KR20170027938A - Composition for encapsulating organic light emitting diode device and organic light emitting diode display using prepared the same - Google Patents

Abstract

The purpose of the present invention is to provide a composition for encapsulating an organic light emitting device which can realize an organic film increasing a color shift reduction rate and brightness. To this end, provided are a composition for encapsulating an organic light emitting device comprising silicon-based particles having the average particle diameter of 0.70 to 10.0 m, one or more curable compounds and initiators, and an organic light emitting device display comprising the organic film formed therefrom.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composition for encapsulating organic light emitting diodes and an organic light emitting diode (OLED)

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composition for encapsulating an organic light emitting device and an organic light emitting diode display device manufactured therefrom.

An OLED display is a display device that emits light by using an electroluminescent phenomenon, and includes an organic light emitting device. Since the organic light emitting device is an organic material, the lifetime of the organic light emitting device may be shortened due to deterioration. Shortened lifetime 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 the intensity of light and reducing the width of the emission wavelength, thereby reducing power consumption and improving color purity. That is, the distance between the anode and the cathode of the organic light emitting diode is designed to match the representative wavelength of red (R), green (G), and blue (B), and only light corresponding to the wavelength is resonated, And light other than the wavelength is weakened. As a result, the intensity of light emitted to the outside of the organic light emitting element becomes stiff and sharp, thereby increasing brightness and color purity.

Even if the organic light emitting display device includes the microcavity structure, if the organic light emitting display device sees the organic light emitting device on the side other than the front side, the path length of the light on the side surface is different from the path length of the light on the front surface side. This results in the same effect as that of the thickness of the organic light emitting layer, thereby changing the wavelength to be amplified. That is, as the viewing angle of the organic light emitting diode increases from the front side to the side, the maximum resonance wavelength appears on the short wavelength side, and a color shift occurs on the short wavelength side. Therefore, a blue shift occurs on the front surface of the organic light emitting diode as a white color, and a blue color shifts toward the side surface, thereby causing a problem that a blue color appears on the side.

In order to suppress such color change, an optical film for reducing the color change can be introduced into the organic light emitting display as disclosed in Korean Patent Laid-Open Publication No. 2014-0137954. However, it is not possible to thin the organic light emitting display device by separately introducing an optical film for reducing the color change.

On the other hand, since the organic light emitting element is damaged by moisture and / or oxygen outside, it must be sealed by a thin film encapsulation structure of an organic film and an inorganic film.

The background art of the present invention is disclosed in Korean Patent Publication No. 2012-0115841.

SUMMARY OF THE INVENTION It is an object of the present invention to provide a composition for encapsulating an organic light emitting device capable of realizing an organic film which increases the rate of color shift reduction in front side contrast and increases brightness.

Another object of the present invention is to provide a composition for encapsulating an organic light emitting device, which can realize an organic film which increases a color change reduction rate on a shorter wavelength side and increases brightness.

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

It is still another object of the present invention to provide a composition for encapsulating an organic light emitting device capable of realizing an organic film having a high light transmittance.

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

The present invention provides a composition for encapsulating an organic light emitting device capable of preventing the penetration of moisture and / or oxygen from the outside to improve the reliability of the organic light emitting device and the organic film having a low plasma etching rate.

It is still another object of the present invention to provide an OLED display device including the organic layer.

The composition for encapsulating an organic luminescent element of the present invention may comprise silicon-based particles having an average particle diameter of 0.70 to 10.0 탆, at least one curable compound and an initiator.

The organic electroluminescent display device of the present invention includes an organic light emitting device and a thin film encapsulation layer formed on the organic electroluminescence device and including at least one inorganic film and at least one organic film, / RTI >

The present invention provides a composition for encapsulating an organic light emitting device capable of realizing an organic film which increases a color change reduction ratio in front side contrast and increases brightness.

The present invention provides a composition for encapsulating an organic light emitting device capable of realizing an organic film which enhances a reduction rate of a color change in a short wavelength side and increases brightness.

The present invention provides a composition for encapsulating an organic light emitting device, which can realize an organic film that suppresses color change from white to blue on the side and increases brightness.

The present invention provides a composition for encapsulating an organic light emitting device capable of realizing an organic film having a high light transmittance.

The present invention provides a composition for encapsulating an organic light emitting device having an appropriate light scattering property and capable of realizing an organic film having a color improving effect.

The present invention provides a composition for encapsulating an organic light emitting device capable of preventing the penetration of moisture and / or oxygen from the outside to improve the reliability of the organic light emitting device and the organic film having a low plasma etching rate.

The present invention provides an OLED display device including the organic layer.

1 is a cross-sectional view of an OLED display device according to an embodiment of the present invention.
2 is a cross-sectional view of an OLED display device according to another embodiment of the present invention.

The present invention will now be described more fully hereinafter with reference to the accompanying drawings, in which preferred embodiments of the invention are shown. The present invention may be embodied in many different forms and is not limited to the embodiments described herein. In order to clearly illustrate the present invention, parts not related to the description are omitted, and the same or similar components are denoted by the same reference numerals throughout the specification.

As used herein, "(meth) acrylic" means acrylic and / or methacrylic.

As used herein, "substituted" means that at least one hydrogen atom of the functional group is replaced by a halogen (e.g. F, Cl, Br or I), a hydroxy group, a nitro group, a cyano group, , = NR, R is C1 to C10 alkyl groups), amino groups _{(-NH 2, -NH (R '} ), -N (R ") (R"'), wherein R ', R ", R"' are each A C1 to C30 alkyl group, a C6 to C30 aryl group, a C3 to C30 cycloalkyl group, a C3 to C30 heteroaryl group, a C3 to C30 heteroaryl group, a C3 to C30 heteroaryl group, Or a C2 to C30 heterocycloalkyl group.

As used herein, the term " aryl group "means a functional group in which all the elements of the substituent which is cyclic are p-orbital, and these p-orbital forms a conjugation. The aryl group includes monocyclic, non-fused polycyclic or fused polycyclic functional groups. In this case, fusion refers to a ring shape in which carbon atoms divide adjacent pairs. The aryl group also includes a biphenyl group, a terphenyl group, or a quarter-phenyl group in which two or more aryl groups are connected through a sigma bond. The aryl group may mean a phenyl group, a naphthyl group, an anthracenyl group, a phenanthrenyl group, a pyrenyl group, or a chrysenyl group.

