WO2023048351A1 - Composition for encapsulating organic light-emitting device and organic light-emitting device display apparatus comprising organic layer prepared therefrom - Google Patents

Abstract

Provided are a composition for encapsulating an organic light-emitting device, and an organic light-emitting device display apparatus comprising an organic layer prepared therefrom. The composition comprises: an allyl-based or metaallyl-based compound having a nitrogen-containing cyclic structure; a nitrogen-linked, allylic or metaallyl-based compound; and an initiator, wherein the initiator is a phosphorus-based initiator.

Description

Organic light emitting device display device including a composition for encapsulating an organic light emitting device and an organic layer prepared therefrom

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

When external moisture, oxygen, or the like permeates the organic light emitting device, it is easily damaged and loses its function, resulting in low reliability. Therefore, the organic light emitting device must be sealed by an encapsulation layer including an organic layer and an inorganic layer formed of a composition for encapsulating the organic light emitting device.

Meanwhile, in the organic light emitting device display device, various display elements are additionally stacked on upper and lower portions of the organic light emitting device in addition to the encapsulation layer. However, various types of electricity, static electricity, or electromagnetic waves emitted from the display device inevitably affect the organic light emitting device. Due to various types of electricity, static electricity, or electromagnetic waves emitted from these display devices, the organic light emitting device may malfunction or cancel its function.

Therefore, it is necessary to minimize the effect even if additional devices are stacked on the organic light emitting device due to the low dielectric constant while having a basic function of sealing the organic light emitting device. On the other hand, as interest in flexible display devices has rapidly increased recently, a composition capable of forming an organic layer that can be used in a flexible display device with excellent flexibility is required.

The background art of the present invention is described in Korean Patent Publication No. 10-2016-0150255 and the like.

An object of the present invention is to provide a composition for encapsulating an organic light emitting device capable of forming an organic layer having a low permittivity after curing.

Another object of the present invention is to provide a composition for encapsulating an organic light emitting device capable of forming an organic layer having excellent plasma resistance after curing.

Another object of the present invention is to provide a composition for encapsulating an organic light emitting device that forms an organic layer having a uniform surface and has excellent curing rate, hardness, and inkjet jetting property.

Another object of the present invention is to provide a composition for encapsulating an organic light emitting device having excellent flexibility and forming an organic layer applied to a flexible display device.

One aspect of the present invention is a composition for sealing an organic light emitting device.

A composition for encapsulating an organic light emitting device may include an allyl or methallyl compound having a nitrogen-containing cyclic structure; nitrogen-linked, allyl or methallyl compounds; and an initiator, wherein the initiator is a takeover initiator.

The organic light emitting device display device of the present invention includes an organic layer formed of the composition for encapsulating the organic light emitting device of the present invention.

The present invention provides a composition for encapsulating an organic light emitting device capable of forming an organic layer having a low permittivity after curing.

The present invention provides a composition for encapsulating an organic light emitting device capable of forming an organic layer having excellent plasma resistance after curing.

The present invention provides a composition for encapsulating an organic light emitting device that forms an organic layer having a uniform surface and has excellent curing rate, hardness, and inkjet jetting property.

The present invention provides a composition for encapsulating an organic light emitting device having excellent flexibility and forming an organic layer applied to a flexible display device.

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

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

Figure 3 shows the absorbance according to the wavelength of the initiator used in the present invention.

With reference to the accompanying drawings, the present invention will be described in detail by examples so that those skilled in the art can easily practice the present invention. This invention may be embodied in many different forms and is not limited to the embodiments set forth herein.

In order to clearly describe the present invention in the drawings, parts irrelevant to the description are omitted, and the same reference numerals are attached to the same or similar components throughout the specification. The length and size of each component in the drawings are for explaining the present invention, and the present invention is not limited to the length and size of each component described in the drawings.

In this specification, "(meth)acryl" means an acryl and/or a methacryl.

In this specification, unless otherwise defined, "substituted" is a hydrogen atom of one or more functional groups of the present invention, a halogen (F, Cl, Br or I), a hydroxyl group, a nitro group, a cyano group, an imino group (=NH , =NR, R is an alkyl group having 1 to 10 carbon atoms), an amino group (-NH ₂ , -NH(R'), -N(R")(R"'), R',R",R"' each independently an alkyl group having 1-10 carbon atoms), an amidino group, a hydrazine or hydrazone group, a carboxy group, an alkyl group having 1-20 carbon atoms, an aryl group having 6-30 carbon atoms, a cycloalkyl group having 3-30 carbon atoms, and a 3-30 carbon atoms. It may mean that it is substituted with a heteroaryl group of, or a heterocycloalkyl group having 2 to 30 carbon atoms.

