KR20230022644A - Composition for encapsulating organic light emitting diodes and organic light emitting diodes display comprising organic layer prepared using the same - Google Patents

Abstract

Provided are a composition for encapsulating organic light emitting diodes, which comprises: an allyl or methallyl compound having a nitrogen-containing cyclic structure; a thiol group-containing compound consisting only of carbon, hydrogen, sulfur and oxygen; and an initiator, and an organic light emitting diode display device comprising an organic layer formed therefrom. An object of the present invention is to provide the composition for encapsulating the organic light emitting device capable of forming the organic layer having low permittivity after curing.

Description

An 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 hardness, curing rate, 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; a thiol group-containing compound consisting only of carbon, hydrogen, sulfur and oxygen; and an 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 having an appropriate viscosity to form an organic layer having a uniform surface and having excellent hardness, curing rate, 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.

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, referred to as “composition”) may include an allyl or methallyl compound having a nitrogen-containing cyclic structure; a thiol group-containing compound consisting only of carbon, hydrogen, sulfur and oxygen; and an 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 (permitivity, ε) of 3.5 or less, specifically 2.0 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%, and more specifically 0% to 3.5% 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 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.

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 confirmed that an organic layer formed when an allyl-based or metaallyl-based compound having a nitrogen-containing cyclic structure is cured together with a thiol group-containing compound described below has a low dielectric constant and can implement an effect of improving the plasma etch rate.

The allyl or metaallyl-based compound having a nitrogen-containing cyclic structure is a photocurable compound, and has one or more, preferably 1 to 3 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 is a piperidine group, a piperidinone group (not particularly limited, but not limited to Formula 2-1), a piperidine dione group (not particularly limited, but Formula 2-2 below), Rolidine group, pyrrolidine dione group (but not particularly limited, Formula 2-3 below), pyridine group (but not particularly limited, Formula 2-10 below), indole group, at least partially hydrogenated indole group, indole dione group , Isoindole dione group at least partially hydrogenated (but not particularly limited, Formula 2-4, Formula 2-5, Formula 2-8 or Formula 2-9), pyridinedione group (but not particularly limited, Formula 2-9 below) 2-6), a pyrroldion group (but not particularly limited, and may be one or more of Chemical Formulas 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-based or metaallyl-based compound having a nitrogen-containing cyclic structure is 20 parts by weight to 90 parts by weight, preferably 20 parts by weight to 80 parts by weight, based on 100 parts by weight of the total of the component (A) and the component (B) below. may be included as a part. 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) thiol group-containing compound

The compound containing a thiol group (-SH) may be included in the composition to increase the curing rate of the composition, thereby increasing the pencil hardness of the organic layer. The thiol group-containing compound may also improve ink jetting properties by adjusting the viscosity of the composition by being included in the composition.

The thiol group-containing compound may include a photocurable compound having one or more thiol groups. Preferably, the thiol group-containing compound has 1 to 3 thiol groups, more preferably 1 to 2 thiol groups, thereby further increasing the curing rate of the composition and improving ink jetting properties.

A thiol group-containing compound is a compound composed only of carbon, hydrogen, sulfur and oxygen.

The thiol group-containing compound may include a compound of Formula 4 below:

[Formula 4]

(In Chemical Formula 4,

A is a substituted or unsubstituted aliphatic hydrocarbon group having 1 to 10 carbon atoms or a substituted or unsubstituted aromatic hydrocarbon group having 6 to 10 carbon atoms;

R ⁷ , R ⁸ , R ⁹ are each independently a thiol group (—SH), Formula 4-1, Formula 4-2, or Formula 4-3 below;

[Formula 4-1]

(In Chemical Formula 4-1, * is a linking site of an element,

R ¹¹ is a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms)

[Formula 4-2]

(In Chemical Formula 4-2, * is a linking site of an element,

R ¹² and R ¹³ are each independently a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms;

e is 0 or 1)

[Formula 4-3]

(In Chemical Formula 4-3, * is a linking site of an element,

R ¹⁴ and R ¹⁵ are each independently a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms;

f is 0 or 1)

R ¹⁰ is hydrogen, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms;

a, b, c are each an integer from 0 to 5, a+b+c is an integer of 1 or greater,

d is an integer from 0 to 5).