As used herein, a "heteroaryl group" refers to a functional group that contains 1 to 3 heteroatoms selected from the group consisting of N, O, S, P, and Si in the aryl group and the remainder is carbon. Heteroaryl groups also include those wherein two or more heteroaryl groups are linked directly via a sigma bond. The heteroaryl group also includes two or more heteroaryl groups fused together. When the heteroaryl group is fused, each ring may contain one to three of the above heteroatoms. The heteroaryl group may be, for example, a pyridinyl group, a pyrimidinyl group, a pyrazinyl group, a pyridazinyl group, a triazinyl group, a quinolinyl group, an isoquinolinyl group or the like.

More specifically, the C6 to C30 aryl group and / or the C3 to C30 heteroaryl group may be substituted or unsubstituted phenyl group, substituted or unsubstituted naphthyl group, substituted or unsubstituted anthracenyl group, substituted or unsubstituted phenanthryl group A substituted or unsubstituted naphthacenyl group, a substituted or unsubstituted pyrenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted p-terphenyl group, a substituted or unsubstituted m-terphenyl group, a substituted or unsubstituted pyrazinyl group, A substituted or unsubstituted thienyl group, a substituted or unsubstituted thienyl group, a substituted or unsubstituted thienyl group, a substituted or unsubstituted thienyl group, a substituted or unsubstituted thienyl group, a substituted or unsubstituted thienyl group, A substituted or unsubstituted thiazolyl group, a substituted or unsubstituted oxazolyl group, a substituted or unsubstituted pyrazolyl group, a substituted or unsubstituted imidazolyl group, a substituted or unsubstituted thiazolyl group, a substituted or unsubstituted oxazolyl 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 substituted or unsubstituted pyrazinyl group, a substituted or unsubstituted pyrazinyl group, a substituted or unsubstituted pyrazinyl group, A substituted or unsubstituted thiazolyl group, a substituted or unsubstituted benzofuranyl group, a substituted or unsubstituted benzothiophenyl group, a substituted or unsubstituted benzimidazolyl group, a substituted or unsubstituted indolyl group, a substituted or unsubstituted quinoline group, Substituted or unsubstituted quinoxalinyl groups, substituted or unsubstituted quinoxalinyl groups, substituted or unsubstituted naphthyridinyl groups, substituted or unsubstituted benzoxazinyl groups, substituted or unsubstituted quinoxalinyl groups, substituted or unsubstituted quinazolinyl groups, substituted or unsubstituted quinazolinyl groups, substituted or unsubstituted naphthyridinyl groups, A substituted or unsubstituted benzothiazyl group, a substituted or unsubstituted acridinyl group, a substituted or unsubstituted phenazinyl group, a substituted or unsubstituted phenothiazine group, a substituted or unsubstituted pyrazine group, A substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenylene group, or a combination thereof, but is not limited thereto.

In the present specification, "composition for encapsulating an organic luminescent element" may be simply referred to as "encapsulating composition ".

Hereinafter, a composition for encapsulating an organic light emitting diode according to an embodiment of the present invention will be described.

The composition for encapsulating an organic luminescent element according to an embodiment of the present invention may include silicon-based particles having an average particle diameter of 0.70 to 10.0 m, one or more curable compounds and an initiator. For example, the composition for encapsulating an organic luminescent element of the present embodiment contains silicon-based particles having an average particle diameter of 0.70 μm to 10.0 μm, specifically 1 μm to 5 μm, thereby achieving light scattering properties, And an organic film having a high light transmittance can be formed. Particularly, the composition for encapsulating an organic luminescent element of the present embodiment can form an organic film capable of increasing a reduction rate of a color change at a short wavelength side specifically at a blue wavelength. At this time, "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 the front contrast side of the organic light emitting device. Further, the composition for encapsulating an organic luminescent element of the present embodiment can contain an external initiator and / or oxygen, and can form an organic film having a low plasma etching rate by containing at least one curable compound and an initiator described below. Further, in the composition for encapsulating an organic luminescent element of the present embodiment, it is not necessary to use a separate optical film for color change reduction by imparting light scattering property to the organic film which encapsulates the organic luminescent element, so that the organic luminescent display device can be made thin .

Hereinafter, the silicon-based particles will be described.

The silicon-based particles are included in the composition for encapsulating an organic light-emitting device, and have a light scattering property, thereby increasing the rate of decreasing the color change, thereby suppressing the color change and increasing the luminance. The silicon-based particles may have an average particle diameter of 0.70 to 10.0 mu m. In the above range, it is possible to realize an organic film which suppresses color change and increases brightness. Specifically, the average particle diameter of the silicon-based particles may be 1 탆 to 5 탆. The "average particle diameter" may mean a value corresponding to D50 when applied to a particle size analyzer.

The silicon-based particles may have a large difference in refractive index between the refractive index of the matrix of the at least one curable compound and the organic film formed of the initiator. As the refractive index difference is larger, an organic film capable of suppressing color change and increasing brightness can be formed. The silicon-based particles are impregnated in 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 the entire curable compound and the initiator - the refractive index of the silicon-based particle) may be 0.07 or more, specifically 0.078 to 0.2. Within 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 1.5, specifically 1.3 to 1.49, more specifically 1.3 to 1.45. Within this range, an organic film having high light efficiency and excellent surface flatness can be realized. The shape of the silicon-based particles is not limited, but they may have spherical beads, amorphous shapes, and the like.

The silicon-based particles include silicon-containing particles, and may include silicon-based organic particles. Specifically, the silicone-based organic particles may include polysilsesquioxane organic particles. The polysilsesquioxane particles may also provide an organic film having an excellent surface flatness. Specifically, the silicon-based particles may include polysilsesquioxane particles having (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 singly or in combination of two or more. Specifically, the silicon-based particles may include polymethylsilsesquioxane (PMSQ) particles.

The silicon-based particles may be used in an amount of 0.1 to 20% by weight, specifically 1 to 10% by weight, more specifically 1 to 5% by weight, based on the total amount of at least one of the curable compound, the silicone- %. ≪ / RTI > In the above range, it is possible to realize an organic film having a high color change reduction rate, high luminance, and capable of suppressing penetration of moisture and / or oxygen outside.

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

The one or more curable compounds and the initiator may be cured to form a matrix of the organic film. The curing may include one or more of light curing, heat curing. The curable compound may include one or more of a photocurable compound, a thermosetting compound, and the like.

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

The composition for a matrix of an organic film according to an embodiment of the present invention may include at least one curable compound selected from the group consisting of (A) non-silicon di (meth) acrylate, (B) silicone di (meth) acrylate, Acrylate, and (D) an initiator. The refractive index of the composition for a matrix of the organic film may be 1.45 or more, specifically 1.49 to 1.65. In one embodiment of the present invention, the refractive index of the composition for a matrix of an organic film may be 1.55 or more, specifically 1.60 or more. When the refractive index difference from the silicon-based particles is large, the brightness can be increased.