When describing a numerical range in this specification, "X to Y" means X or more and Y or less (X≤ and ≤Y).

A composition for encapsulating an organic light emitting diode according to an embodiment of the present invention (hereinafter, also referred to as “composition”) may include an allyl or methallyl compound having a nitrogen-containing cyclic structure; nitrogen-linked, allyl or methallyl compounds; and an initiator, wherein the initiator is a takeover initiator. The organic layer formed by photocuring the composition of the present invention has a low plasma etching rate and excellent plasma resistance, thereby extending the lifespan of the organic light emitting device, and having a low permittivity to impart insulating performance to the organic layer, thereby providing an organic light emitting device from the outside of the organic layer. By blocking the movement of electricity, static electricity, or electromagnetic waves to the furnace, performance of the organic light emitting device in the encapsulation layer may not be hindered. In addition, the composition of the present invention has a viscosity suitable for inkjet jetting properties, so that an organic layer having a uniform surface can be formed with excellent inkjet jetting properties. In addition, the composition of the present invention has excellent flexibility and can form an organic layer applied to a flexible display device. In addition, the composition of the present invention can form an organic layer with excellent hardness.

In one embodiment, the composition of the present invention after curing may have a dielectric constant of 3.5 or less, specifically 2.3 to 3.3. Within the above range, the performance of the organic light emitting device may be well implemented without being affected by external static electricity or electricity.

In one embodiment, the composition of the present invention may have a plasma etch rate of 6.5% or less, specifically 0% to 6.5% according to Equation 1 below after curing. Within the above range, when the inorganic layer is formed on the organic layer, the organic layer is not damaged, so that the lifespan of the organic light emitting diode can be extended:

[Equation 1]

Etching rate of organic layer by plasma (%) = (T1-T2)/T1 x 100

(In Equation 1, T1 is the initial thickness of the organic layer obtained by depositing the composition on a silicon (Si) wafer and photocuring it by UV irradiation at 100 mW/cm ² for 10 seconds (unit: μm),

T2 is induced using ICP CVD (inductively coupled plasma chemical vapor deposition) on the organic layer under conditions of ICP power: 2500W, RE power: 300W, DC bias: 200V, Ar flow: 50sccm, ethching time: 1min, pressure: 10mtorr Thickness (unit: μm) of the organic layer after treatment with inductively coupled plasma (ICP).

The thickness (or height) of the organic layer may be measured by FE-SEM (Hitachi High Technologies Corporation), but is not limited thereto.

A composition for encapsulating an organic light emitting diode according to an embodiment of the present invention (hereinafter, referred to as “composition”) may include an allyl or methallyl compound having a nitrogen-containing cyclic structure; nitrogen-linked, allyl or methallyl compounds; and an initiator, wherein the initiator is a takeover initiator. The inventor of the present invention is a phosphorus-based initiator, preferably of a wavelength of 360 nm or more, among several initiators known to photo-cure an allyl-based or metaallyl-based compound having a nitrogen-containing cyclic structure and nitrogen-linked allyl-based or metaallyl-based compounds. It was confirmed that all of the aforementioned effects could be obtained by using a phosphorus-based initiator capable of initiating a photocuring reaction upon irradiation with light. An allyl or metaallylic compound having a nitrogen-containing cyclic structure is different from a nitrogen-linked, allyl or metaallylic compound.

Hereinafter, each component in the composition of one embodiment of the present invention will be described in detail.

(A) an allyl or methallyl compound having a nitrogen-containing cyclic structure;

An allyl-based or metaallyl-based compound having a nitrogen-containing cyclic structure may be included in the composition to help reduce the dielectric constant of the organic layer and improve the plasma etch rate. The present inventors have found that an organic layer formed when an allyl or metaallyl-based compound having a nitrogen-containing cyclic structure is cured by the phosphorus-based initiator together with a nitrogen-linked, allyl or metaallyl-based compound described in detail below has a low dielectric constant and a plasma etch rate It was confirmed that the improvement effect could be implemented.

The allyl- or metaallyl-type compound having a nitrogen-containing cyclic structure is a photocurable compound, and has one or more, preferably one to three allyl or metaallyl groups, and can be cured by an initiator detailed below. Through this, the composition of the present invention may be easy to implement the above effects of the present invention.

