20% by weight of the total of the at least one curable compound, the silicon-based particles, and the initiator. The composition of claim 5, wherein the silicon-based particles are included in about 1% by weight to about 5% by weight of the total of the at least one curable compound, the silicon-based particles, and the initiator. The composition of claim 1, wherein a refractive index of the at least one curable compound and the entire initiator is about 1.45 or more. The composition of claim 7, wherein the refractive index of the at least one curable compound and the initiator as a whole is about 1.55 or more. The method of encapsulating an organic light emitting device according to claim 1, wherein the at least one curable compound is a (meth) acrylate containing a dibenzothiophene, dibenzofuran, azadibenzofuran or an azadibenzothiophene moiety. Composition. The compound of claim 1, wherein the at least one curable compound comprises a mixture of (A) non-silicone di (meth) acrylate, (B) silicone di (meth) acrylate and (C) mono (meth) acrylate , The (A) non-silicone di (meth) acrylate is from about 10% to about 70% by weight based on the total weight of the silicon-based particles, (A), (B), (C) and (D) Included, The (B) silicon-based di (meth) acrylate is included in about 20% to about 70% by weight based on the total weight of the silicon-based particles, (A), (B), (C) and (D) , The (C) mono (meth) acrylate is contained in about 5% by weight to about 40% by weight based on the total weight of the silicon-based particles, (A), (B), (C) and (D) Phosphorus, organic light emitting device encapsulation composition. The organic light emitting device encapsulation composition of claim 10, wherein the (B) silicon-based di (meth) acrylate is represented by Formula 1 below: <Formula 1>

(In Formula 1, R ₁ , R ₂ are independently of each other, a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C1 to C30 alkylene ether group, * -N (R ')-(R ")-* (* is a linking site of an element, R' is hydrogen or a substituted or unsubstituted C1 to C30 alkyl group, R" is a substituted or unsubstituted C1 to C20 alkylene group), A substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted C7 to C30 arylalkylene group, or *-(R ')-O-** (where * is a linkage to O in Formula 1) , ** is a linking site for Si in Formula 1, R 'is a substituted or unsubstituted C1 to C30 alkylene group), X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ are each independently hydrogen, hydroxyl, halogen, cyano group, substituted or unsubstituted C1 to C30 alkyl group, substituted or unsubstituted C1 to C30 A heterocycloalkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C1 to C30 alkyl ether group, * -N (R ') (R ") (* is an elemental linking site, R 'And R' are each independently hydrogen or substituted or unsubstituted C1 to C30 alkyl group), substituted or unsubstituted C1 to C30 alkylsulphide group, substituted or unsubstituted C6 to C30 aryl group, substituted Or an unsubstituted C2 to C30 heteroaryl group, or a substituted or unsubstituted C7 to C30 arylalkyl group, At least one of X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ is a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C2 to C30 heteroaryl group, R ₃ and R ₄ are each independently hydrogen or a methyl group, n is 0 To An integer of 30 or an average value of n is 0 to 30). The composition of claim 1, wherein the organic layer formed of the composition for encapsulating the organic light emitting device has a refractive index of about 1.45 or more. An organic light emitting device, and a thin film encapsulation layer formed on the organic light emitting device and including at least one inorganic film and at least one organic film, The organic light emitting diode display device of claim 1, wherein the organic layer is formed of the organic light emitting element encapsulation composition of any one of claims 1 to 12. The organic light emitting diode display device of claim 13, wherein the organic layer has silicon particles having an average particle diameter of about 1 μm to about 5 μm. The organic light emitting diode display of claim 13, wherein the organic layer has a refractive index of about 1.47 to about 1.65.

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