Specifically, the composition for a matrix of an organic film comprises 10 to 70% by weight of (A) non-silicon di (meth) acrylate based on the total weight of (A), (B), (C) (B) 20 to 70% by weight, specifically 25 to 45% by weight of silicone di (meth) acrylate, (C) mono ( (Meth) acrylate in an amount of 5 wt% to 40 wt%, specifically 5 wt% to 30 wt%. Within the above range, the photo-curability of the sealing composition can be improved, and an organic film having a high light transmittance and a low plasma etching rate can 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 film is etched by the plasma, the penetration of moisture and / or oxygen outside can be facilitated. The composition for a matrix of an organic film preferably contains 1 to 10% by weight, specifically 2 to 5% by weight, based on the total weight of (A), (B), (C) and (D) As shown in FIG. Within this range, the composition for encapsulation can sufficiently undergo photopolymerization upon exposure. In addition, the unreacted initiator remaining after the photopolymerization can be reduced, and the light transmittance of the organic film can be further improved. The (B) silicon-based di (meth) acrylate may be represented by the following formula (1)

≪ Formula 1 >

R ₁ , R ₂ , R ₃ , R ₄ , X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ and n are described below.

In the above range, the composition is remarkably improved in photo-curability, has excellent light transmittance, has a low etching rate by plasma, protects the display device from the influence of the environment including moisture and gas, Can be implemented.

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

(A) a non-silicone-based di (meth) acrylate

(A) Non-silicone di (meth) acrylate is a photocurable monomer that does not contain silicon (Si) and has two (meth) acrylate groups. Thus, the composition for encapsulation can improve the photo-curability and the light transmittance after curing. Further, the non-silicone di (meth) acrylate (A) has a low viscosity at 25 占 폚 and can lower the viscosity of the bag composition. Accordingly, the sealing composition can easily form an organic film on the inorganic film which encapsulates the organic light emitting device or the organic light emitting device by an ink jet method or the like.

(A) Non-silicon based di (meth) acrylates are non-aromatic systems which do not contain aromatic groups and may include non-silicon based di (meth) acrylates containing substituted or unsubstituted long chain alkylene groups .

Specifically, (A) the non-silicone di (meth) acrylate may be a di (meth) acrylate having a substituted or unsubstituted C1 to C20 alkylene group. More specifically, (A) the non-silicone based di (meth) acrylate may include a di (meth) acrylate having an unsubstituted C1 to C15 alkylene group between the (meth) acrylate groups. Here, the number of carbon atoms in the alkylene group means only the number of carbon atoms in the alkylene group itself excluding the carbon in the di (meth) acrylate group. In one embodiment, (A) the non-silicon based di (meth) acrylate can be represented by the following formula:

(2)

(Wherein R ₃ and R ₄ are each independently hydrogen or a methyl group, and R ₅ is a substituted or unsubstituted C1 to C20 alkylene group). For example, in Formula 2, R ₅ may be an unsubstituted C 8 to C 12 alkylene group. More specifically, (A) the non-silicone based di (meth) acrylate is selected from the group consisting of octanediol di (meth) acrylate, nonanediol di (meth) acrylate, decanediol di (meth) acrylate, undecanediol Acrylate, and dodecanediol (meth) acrylate.

(A) non-silicon based di (meth) acrylate is used in an amount of 10 to 70% by weight, more preferably 10 to 30% by weight, based on the total weight of the silicone particles, (A), (B), (C) % To 60 wt%, specifically 25 wt% to 50 wt%. Within the above range, the photocuring ratio of the composition for encapsulating an organic light emitting element may be remarkably improved.

(B) a silicone-based di (meth) acrylate

(B) silicone-based di (meth) acrylate includes at least one substituted or unsubstituted C6 to C30 aryl group connected to a silicon atom. (B) a silicone-based di (meth) acrylate can be represented by the following formula (1):

≪ Formula 1 >

(Wherein R ₁ and 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 hydrogen or a substituted or unsubstituted C1 to C30 alkyl group, R''is a substituted or unsubstituted C1 to C20 alkylene group), - (R' Substituted or unsubstituted C6 to C30 arylene groups, substituted or unsubstituted C7 to C30 arylalkylene groups, or * - (R ') - O - ** wherein * , ** is a connecting site for Si in formula (1), and R 'is a substituted or unsubstituted C1 to C30 alkylene group)

X ₁ , X ₂ , X ₃ , X ₄ , X ₅ and X ₆ each independently represent a hydrogen atom, a hydroxyl group, a halogen atom, a cyano group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C1 to C30 A substituted or unsubstituted C 3 to C 30 cycloalkyl group, a substituted or unsubstituted C 1 to C 30 alkyl ether group, * -N (R ') (R ") (* And R "are each independently hydrogen or a substituted or unsubstituted C1 to C30 alkyl group), a substituted or unsubstituted C1 to C30 alkylsulfide group, a substituted or unsubstituted C6 to C30 aryl group, a 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 and 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 Or an average value of n is 0 to 30).

Said "single bond" means that Si and O in formula (1) are directly connected (Si-O).

Specifically, in Formula 1, R ₁ and R ₂ independently of each other may be a single bond, a substituted or unsubstituted C1 to C20 alkylene group, or a substituted or unsubstituted C1 to C30 alkylene ether group . X ₁ , X ₂ , X ₃ , X ₄ , X ₅ and X ₆ are each independently selected from the group consisting of hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 alkyl group, A substituted or unsubstituted C1 to C30 alkyl ether group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heteroaryl group, or a substituted or unsubstituted C7 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, R ₁ and R ₂ in formula (1) may each independently be a single bond or a substituted or unsubstituted C1 to C20 alkylene group. In this case, there may be more effects of lowering the plasma etching rate.

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

More specifically, n may be an integer of 1 to 5. In this case, there may be more effects of lowering the plasma etching rate.

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

≪ Formula 1-1 >

(1-2)

<Formula 1-3>

<Formula 1-4>

&Lt; Formula 1-5 >

<Formula 1-6>

.

.

(B) silicone-based di (meth) acrylate can be prepared by a conventional method. For example, (B) a silicone-based di (meth) acrylate is a compound in which a substituted or unsubstituted C6 to C30 aryl group or a substituted or unsubstituted C2 to C30 heteroaryl group is bonded to at least one silicon atom, (Meth) acryloyl chloride by reacting a compound (for example, an allyl alcohol) which reacts with (meth) acryloyl chloride. Or (B) a silicone-based di (meth) acrylate is 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 bonded to at least one silicon atom and (meth) &Lt; / RTI &gt; but not limited thereto.