The nitrogen-containing cyclic structure may include an alicyclic or aromatic cyclic structure formed of one or more nitrogen and carbon. In one embodiment, the cyclic structure has 3 to 10 carbon atoms forming the cyclic structure, and may include a monocyclic or heterocyclic, alicyclic or aromatic cyclic structure. Preferably, the cyclic structure may have one or more, preferably one to three carbonyl groups (-(C=O)-), so that the effect of the present invention may be more easily implemented.

For example, the nitrogen-containing cyclic structure is an isocyanurate group, a piperidine group, a piperidinone group, a piperidine dione group, a pyrrolidine group, a pyrrolidine dione group, a pyridine group, an indole group, at least partially hydrogenated and at least one of a modified indole group, an indole dione group, an isoindole dione group in which at least a part is hydrogenated, a pyridinedione group, and a pyrroldione group. Preferably, the nitrogen-containing cyclic structure may be an isocyanurate group.

In one embodiment, the compound may include one or more of Formula 1 and Formula 2 below:

[Formula 1]

(In Formula 1 above,

R ¹ , R ² , R ³ are each an allyl group, metaallyl group, hydrogen, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, or a substituted or unsubstituted carbon atom group. An aryl group having 6 to 10, a substituted or unsubstituted arylalkyl group having 7 to 10 carbon atoms, or a glycidyl group,

At least one of R ¹ , R ² , and R ³ is an allyl group or a methallyl group)

[Formula 2]

(In Formula 2 above,

R ⁴ is an allyl group or a metaallyl group;

R ⁵ is a substituted or unsubstituted, nitrogen-containing cyclic functional group;

R ⁶ is an allyl group, metaallyl group, hydrogen, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, A substituted or unsubstituted arylalkyl group or glycidyl group having 7 to 10 carbon atoms, or

R ⁵ and R ⁶ are linked to each other to form a substituted or unsubstituted nitrogen-containing cyclic functional group)

In Formula 2, the nitrogen-containing cyclic functional group formed by connecting R ⁵ or R ⁵ and R ⁶ to each other is a piperidine group, a piperidinone group (although not particularly limited, the following Formula 2-1), a piperidinedione group ( Although not particularly limited, a pyrrolidine group, a pyrrolidinedione group (not particularly limited, but not limited to Formula 2-3), a pyridine group (not particularly limited, but Formula 2-10), indole group, an indole group at least partially hydrogenated, an indole dione group, an isoindole dione group at least partially hydrogenated (but not particularly limited, represented by Formula 2-4 below, Formula 2-5 below, Formula 2-8 below, or Formula 2- 9), a pyridinedione group (but not particularly limited, the following Chemical Formula 2-6), and a pyrroldion group (but not particularly limited, the following Chemical Formula 2-7).

[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

[Formula 2-4]

[Formula 2-5]

[Formula 2-6]

[Formula 2-7]

[Formula 2-8]

[Formula 2-9]

[Formula 2-10]

(In Chemical Formulas 2-1 to 2-10, * is a linking site with R ⁴ in Chemical Formula 2)

Preferably, the allyl or methallyl compound having a nitrogen-containing cyclic structure may include one or more of the following Formulas 3-1 to 3-11:

[Formula 3-1]

[Formula 3-2]

[Formula 3-3]

[Formula 3-4]

[Formula 3-5]

[Formula 3-6]

[Formula 3-7]

[Formula 3-8]

[Formula 3-9]

[Formula 3-10]

[Formula 3-11]

The allyl or metaallyl-based compound having a nitrogen-containing cyclic structure is 20 parts by weight to 90 parts by weight, 20, 21, 22, 23, 24, 25 , 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50 , 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75 , 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90 parts by weight, for example, may be included in 20 parts by weight to 80 parts by weight. Within the above range, the dielectric constant of the organic layer formed of the composition is lowered and it may help to improve the plasma etch rate.

(B) a nitrogen-linked, allyl or methallyl compound

Nitrogen-linked, allyl-based or methallyl-based compounds can be included in the composition to increase the curing rate of the composition, thereby increasing the pencil hardness of the organic layer. A nitrogen-linked, allyl or methallyl compound may also improve inkjet jetting properties by adjusting the viscosity of the composition by being included in the composition.

Nitrogen-linked, allyl or methallyl compounds may include compounds having one or more allyl or methallyl groups linked to nitrogen. Preferably, the nitrogen-linked, allyl-based or metaallyl-based compound can increase the curing rate of the composition by having 2 to 3 allyl groups or metaallyl groups.