(B) silicon-based di (meth) acrylate is contained in an amount of 20 to 70% by weight, specifically 25 to 90% by weight, based on the total weight of the silicone-based particles, (A), (B), (C) 45% by weight. Within this range, the transmittance of the organic film can be increased and the plasma etching rate can be lowered.

(C) mono (meth) acrylate

(C) mono (meth) acrylate is contained in the composition for encapsulating an organic light emitting element, and the light curing rate of the sealing composition can be increased. In addition, (C) mono (meth) acrylate can increase the light transmittance of the organic film and lower the plasma etching rate. (C) Mono (meth) acrylates may include non-silicone mono (meth) acrylates that do not include silicon. (C) The mono (meth) acrylate may include at least one of an aromatic mono (meth) acrylate having an aromatic group and a non-aromatic mono (meth) acrylate having no aromatic group.

In one embodiment, (C) mono (meth) acrylate may comprise a mono (meth) acrylate having an aromatic group. The mono (meth) acrylate having an aromatic group and the above-mentioned (B) silicone di (meth) acrylate have an aromatic group, and when they are used together, they are particularly excellent in compatibility in a composition for encapsulating an organic light emitting device. Accordingly, (C) the mono (meth) acrylate can further improve the miscibility with the (B) silicone-based di (meth) acrylate. In such a case, the sealing composition may be more effective in remarkably lowering the plasma etching rate of the organic film.

The aromatic mono (meth) acrylate may include a mono (meth) acrylate having a substituted or unsubstituted aromatic group. The term 'aromatic group' means a polycyclic aromatic group including a monocyclic or fused form, or a form in which a single ring is connected by a sigma bond. For example, the aromatic group may be a substituted or unsubstituted C6 to C50 aryl group, a substituted or unsubstituted C7 to C50 arylalkyl group, a substituted or unsubstituted C3 to C50 heteroaryl group, a substituted or unsubstituted C3 to C50 heteroaryl group, C50 &lt; / RTI &gt; heteroaryl &lt; RTI ID = 0.0 &gt; alkyl &lt; / RTI &gt; More specifically, the aromatic group is selected from the group consisting of phenyl, biphenyl, terphenyl, quaterphenyl, naphthyl, anthracenyl, phenanthrenyl, chrysenyl, triphenylenyl, tetracenyl, pyrenyl, benzopyranyl, pentacenyl, , Ovalenyl, coranprenyl, benzyl, pyridinyl, pyrazinyl, pyrimidinyl, pyridazinyl, triazinyl, quinolinyl, isoquinolinyl, quinoxalinyl, acridinyl, quinazolinyl, Thiazolyl, benzothiazolyl, oxazolyl, benzoxazolyl, pyrazolyl, indazolyl, imidazolyl, benzimidazolyl, furidinyl, thiophenyl, Benzothiophenyl, furanyl, benzofuranyl, isobenzofuranyl. &Lt; / RTI &gt;

For example, the aromatic mono (meth) acrylate can be represented by the following formula:

(3)

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

For example, R ₆ may be a phenylphenoxy group, a phenoxyethyl group, a benzyl group, a phenyl group, a phenylphenoxy group, a phenoxy group, a phenylethyl group, a phenylpropyl group, a phenylbutyl group, a methylphenylethyl group, a propylphenylethyl group, , A cyclohexylphenylethyl group, a chlorophenylethyl group, a bromophenylethyl group, a methylphenyl group, a methylethylphenyl group, a methoxyphenyl group, a propylphenyl group, a cyclohexylphenyl group, a chlorophenyl group, a bromophenyl group, a phenylphenyl group, a biphenyl group, a terphenyl ), A quaterphenyl group, an anthracenyl group, a naphthalene group, a triphenylenyl group, a methylphenoxy group, an ethylphenoxy group, a methylethylphenoxy group, a methoxyphenyloxy group, a propylphenoxy group, a cyclohexyl A phenoxy group, a chlorophenoxy group, a bromophenoxy group, a biphenyloxy group, a terphenyloxy group, a quaterphenyloxy group, an anthracenyloxy group, a naphthalenyloxy group (na phthalenyloxy group, and triphenylenyloxy group.

Specific examples of the aromatic mono (meth) acrylate include 2-phenylphenoxyethyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenyl (meth) acrylate, phenoxy (meth) (Meth) acrylate, benzyl (meth) acrylate, 2-phenylethyl (meth) acrylate, 3-phenylpropyl (meth) (Meth) acrylate, 2- (4-methylphenyl) ethyl (meth) acrylate, 2- (Meth) acrylate, 2- (4-cyclohexylphenyl) ethyl (meth) acrylate, 2- (Meth) acrylate, 2- (4-chlorophenyl) ethyl (meth) acrylate, 2- Acrylate, 2- (3-phenylphenyl) ethyl (meth) acrylate, 4- (biphenyl-2- yloxy) butyl (meth) (Meth) acrylate, 1- (biphenyl-2-yloxy) butyl (meth) acrylate, 2- (Meth) acrylate, 2- (biphenyl-2-yloxy) propyl (meth) acrylate, 3- (Meth) acrylate, 3- (biphenyl-2-yloxy) ethyl (meth) acrylate, (Meth) acrylate, 2- (biphenyl-2-yloxy) ethyl (meth) acrylate, 1- (Meth) acrylate, 1- (4-benzylphenyl) ethyl (meth) acrylate, or a structural isomer thereof But is not limited thereto. In other words, the (meth) acrylate mentioned in the present invention is not limited to only one example, and the present invention includes all the acrylates having the structural isomerism. For example, although only 2-phenylethyl (meth) acrylate is mentioned as an example of the present invention, the present invention includes all of 3-phenylethyl (meth) acrylate and 4-phenyl (meth) acrylate.

Specifically, in the general formula (3), s is an integer of 1 to 5, R ₆ is a substituted or unsubstituted phenylphenoxy group, a substituted or unsubstituted phenylphenylthiol group, a substituted or unsubstituted biphenylphenoxy group, A substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted heteroaryl group, or an unsubstituted terphenylphenoxy group, and the substituted or unsubstituted substituent may be deuterium, a C1 to C10 alkyl group, a C1 to C10 alkoxy group, .

The non-aromatic mono (meth) acrylate may be a mono (meth) acrylate having a substituted or unsubstituted C1 to C20 alkyl group. Specifically, the non-aromatic mono (meth) acrylate is a mono (meth) acrylate having an unsubstituted straight-chain C1 to C20 alkyl group, more specifically an unsubstituted straight-chain C10 to C20 alkyl group (Meth) acrylate. For example, the non-aromatic mono (meth) acrylate is selected from the group consisting of decyl (meth) acrylate, undecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, (Meth) acrylate, nonadecyl (meth) acrylate, heptadecyl (meth) acrylate, octadecyl (meth) acrylate, Rate, but is not limited thereto.

(C) Mono (meth) acrylate is used in an amount of 5 to 40% by weight, specifically 5 to 30% by weight, based on the total weight of the silicone particles, (A), (B), (C) By weight, more specifically from 10% by weight to 25% by weight. Within the above range, the photo-curing rate of the sealing composition can be increased.

(D) initiator

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

(D) The initiator may include, but is not limited to, one or more of a triazine-based initiator, an acetophenone-based initiator, a benzophenone-based initiator, a thioxanone-based initiator, a benzoin-based initiator, a phosphorus-based initiator, and a oxime-based initiator. Examples of the phosphorus initiator include diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide, benzyl (diphenyl) phosphine oxide, bis (2,6-dimethoxybenzoyl) 4-trimethylpentyl) phosphine oxide or mixtures thereof. For example, when using a phosphorus initiator, the composition of the present invention may exhibit better initiation performance at long wavelength UVs. These may be included singly or in combination of two or more.

(D) The initiator may be included in an amount of 1 wt% to 10 wt%, specifically 2 wt% to 5 wt%, based on the total weight of the silicone particles, (A), (B), (C) have. Within this range, photopolymerization can sufficiently take place upon exposure of the encapsulating composition.

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

A composition for a matrix of an organic film according to another embodiment of the present invention may include at least one curable compound (E), a (meth) acrylic compound represented by the following formula (4)

&Lt; Formula 4 >

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

,

, *-SO-*, *-SO₂-*,

,

,

또는

(X₁은 O 또는 S, X₂는 H, 탄소수 1 내지 5의 알킬기 또는 탄소수 6 내지 20의 아릴기이고, m은 1 내지 10의 정수이고, n은 1 내지 5의 정수임)이고,(In the 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, and n is an integer of 1 to 5)

Y is a single bond, * -CH ₂ - or a -, A ₁ and _{A 2 - *, * -O- *} , * -S- *, * -NH- *, * -SO- *, * -SO 2 Each of the two hydrogen atoms bonded to each other, wherein * represents a bonding site,

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

또는

(R은 Z₁ 및 Z₂ 각각 독립적으로 탄소수 1 내지 5의 알킬렌기, n은 Z₁ 및 Z₂ 각각 독립적으로 1 내지 10의 정수이고, R'은 수소 또는 메틸기이고, *은 결합부위를 나타낸다)이고, Z₁ 및 Z₂가 모두 수소인 경우는 제외된다).Z ₁ and Z ₂ are each independently hydrogen,

or

(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 ) And Z ₁ and Z ₂ are both hydrogen).

For example, the composition for a matrix of an organic film of the present invention is one or more curable compounds (E): (E) a specific example of a (meth) acrylic compound represented by the following formula (4): (meth) acrylate containing a dibenzothiophene structure, (Meth) acrylate containing a dibenzofuran structure.

The refractive index of the composition for a matrix of the organic film may be 1.55 or more, specifically 1.55 to 1.65. In this case, the difference in refractive index between the silicon-based particles is large, and the luminance can be further increased.

When the Y is a "two hydrogen bonded to each A1 and A _2" is as in the following formula 4b, A ₁ and A ₂ is not connected, it means a case where Y is hydrogen.

Specifically, the (meth) acrylic compound represented by the formula (4) may be any one of the formulas (4a) to (4f).

&Lt; Formula 4a &

<Formula 4b>

<Formula 4c>

<Formula 4d>

<Formula 4e>

(4f)

(Wherein X, Y, Z ₁ and Z ₂ are as defined in the above formula (4), and Q ₁ and Q ₂ are each independently -S-, -NH- or -O-).

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

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

The (meth) acrylic compounds of the formula (4) may be contained singly or in combination of two or more. In an embodiment, the mixture of the (meth) acrylic compound of Formula 4 may be a mixture of mono (meth) acrylic compound of Formula 4 and di (meth) acrylic compound of Formula 4. By including the mixture, the refractive index and the viscosity can be balanced, and the brightness and moldability of the organic film can be good.

In an embodiment of the present invention, a composition for a matrix of an organic film comprises at least one curable compound selected from the group consisting of a dibenzofuran moiety, a dibenzothiophene moiety, an azadibenzofuran moiety or an azadibenzothiophene moiety (Meth) acrylate.

The mixture of the (meth) acrylic compound of Formula 4 may have a refractive index of 1.58 to 1.70, specifically 1.59 to 1.68, more specifically 1.60 to 1.68. In 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) can be prepared by a conventional method, and can be carried out by the method of chloromethylation, but is not limited thereto. Chloromethylation utilizes a mechanism to introduce chloromethyl groups into aromatic compounds, introducing chloromethyl groups into aromatic compounds with (para) formaldehyde and hydrochloric acid in the aromatic compounds. At this time, the chloromethyl group can be introduced at any position of the aromatic compound such as ortho, meta or para. The above monofunctional or bifunctional compound can be simultaneously prepared by adding sodium acrylate to the chloromethyl-introduced product. The production method by chloromethylation is advantageous in that a mixture of a monofunctional (meth) acrylic compound and a bifunctional (meth) acrylic compound can be produced at the same time.

(E) The compound of formula (4) may be contained in an amount of 75.0 wt% to 98.0 wt%, specifically 90.0 wt% to 98.0 wt% based on the total weight of the silicone-based particles (E) and (D). Also, 92.0 wt% to 97.0 wt% can be included. Within this range, there may be a color improvement effect.

(E) The compound of formula (IV) may be contained in an amount of 90% by weight to 99% by weight, specifically 95% by weight to 98% by weight, based on the total weight of (E) and (D) Also, 92.0 wt% to 98.0 wt% can be included. Within this range, there may be a color improvement effect.

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

(D) The initiator may be included in an amount of 1 wt% to 10 wt%, specifically 2 wt% to 5 wt%, based on the total weight of the silicone-based particles (E) and (D). Within this range, photopolymerization can sufficiently take place upon exposure of the encapsulating composition.

(D) The initiator may be included in an amount of 1 wt% to 10 wt%, specifically 2 wt% to 5 wt% based on the total weight of (E) and (D). Within this range, photopolymerization can sufficiently take place upon exposure of the encapsulating composition.