Nitrogen-linked, allyl- or methallyl-based compounds may include compounds of Formula 4:

[Formula 4]

(In Chemical Formula 4,

R ⁷ , R ⁸ , R ⁹ are each independently hydrogen, an allyl group, a metaallyl group, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, substituted or unsubstituted an arylalkyl group having 7 to 10 carbon atoms, or a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms,

At least one of R ⁷ , R ⁸ , and R ⁹ is an allyl group or a metaallyl group;

R ¹⁰ is hydrogen, an allyl group, a metaallyl group, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a substituted or unsubstituted arylalkyl group having 7 to 10 carbon atoms, or a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms;

n is an integer from 0 to 2).

Preferably, the nitrogen-linked, allyl or methallyl compounds may include one or more of Formulas 4-1 to 4-4:

[Formula 4-1]

[Formula 4-2]

[Formula 4-3]

[Formula 4-4]

.

Nitrogen-linked, allyl-based or methallyl-based compounds are 10 parts by weight to 80 parts by weight, specifically 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90 parts by weight, for example, may be included in 20 parts by weight to 80 parts by weight. Within this range, it is possible to increase the curing rate of the composition to increase the pencil hardness of the formed organic layer, and help to improve the plasma etching rate and permittivity.

The total of (A) an allyl or methallyl compound having a nitrogen-containing cyclic structure and (B) a nitrogen-linked allyl or metaallyl compound is 95 parts by weight or more out of 100 parts by weight of the photocurable component in the composition, for example For example, it may be included in 98 parts by weight to 100 parts by weight, for example, 100 parts by weight.

initiator

The initiator is a phosphorus initiator as a photo-radical initiator. When the phosphorus-based initiator is used, the composition of the present invention can show photocuring reaction initiation performance when irradiated with long-wavelength UV light (eg, wavelength 360 nm or more, for example, 360 nm to 410 nm), and all the effects of the present invention described above can be obtained. there is.

The initiator may have a photoreaction initiation wavelength at 200 nm to 410 nm, preferably at 300 nm to 400 nm, and more preferably at 360 nm to 400 nm. Within the above range, when combined with the two types of allyl or methallyl compounds of the present invention, the curing rate may be increased and the effect of the present invention may be easily realized. The "light onset wavelength" and "maximum absorption wavelength" may be measured by conventional methods known to those skilled in the art or values obtained by referring to product catalogs.

The initiator is a phosphorus initiator and may have one or more absorption peaks at a wavelength of 350 nm to 410 nm. The takeover initiator may facilitate implementation of the effects of the present invention. The "absorption peak" refers to a peak in which the absorbance increases and then decreases when the initiator is dissolved in the solvent acetonitrile at a concentration of 0.1% and then the absorbance is measured according to the wavelength, and the absorbance continues to increase or the absorbance continues to decrease. peaks that increase or decrease and then rise are not meant.

Figure 3 shows the absorbance according to the wavelength of the phosphorus initiator used in the present invention. As shown in FIG. 3 , the phosphorus initiator used in the present invention may have one or more absorption peaks at a wavelength of 350 nm to 410 nm.

Phosphorus-based initiators include ethyl (2,4,6-trimethylbenzoyl) phenyl phosphinate (TPOL), diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide (TPO), phenyl bis (2,4, 6-trimethylbenzoyl)phosphine oxide (BAPO), 2,4,6-trimethylbenzoyl diphenyl phosphinate, (2,4,6-trimethylbenzoyl) ethoxy phenyl phosphinate, (2,4,6 -trimethylbenzoyl) methoxy phenyl phosphinate, bisacyl phosphine oxide, methyl (2,4,6-trimethylbenzoyl) phenyl phosphinate, or mixtures thereof. For example, the initiator may be included alone or in combination of two or more.

The initiator may be included in an amount of 0.01 part by weight to 10 parts by weight, preferably 1 part by weight to 5 parts by weight, based on 100 parts by weight of the total sum of components (A) and (B). Within this range, the effects of the present invention can be easily implemented.

The composition of the present invention may be formed by mixing the component (A), the component (B) and an initiator. For example, the composition of the present invention can be formed in a solvent-free type that does not contain a solvent.

The composition of the present invention is a photocurable composition, and may form an encapsulation layer by being photocured by UV irradiation at 10mW/cm ² to 500mW/cm ² at a wavelength of 360 nm or more among UV wavelengths for 1 second to 50 seconds.

The composition of the present invention may further contain conventional additives known to those skilled in the art. The additives may include, but are not limited to, heat stabilizers, antioxidants, UV absorbers, and the like.