The composition for encapsulating an organic luminescent element of the present invention may further comprise a heat stabilizer. As a result, it is possible to suppress the viscosity change of the sealing composition at room temperature. The heat stabilizer is included in the sealing composition to inhibit the viscosity change of the sealing composition at room temperature. The heat stabilizer can be used without limitation, but a sterically hindered phenolic heat stabilizer can be used . Specifically, the heat stabilizer is pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], stearyl-3- (3,5- (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- (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, , But is not limited thereto. The thermal stabilizer is present in the total weight of (A), (B), (C) and (D) or up to 2000 ppm, specifically from 0.01 ppm to 2000 ppm, more specifically from 100 ppm to 800 ppm. In the above range, the heat stabilizer can improve the storage stability and fairness of the liquid state of the sealing composition.

The composition for encapsulating an organic luminescent element of the present invention may be of a solventless type which does not contain a solvent.

The composition for encapsulating an organic light emitting diode of the present invention may have a viscosity of 0 cps to 200 cps, specifically 100 cps or less, more specifically 5 cps to 50 cps, 5 cps to 40 cps or 5 cps to 30 cps at 25 占 폚 (23 占 폚 to 27 占 폚) have. In the above range, the composition for encapsulating an organic luminescent element can facilitate the formation of an organic film. In addition, within the above range, it may be advantageous to carry out a method such as vapor deposition, ink jet, or the like in forming an organic film.

An organic light-emitting element encapsulation compositions of the present invention can be cured by photocuring a composition, irradiation in the UV wavelength 10mJ / cm ² to at 1000mJ / cm ² for 1 second to 100 seconds, but is not limited thereto. Curing can be repeated one or more times. UV is not particularly limited, but can be inspected by a UV LED lamp.

The composition for encapsulating an organic luminescent element of the present invention can be used for encapsulating an organic luminescent element. Specifically, an organic film can be formed from a multilayer encapsulating film in which an inorganic film and an organic film are sequentially formed. For example, the composition for encapsulating an organic light emitting device can form an organic film by a method such as evaporation, ink jet, gravure coating, die coating, lip coating, spin coating, spin coating, etc., but is not limited thereto.

Hereinafter, an OLED display of the present invention will be described.

The organic light emitting diode display of the present invention may include an organic layer formed of the composition for encapsulating an organic light emitting diode of the present invention. Specifically, the organic light emitting diode display device includes 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, and the organic film is a composition for encapsulating an organic luminescence element As shown in FIG. As a result, the organic light emitting element display device can suppress the color change at the side and can have a high luminance. In particular, it is possible to suppress the blue shift from white to blue on the side surface and increase the luminance.

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

Since the inorganic film is different from the organic film in composition, the effect of the organic film can be compensated. The inorganic film may be formed of an inorganic material excellent in light transmittance and excellent in water and / or oxygen barrier properties. For example, the inorganic film may be formed of a metal, a nonmetal, an intermetallic compound or alloy, an 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, Oxygen nitride, boron of metal or non-metal, oxygen boride of metal or non-metal, silicide of metal or non-metal, or a mixture thereof. The metal or base metal may be selected from the group consisting of Si, Al, Selenium, Zn, Sb, In, Ge, Sn, Bi, Metal, lanthanide metal, and the like, but are not limited thereto. Specifically, an inorganic film of silicon oxide (SiOx), AlOx comprises silicon nitride (SiNx), silicon oxygen nitride (SiOxNy), ZnSe, ZnO, Sb 2 O 3, Al 2 O 3 , etc., In ₂ O _3, SnO ₂ . 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 of the inorganic films is not particularly limited, but may be 100 Å to 2000 Å. In the above range, there may be a sealing effect that is excellent in light transmittance and excellent in water or oxygen barrier property. The inorganic film may further include at least one of the silicon-based particles, alumina oxide, titanium oxide, and zirconium oxide to enhance the light scattering effect.

The refractive index of one organic film may be 1.45 or more, specifically 1.47 to 1.65. Within this range, there may be a front brightness increasing effect. The thickness of one of the organic films may be 5 탆 to 35 탆. Within this range, there may be a color improvement effect.

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

Referring to FIG. 1, the OLED display 100 includes a substrate 18; A driving transistor unit 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 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; A cover film 27 formed on the second pixel electrode 26; And a thin film encapsulation layer 20 formed on the encapsulation film 27. The thin encapsulation layer includes an inorganic film 201 and an organic film 202 which are alternately stacked and an organic film 202, May be formed from the composition for encapsulating an organic luminescent element 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 identical to each other can also be included in the scope of the present invention.

Hereinafter, an OLED display according to another embodiment of the present invention will be described with reference to FIG. 2 is a cross-sectional view of an OLED display device according to another embodiment of the present invention.

Referring to FIG. 2, the OLED display 100 'includes a substrate 18; A driving transistor unit 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 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; A cover film 27 formed on the second pixel electrode 26; And a thin film encapsulation layer 20 'formed on the encapsulation film 27. The thin encapsulation layer 20' includes inorganic films 201 and 203 alternately stacked and organic films 202 and 204 And the organic films 202 and 204 may be formed of the composition for encapsulating an organic light emitting diode of the present invention. Is substantially the same as the organic light emitting display according to an embodiment of the present invention, except that an organic film 204 is further formed.

2 shows a case where both the organic film 202 and the organic film 204 are formed of the composition for encapsulating an organic light emitting device of the present invention. However, any one of the organic film 202 and the organic film 204 may be used as a conventional composition for encapsulating an organic light emitting element, for example, a film containing no silicon-based particles or containing zirconium oxide, titanium oxide, Alumina, or silicon-based particles outside the average particle diameter.

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.