The composition of the present invention may have a viscosity of 7cps to 100cps, preferably 7cps to 60cps, more preferably 7cps to 50cps at 25±2°C (23°C to 27°C). Within this range, the inkjet jetting property of the composition for encapsulation may be excellent.

The composition of the present invention may have a light curing rate of 85% or more, specifically 85% to 100%. Within the above range, the film strength of the organic layer formed of the composition is excellent, and thus the life of the device may be extended.

In the composition of the present invention, the organic layer obtained after photocuring may have a pencil hardness of 3H or more, for example, 3H to 5H. Within the above range, subsequent processes may be stably performed due to film strength enhancement.

The composition of the present invention can be used to encapsulate an organic light emitting device. Specifically, the composition may form an organic layer in an encapsulation structure in which an inorganic layer and an organic layer are sequentially formed.

The composition of the present invention is a member for a device, particularly a member for a display device, and is decomposed by permeation of gases or liquids in the surrounding environment, such as oxygen and/or moisture and/or water vapor in the air and chemicals used in processing electronic products. It can also be used for encapsulation of device members that may be damaged or defective. For example, the member for the device may be a lighting device, a metal sensor pad, a microdisk laser, an electrochromic device, a photochromic device, a microelectromechanical system, a solar cell, an integrated circuit, a charge-coupled device, a light emitting polymer, etc. Not limited to this.

The organic light emitting device display device of the present invention may include an organic layer formed of the composition for encapsulating the organic light emitting device of one embodiment of the present invention. Specifically, the organic light emitting device display device includes an organic light emitting device and a barrier stack formed on the organic light emitting device and including an inorganic layer and an organic layer, and the organic layer may be formed of the composition for encapsulating the organic light emitting device according to the embodiment of the present invention. . As a result, the reliability of the organic light emitting device display may be improved.

Preferably, the organic light emitting diode display device may be a flexible organic light emitting diode display device.

Hereinafter, an organic light emitting diode display device 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 device according to an exemplary embodiment of the present invention.

Referring to FIG. 1 , an organic light emitting device display device 100 includes a substrate 10, an organic light emitting device 20 formed on the substrate 10, and an inorganic layer 31 and an organic layer formed on the organic light emitting device 20. (32), the inorganic layer 31 is in contact with the organic light emitting device 20, and the organic layer 32 is the composition for encapsulating the organic light emitting device according to the embodiment of the present invention. can be formed as

The substrate 10 is not particularly limited as long as it is a substrate on which an organic light emitting device can be formed. For example, it may be made of a material such as transparent glass, plastic sheet, silicon or metal substrate.

The organic light emitting device 20 is commonly used in an organic light emitting device display device, and although not shown in FIG. 1, includes a first electrode, a second electrode, and an organic light emitting film formed between the first electrode and the second electrode. The light emitting film may be formed by sequentially stacking a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer, but is not limited thereto.

The barrier stack 30 includes an organic layer and an inorganic layer, and the organic layer and the inorganic layer have different components constituting each layer, so that each organic light emitting diode encapsulation function can be realized.

The inorganic layer may supplement the effect of the organic layer by having a different component from the organic layer. For example, the inorganic layer may be a metal, nonmetal, intermetallic compound or alloy, nonmetallic compound or alloy, metal or nonmetal oxide, metal or nonmetal fluoride, metal or nonmetal nitride, metal or nonmetal carbide, metal or nonmetal oxynitride of, metal or nonmetal borides, metal or nonmetal oxyborides, metal or nonmetal silicides, or mixtures thereof. Metals or non-metals are silicon (Si), aluminum (Al), selenium (Se), zinc (Zn), antimony (Sb), indium (In), germanium (Ge), tin (Sn), bismuth (Bi), transition metal, lanthanide metal, and the like, but is not limited thereto. Specifically, the inorganic layer includes silicon oxide (SiOx), silicon nitride (SiNx), silicon oxygen nitride (SiOxNy), ZnSe _, ZnO, Sb ₂ O ₃ , AlOx including Al _{2 O 3 , In 2 O 3} , SnO can be ₂

The inorganic layer may 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.

When the organic layer and the inorganic layer are alternately deposited, smoothing characteristics of the inorganic layer may be secured and defects of the inorganic layer may be prevented from propagating to another inorganic layer.

The organic layer may be formed by a combination of coating, deposition, and curing of the composition for encapsulating an organic light emitting device according to an exemplary embodiment of the present invention. For example, a composition for encapsulating an organic light emitting device may be coated to a thickness of 1 μm to 50 μm, and cured by UV irradiation at 10 mW/cm ² to 500 mW/cm ² for 1 second to 50 seconds.

The barrier stack includes organic and inorganic layers, but the total number of organic and inorganic layers is not limited. The total number of organic and inorganic layers may vary depending on the level of permeation resistance to oxygen and/or moisture and/or water vapor and/or chemicals. For example, the total number of organic layers and inorganic layers may be 10 layers or less, for example, 2 to 7 layers, specifically in the order of inorganic layer/organic layer/inorganic layer/organic layer/inorganic layer/organic layer/inorganic layer. It can be formed in 7 layers.

In the barrier stack, organic and inorganic layers may be deposited alternately. This is due to the effect on the organic layer formed due to the physical properties of the above-described composition. Due to this, the organic layer and the inorganic layer can supplement or enhance the encapsulation effect of the device.

Hereinafter, an organic light emitting diode display device according to another 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 device according to another embodiment of the present invention.

Referring to FIG. 2 , an organic light emitting device display device 200 includes a substrate 10, an organic light emitting device 20 formed on the substrate 10, and an inorganic layer 31 and an organic layer formed on the organic light emitting device 20. The barrier stack 30 including 32 is included, the inorganic layer 31 seals the internal space 40 in which the organic light emitting device 20 is accommodated, and the organic layer 32 is the organic light emitting device of the embodiment of the present invention. It may be formed as a composition for encapsulation. Except for the fact that the inorganic layer does not contact the organic light emitting device, it is substantially the same as the organic light emitting device display device according to the embodiment of the present invention.

Hereinafter, the configuration and operation of the present invention will be described in more detail through preferred embodiments of the present invention. However, this is presented as a preferred example of the present invention and cannot be construed as limiting the present invention by this in any sense.

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

(A) an allyl or methallyl compound having a nitrogen-containing cyclic structure;

(A1) Triallyl Isocyanurate (Aldrich Co.)

(A2) 1,3-diallyl-5-glycidyl isocyanurate (Shikoku Co.)

(A3) Diallyl n-propyl isocyanurate (TCI)

(A4) Trimethallyl isocyanurate (TCI)

(A5) 1-allyl-4-piperidinone (TCI Co.)

(B) a nitrogen-linked, allyl or methallyl compound

(B1) 1,3-Diallylurea (TCI)

(B2) Triallylamine (TCI)

(C) vinyl ether compounds

(C1) Diethylene glycol divinyl ether (Aldrich Co.)

(C2) Triethylene glycol divinyl ether (Aldrich Co.)

(D) initiator

(D1) phosphorus-based initiator (Irgacure TPO-H, (2,4,6-trimethylbenzoyl) diphenyl phosphinate, IGM Co., photoreaction onset wavelength: 225 to 410 nm, maximum absorption wavelength: 360 nm)

(D2) Phosphorus-based initiator (Irgacure TPO-L, (2,4,6-trimethylbenzoyl) ethoxy phenyl phosphinate, photoreaction onset wavelength: 225 to 410 nm, maximum absorption wavelength: 360 nm)

(D3) Phosphorus-based initiator (Irgacure 819, phenyl bis(2,4,6-trimethylbenzoyl) phosphine oxide, IGM Co., photoreaction onset wavelength: 225 to 410 nm, maximum absorption wavelength: 360 nm)

(D4) Photoacid generator (Miphoto NIT, Miwon Corporation, photoreaction initiation wavelength: 360nm)

(D5) Ketone initiator (Irgacure 369, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, IGM, photoreaction initiation wavelength: 260 to 390 nm)

Example 1

(A1) 60 parts by weight, (B1) 30 parts by weight, (B2) 10 parts by weight, (D1) 3 parts by weight were put in a 125 ml brown polypropylene bottle and mixed at room temperature for 3 hours using a shaker for solvent-free sealing A composition was prepared.

Examples 2 to 9 and Comparative Examples 1 to 6

A composition for sealing was prepared in the same manner as in Example 1, except that the content of each component in Example 1 was changed as shown in Table 1 (unit: parts by weight). In Table 1 below, "-" means that the corresponding component is not contained.

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

(1) Viscosity (unit: cps): The encapsulation compositions of Examples and Comparative Examples were measured at 24.8° C. with a spindle number of 40 using a viscosity meter LV DV-II Pro (Brookfield Co.).

(2) Permittivity (no unit): The encapsulation compositions of Examples and Comparative Examples were applied to a predetermined thickness on a chromium (Cr) plate, and UV irradiation was performed at 100 mW/cm ² for 10 seconds to photo-cure to form a coating film having a thickness of 8 μm. formed. After depositing aluminum on the coating film, the dielectric constant was measured at 200 kHz and 25° C. with an impedance measuring instrument (RDMS-200).