Production Example 1: Preparation of silicone-based di (meth) acrylate

To a 1000 ml flask equipped with a cooling tube and a stirrer was added 300 ml of ethyl acetate and 25 g of 3-phenyl-1,1,3,5,5-pentamethyltrisiloxane (Gelest) and 43 g of allyl alcohol Gold) was purged with nitrogen for 30 minutes. Thereafter, 72 ppm of Pt on carbon black powder (Aldrich) was added to the mixture, the temperature in the flask was raised to 80 캜, and the mixture was stirred for 4 hours. The residual solvent was removed by distillation to obtain the 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 added slowly while stirring at 0 占 폚. The residual solvent was removed by distillation to obtain a monomer (molecular weight: 522.85 g / mol) of the following formula 1-1 as an HPLC purity of 97%. D, 2H,? 5.82, t, 1H;? 5.59, d, 2H, 2H,? 3.87, m, 4H;? 1.54, m, 4H;? 0.58, m, 4H;

&Lt; Formula 1-1 >

Preparation Example 2: Preparation of acrylate having a dibenzothiophene structure

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

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

<Formula 4-1a>

<Formula 4-1b>

(2) Preparation of a compound represented by the formula (4-2a) or (4-2b) (dibenzothiophene acrylate)

10 g of 2,6-ditertbutyl-4-methylphenol, 10 g of sodium acrylate, 10 g of a compound of the formula 4-1a and 4-2b, ) And 20 mg of tetrabutylammonium bromide were placed in a round-bottomed flask, and 80 g of toluene was added thereto. The mixture was heated to 105 ° C and stirred for 12 hours. After the reaction was completed, the temperature of the reaction was lowered 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 then dried. The dried compound was found to be a colorless liquid (11.2 g), containing the following formulas (4-2a) and (4-2b), and maintaining 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)

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

(C) Mono (meth) acrylate: M1142 (Miewon Specialty)

(D) Initiator: Darocur TPO (BASF)

(E) Mixture of (meth) acrylic compound of formula (4): mixture of preparation example 2

Example 1

44.6 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 a matrix composition for an organic film. 5 parts by weight of polymethylsilsesquioxane particles (SL-100M, Samsung SDI, average particle diameter: 1 mu m) were mixed into the matrix composition for an organic film. To the obtained mixture was added a predetermined amount of zirconia beads (particle diameter: 0.5 mm) and stirred so as to be uniform, and the zirconia beads were removed to prepare a composition for encapsulating an organic luminescent element.

Example 2

(E) 96 parts by weight and (D) 3 parts by weight were mixed to prepare 99 parts by weight of a matrix composition for an organic film. One part by weight of polymethylsilsesquioxane particles (SL-030M, Samsung SDI, average particle diameter: 1 mu m) was mixed with the matrix composition for an organic film thus prepared. To the obtained mixture was added a predetermined amount of zirconia beads (particle diameter: 0.5 mm) and stirred so as to be uniform, and the zirconia beads were removed to prepare a composition for encapsulating an organic luminescent element.

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 a matrix composition for an organic film. 3 parts by weight of polymethylsilsesquioxane particles (SL-030M, Samsung SDI, average particle size: 1 mu m) were mixed into the matrix composition for an organic film. To the obtained mixture was added a predetermined amount of zirconia beads (particle size: 0.5 mm) and stirred so as to be uniform, and the zirconia beads were removed to prepare a composition for encapsulating an organic luminescent element.

Examples 4 and 5

A composition for sealing an organic luminescent element was prepared in the same manner as in Example 3, except that the average particle diameter of the polymethylsilsesquioxane particles was changed as shown in Table 1 below. SL-300M (Samsung SDI) was used as polymethylsilsesquioxane particles having an average particle size of 3 μm and SL-500M (Samsung SDI) was used as polymethylsilsesquioxane particles having an average particle diameter of 5 μm.

Comparative Example 1

(A), 29.7 parts by weight of (B), 19.8 parts by weight of (C), and 3.0 parts by weight of (D) were mixed to prepare 99.0 parts by weight of a matrix composition for an organic film. One part by weight of aluminum oxide particles (SG-AL01P5S, manufactured by Kusumyu AT Co., average particle size: 0.3 mu m) was mixed with the matrix composition for an organic film. To the obtained mixture, a predetermined amount of zirconia beads (0.5 mm in particle diameter) was added and stirred so as to become uniform, and zirconia beads were removed to prepare a composition for encapsulating an organic luminescent element.

Comparative Examples 2 to 6

Except that (A), (B), (C), (D) and / or the content of aluminum oxide particles and / or the average particle diameter of aluminum oxide particles in Comparative Example 1 were changed as shown in Table 2, To prepare a composition for encapsulating an organic luminescent element.

Comparative Example 7

(A), 29.9 parts by weight of (B), 19.9 parts by weight of (C) and 3.0 parts by weight of (D) were mixed to prepare 99.7 parts by weight of a matrix composition for an organic film. To the resulting matrix composition was added titanium oxide particles (SG-AL01P5S, manufactured by Kyoei Kogyo Co., average particle size: 0.3 탆, 0.3 part by weight), and a predetermined amount of zirconia beads (particle diameter 1 mm) was added to the resulting mixture. And zirconia beads were removed to prepare a composition for encapsulating an organic light emitting device.

Comparative Examples 8 to 12

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

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 to prepare a matrix composition for an organic film.

Example One 2 3 4 5 (A) (parts by weight) 44.6 - - - - (B) (parts by weight) 28.5 - - - - (C) (parts by weight) 19.0 - - - - (D) (parts by weight) 2.9 3 2.9 2.9 2.9 (E) (parts by weight) - 96 94.1 94.1 94.1 (Parts by weight) of (A), (B), (C) and (D) 95.0 - - - - (Parts by weight) of (D) and (E) - 99 97 97 97 The content (parts by weight) 5 One 3 3 3 (A), (B), (C), and (D) 1.498 - - - - (D), (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 The average particle diameter (mu m) of the silicon- One One One 3 5

Comparative Example One 2 3 4 5 6 (A) (parts by weight) 46.5 45.6 44.6 46.5 45.6 44.6 (B) (parts by weight) 29.7 29.1 28.5 29.7 29.1 28.5 (C) (parts by weight) 19.8 19.4 19.0 19.8 19.4 19.0 (D) (parts by weight) 3.0 2.9 2.90 3.0 2.9 2.9 (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 (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 diameter (탆) of aluminum oxide particles 0.3 0.3 0.3 2.6 2.6 2.6

Comparative Example 7 8 9 10 11 12 13 (A) (parts by weight) 46.9 46.8 46.5 46.9 46.8 46.9 47 (B) (parts by weight) 29.9 29.9 29.7 29.9 29.9 29.7 30 (C) (parts by weight) 19.9 19.9 19.8 19.9 19.9 19.8 20 (D) (parts by weight) 3.0 2.9 3.0 3.0 2.9 3.0 3.0 (Parts by weight) of (A), (B), (C) and (D) 99.7 99.5 99.0 99.7 99.5 99.0 100 Content (parts by weight) of titanium oxide particles 0.3 0.5 One 0.3 0.5 One - (A), (B), (C), and (D) 1.498 1.498 1.498 1.498 1.498 1.498 1.498 The refractive index of titanium oxide particles 2.488 2.488 2.488 2.488 2.488 2.488 - Average particle diameter (占 퐉) of titanium oxide particles 0.3 0.3 0.3 2.6 2.6 2.6 -

The properties of the compositions shown in Tables 4 and 5 were evaluated for the compositions for encapsulating organic luminescent elements in 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 luminance (%) 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 luminance (%) 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

It is possible to visually confirm the WAD improvement effect when the color change rate reduction rate is 30% or more in the composition for encapsulating an organic light emitting element, and the higher the relative luminance is, the better the value is, do.