(3) Pencil hardness: Coating the composition for encapsulation on a glass substrate and UV curing by light irradiation at 100 mW/cm ² for 10 seconds to obtain an organic layer specimen. Pencil hardness was measured for the organic layer specimen. When measuring pencil hardness, an electric pencil hardness tester (Lab-Q D300A) and pencils of 6B to 9H from Mitsubishi were used. The load of the pencil on the specimen was 500 g, the pencil drawing angle was 45°, and the pencil drawing speed was 48 mm/min. If more than one scratch occurs after 5 evaluations, the pencil hardness is measured using a pencil at the lower level, and this is the maximum pencil hardness value when there is no scratch in all 5 evaluations.

(4) Plasma etching rate (unit: %): The composition for encapsulation was deposited on a Si wafer and photocured by UV irradiation at 100 mW/cm ² for 10 seconds to form an organic layer. After photocuring, the initial thickness (T1, unit: μm) of the organic layer was measured. ICP power: 2500W, RE power: 300W, DC bias: 200V, Ar flow: 50sccm, ethching time: 1min, pressure: 10mtorr, the organic layer was treated with inductively coupled plasma using ICP CVD (BMR Technology Co.), and then the organic layer was The thickness (T2, unit: μm) was measured. The etching rate of the organic layer by the plasma was calculated according to Equation 2 below. The height (thickness) of the organic layer was measured by FE-SEM Hitachi High Technologies Corporation.

[Equation 1]

Etching rate of organic layer by plasma (%) = (T1-T2)/T1 x 100

		Example									comparative example
		One	2	3	4	5	6	7	8	9	One	2	3	4	5	6
A	A1	60	-	-	-	40	-	-	60	-	-	-	-	60	50	50
	A2	-	20	-	-	-	50	-	-	20	-	-	-	-	-	-
	A3	-	-	80	-	-	-	-	-	-	-	-	-	-	-	-
	A4	-	-	-	50	-	-	30	-	-	-	-	-	-	-	-
	A5	-	60	-	30	35	-	-	-	60	-	-	-	-	-	-
B	B1	30	-	10	-	-	30	50	30	-	-	-	-	30	-	-
	B2	10	20	10	20	25	20	20	10	20	-	-	-	10	-	-
C	C1	-	-	-	-	-	-	-	-	-	100	-	100	-	50	-
	C2	-	-	-	-	-	-	-	-	-	-	100	-	-	-	50
D	D1	3	3	3	3	3	3	-	-	-	-	-	3	-	-	-
	D2	-	-	-	-	-	-	3	-	-	-	-	-	-	-	-
	D3	-	-	-	-	-	-	-	3	3	-	-	-	-	-	-
	D4	-	-	-	-	-	-	-	-	-	0.2	0.2	-	-	0.2	0.2
	D5	-	-	-	-	-	-	-	-	-	-	-	-	3	-	-
viscosity		20.8	9.7	52.6	30.8	22.5	18.9	22.6	21.3	10.2	1.7	3.5	2	20.7	12	21
permittivity		2.35	2.73	2.48	2.62	2.62	2.85	3.1	2.34	2.72	4.6	5.5	not hardenable	not hardenable	not hardenable	not hardenable
pencil hardness		3H	4H	4H	3H	5H	4H	4H	3H	4H	2B	1B	--	--	--	--
plasma etch rate		5.8	6.3	5.5	5.9	6.3	6.2	6.5	5.8	6.3	8.9	9.4	--	--	--	--

*In Table 1 above, "--" means that the corresponding physical properties could not be evaluated due to uncurability.

As shown in Table 1, the composition for encapsulating an organic light emitting device of the present invention can form an organic layer having a low dielectric constant, excellent plasma resistance, and excellent hardness after curing. In addition, although the composition of the present invention has an appropriate viscosity and is not shown in Table 1, it is expected to have excellent inkjet jetting properties.

On the other hand, the composition of Comparative Example outside the composition of the present invention could not obtain all the effects of the present invention.