In this regard, as shown in Table 4, the composition for encapsulating an organic light emitting diode of the present invention has a light transmittance of 85% or more, a color change rate reduction rate of 30% or more, The organic film having a 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 the titanium oxide particles had a high rate of decreasing the rate of change of color, but a low rate of decrease in the rate of change of color with low relative luminance and high relative luminance.

&Lt; Property evaluation method &

(1) Color shift: A composition for encapsulating an organic light emitting element in Examples and Comparative Examples was coated on a plastic film and cured twice at a wavelength of 390 nm and 180 mJ / cm ² using a Belt type LED lamp to obtain a thickness of 30 Mu m. An organic film was attached to the panel where the organic light emitting device was formed. The luminance and the color coordinate (u'v ') are measured in units of 1 ° from 0 ° to 60 ° using EZcontrast (Eldim) with the front face of the panel at 0 ° and the front face at 90 °. Value. The difference between the value at 0 ° and the value at intervals of 1 ° from 0 ° to 60 ° was calculated as the color change rate (? U'v '). The intermediate color change rate from 0 ° to 60 ° was high.

(2) Reduction rate of color change rate: The color change rate was obtained by the method (1). The color change ratio in Comparative Example 13 was A, and the color change ratio in Example or Comparative Example was B. The color change rate reduction rate is expressed as | (A-B) / A | x &lt; / RTI &gt; The higher the reduction rate of the color change rate, the more the color change in the frontal confrontation side is suppressed. The color change rate reduction effect can be seen when the color change rate reduction rate is 30% or more.

(3) Relative luminance: An organic film was prepared by the method of (1). An organic film was attached to the panel where the organic light emitting device was formed. The front face of the panel was set at 0 °, and a luminance value was obtained at 0 ° using EZcontrast (Eldim). The luminance value of Comparative Example 13 is denoted by C, and the luminance value obtained from the Example or Comparative Example is denoted by D. The relative luminance is expressed as | (C-D) / C | x &lt; / RTI &gt; The higher the relative luminance, the higher the luminance at the front. When the relative luminance is 80% or more, the luminance is high.

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

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

Claims (15)

A silicon-based particle having an average particle diameter of 0.70 mu m to 10.0 mu m, at least one curable compound and an initiator. The composition for encapsulating an organic luminescent element according to claim 1, wherein the difference between the refractive index of the at least one curable compound and the initiator as a whole and the refractive index difference of the silicone-based particles is 0.07 or more. The composition according to claim 1, wherein the silicon-based particles comprise polysilsesquioxane organic particles. 4. The composition for encapsulating an organic luminescent element according to claim 3, wherein the silicone-based particles comprise polymethylsilsesquioxane particles. The composition for encapsulating an organic light emitting element according to claim 1, wherein the silicon-based particles are contained in an amount of 0.1 to 20% by weight based on the total amount of the at least one curable compound, the silicon-based particles and the initiator. 6. The composition for encapsulating an organic luminescent element according to claim 5, wherein the silicon-based particles are contained in an amount of 1 to 5% by weight based on the total amount of the at least one curable compound, the silicon-based particles and the initiator. The composition for encapsulating an organic luminescent element according to claim 1, wherein the refractive index of the at least one curable compound and the initiator is 1.45 or more. 8. The composition for encapsulating an organic luminescent element according to claim 7, wherein the refractive index of the at least one curable compound and the initiator is 1.55 or more. The organic electroluminescent device of claim 1, wherein the at least one curable compound is a (meth) acrylate containing dibenzothiophene, dibenzofuran, azadibenzofurane, or azadibenzothiophene moieties Composition. The composition of claim 1, wherein the at least one curable compound comprises a mixture of (A) non-silicon di (meth) acrylate, (B) silicone di (meth) acrylate, and (C) mono (meth) ,
The non-silicone di (meth) acrylate (A) is contained in an amount of 10% by weight to 70% by weight, based on the total weight of the silicon-based particles, (A), (B), (C) ,
The silicone-based di (meth) acrylate (B) is contained in an amount of 20% by weight to 70% by weight based on the total weight of the silicon-based particles, (A), (B), (C)
Wherein the (C) mono (meth) acrylate is contained in an amount of 5% by weight to 40% by weight based on the total weight of the silicone particles, (A), (B), (C) (EN) Composition for encapsulating an organic luminescent element. 11. The composition for encapsulating an organic light emitting device according to claim 10, wherein the (B) silicone-based di (meth) acrylate is represented by the following formula (1)
&Lt; Formula 1 >

(Wherein R ₁ and 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 hydrogen or a substituted or unsubstituted C1 to C30 alkyl group, R''is a substituted or unsubstituted C1 to C20 alkylene group), - (R' Substituted or unsubstituted C6 to C30 arylene groups, substituted or unsubstituted C7 to C30 arylalkylene groups, or * - (R ') - O - ** wherein * , ** is a connecting site for Si in formula (1), and R 'is a substituted or unsubstituted C1 to C30 alkylene group)
X ₁ , X ₂ , X ₃ , X ₄ , X ₅ and X ₆ each independently represent a hydrogen atom, a hydroxyl group, a halogen atom, a cyano group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C1 to C30 A substituted or unsubstituted C 3 to C 30 cycloalkyl group, a substituted or unsubstituted C 1 to C 30 alkyl ether group, * -N (R ') (R ") (* And R "are each independently hydrogen or a substituted or unsubstituted C1 to C30 alkyl group), a substituted or unsubstituted C1 to C30 alkyl sulfide group, a substituted or unsubstituted C6 to C30 aryl group, a 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 and 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 Or an average value of n is 0 to 30). The composition for encapsulating an organic luminescent element according to claim 1, wherein the organic film formed from the composition for encapsulating an organic luminescent element has a refractive index of 1.45 or more. A thin film encapsulation layer formed on the organic light emitting element and including at least one inorganic film and at least one organic film,
Wherein the organic film is formed of the composition for encapsulating an organic light emitting device according to any one of claims 1 to 12. 14. The organic electroluminescent display device according to claim 13, wherein the organic film has silicon-based particles having an average particle diameter of 1 to 5 占 퐉 dispersed. 14. The OLED display as claimed in claim 13, wherein the organic layer has a refractive index of 1.47 to 1.65.

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