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

Claims (11)

1. an allyl or methallyl compound having a nitrogen-containing cyclic structure; nitrogen-linked, allyl or methallyl compounds; and an initiator, wherein the initiator is a phosphorus-based initiator.
2. According to claim 1, wherein the phosphorus initiator has a photoreaction initiation wavelength of 200 to 410nm, a maximum absorption wavelength of 360nm or more, the composition for encapsulating an organic light emitting device.
3. The method of claim 1, wherein the phosphorus-based initiator is ethyl (2,4,6-trimethylbenzoyl) phenyl phosphinate, diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide, phenyl bis(2,4, 6-trimethylbenzoyl)phosphine oxide, 2,4,6-trimethylbenzoyl diphenyl phosphinate, (2,4,6-trimethylbenzoyl) ethoxy phenyl phosphinate, (2,4,6-trimethylbenzoyl ) Methoxy phenyl phosphinate, bisacyl phosphine oxide, methyl (2,4,6-trimethylbenzoyl) phenyl phosphinate, or a mixture thereof, a composition for encapsulating an organic light emitting device.
4. The method of claim 1, wherein the composition

   20 parts by weight to 90 parts by weight of an allyl or metaallyl compound having the nitrogen-containing cyclic structure,

   10 parts by weight to 80 parts by weight of the nitrogen-linked, allyl or methallyl compound,

   0.01 part by weight to 10 parts by weight of the initiator based on 100 parts by weight of the total of the allyl or metaallyl-based compound having the nitrogen-containing cyclic structure and the nitrogen-linked allyl or metaallyl-based compound, organic light emitting Composition for device encapsulation.
5. The composition for encapsulating an organic light emitting diode according to claim 1, wherein the allyl-based or metaallyl-based compound having a nitrogen-containing cyclic structure includes at least one of Formula 1 and Formula 2 below:

   [Formula 1]

   

   (In Formula 1,

   R ¹ , R ² , R ³ are each an allyl group, metaallyl group, hydrogen, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, or a substituted or unsubstituted carbon atom group. An aryl group having 6 to 10, a substituted or unsubstituted arylalkyl group having 7 to 10 carbon atoms, or a glycidyl group,

   At least one of R ¹ , R ² , and R ³ is an allyl group or a methallyl group)

   [Formula 2]

   

   (In Formula 2,

   R ⁴ is an allyl group or a metaallyl group;

   R ⁵ is a substituted or unsubstituted, nitrogen-containing cyclic functional group;

   R ⁶ is an allyl group, metaallyl group, hydrogen, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, A substituted or unsubstituted arylalkyl group or glycidyl group having 7 to 10 carbon atoms, or

   R ⁵ and R ⁶ are linked to each other to form a substituted or unsubstituted nitrogen-containing cyclic functional group).
6. The composition for encapsulating an organic light emitting diode according to claim 1, wherein the allyl or methallyl compound having a nitrogen-containing cyclic structure includes at least one of the following Chemical Formulas 3-1 to 3-11:

   [Formula 3-1]

   

   [Formula 3-2]

   

   [Formula 3-3]

   

   [Formula 3-4]

   

   [Formula 3-5]

   

   [Formula 3-6]

   

   [Formula 3-7]

   

   [Formula 3-8]

   

   [Formula 3-9]

   

   [Formula 3-10]

   

   [Formula 3-11]

   

   .
7. The composition for encapsulating an organic light emitting diode according to claim 1, wherein the nitrogen-linked, allyl-based or metaallyl-based compound comprises a compound represented by Formula 4 below:

   [Formula 4]

   

   (In Chemical Formula 4,

   R ⁷ , R ⁸ , R ⁹ are each independently hydrogen, an allyl group, a metaallyl group, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, substituted or unsubstituted an arylalkyl group having 7 to 10 carbon atoms, or a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms,

   At least one of R ⁷ , R ⁸ , and R ⁹ is an allyl group or a metaallyl group;

   R ¹⁰ is hydrogen, an allyl group, a metaallyl group, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a substituted or unsubstituted arylalkyl group having 7 to 10 carbon atoms, or a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms;

   n is an integer from 0 to 2).
8. The composition for encapsulating an organic light emitting diode according to claim 1, wherein the nitrogen-linked, allyl-based or methallyl-based compound comprises at least one of the following Chemical Formulas 4-1 to 4-4:

   [Formula 4-1]

   

   [Formula 4-2]

   

   [Formula 4-3]

   

   [Formula 4-4]

   

   .
9. According to claim 1, wherein the composition is a non-solvent type, organic light emitting device sealing composition.
10. According to claim 1, wherein the composition has a viscosity of 7cps to 100cps at 25 ± 2 ℃, the composition for encapsulating an organic light emitting device.
11. An organic light emitting diode display device comprising an organic layer formed of the composition for encapsulating an organic light emitting diode according to any one of claims 1 to 10.

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