In the 'substitution' in Formula 4, the substituent is composed of only carbon, hydrogen, sulfur, and oxygen.

The "aliphatic hydrocarbon group" and "aromatic hydrocarbon group" in Formula 4 may be a monovalent to tetravalent hydrocarbon group. In one embodiment, the "C1-C10 aliphatic hydrocarbon group" may be a C1-C10 alkyl group or a C1-C10 alkylene group. In one embodiment, the "aromatic hydrocarbon group having 6 to 10 carbon atoms" may be an arylene group having 6 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms.

Preferably, each of a, b, and c may be an integer from 0 to 3. Preferably, a+b+c may be an integer of 1 to 5 or 1 to 3. Preferably, d may be an integer from 0 to 3.

Preferably, the thiol group-containing compound may include one or more of the following Formulas 5-1 to 5-9:

[Formula 5-1]

[Formula 5-2]

[Formula 5-3]

[Formula 5-4]

[Formula 5-5]

[Formula 5-6]

[Formula 5-7]

[Formula 5-8]

[Formula 5-9]

The thiol group-containing compound may be included in an amount of 10 parts by weight to 80 parts by weight, preferably 20 parts by weight to 80 parts by weight, based on 100 parts by weight of the total of the components (A) and (B). 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.

initiator

The initiator may include, without limitation, a conventional photopolymerization initiator capable of performing a photocurable reaction as a photoradical initiator. For example, the photopolymerization initiator may include a triazine-based, acetophenone-based, benzophenone-based, thioxanthone-based, benzoin-based, phosphorus-based, ketone-based, oxime-based, or a mixture thereof.

Preferably, the initiator may include at least one of a phosphorus-based initiator and a ketone-based initiator having a photoreaction initiation wavelength of 200 nm to 410 nm, preferably 300 nm to 400 nm, and more preferably 360 nm to 400 nm. When the initiator is used, the composition of the present invention may exhibit better initiation performance in long wavelength UV (eg, 300 nm to 410 nm). The "light reaction onset wavelength" can be measured by a conventional method known to those skilled in the art or refer to the product catalog of the corresponding material.

Phosphorus-based initiators include 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 mixtures thereof.

The ketone-based initiator may be 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1 or the like, but is not limited thereto.

The "light reaction initiation wavelength" may be measured by a conventional method known to those skilled in the art or a value obtained by referring to a product catalog.

Initiators 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). In the above range, the curing rate of the composition is increased and the light transmittance is prevented from being lowered due to the remaining amount of the initiator.

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 a UV wavelength of 10mW/cm ² to 500mW/cm ² 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 ink 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 light curing may have a pencil hardness of 4H or more, for example, 4H to 6H. Within this range, stable progress of subsequent processes may be possible with strong film strength.

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 diode, it is substantially the same as the organic light emitting diode 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)

(B) thiol group-containing compound

(B1) 1,10-decanedithiol (TCI)

(B2) 1,4-butanediol bis(thioglycolate) (TCI)

(B3) Bis(2-mercaptoethyl) sulfide (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-L, (2,4,6-trimethylbenzoyl) ethoxy phenyl phosphinate, BASF Company, IGM Company, photoreaction initiation wavelength 225-410 nm))

(D2) Mine Generator (Miphoto NIT, Miwon Corporation)

(D3) Ketone initiator (Irgacure 369, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, IGM, photoreaction initiation wavelength: 260-390 nm)

Example 1

55 parts by weight of (A1), 45 parts by weight of (B3), and 3 parts by weight of (D1) were put in a 125ml brown polypropylene bottle and mixed at room temperature for 3 hours using a shaker to prepare a composition for sealing.

Examples 2 to 8 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.

Example comparative example One 2 3 4 5 6 7 8 One 2 3 4 5 6 A A1 55 - - - 45 - - - 100 - - 50 50 - A2 - 20 - - - 50 - 20 - - - - - - A3 - - 70 - - - - - - - - - - - A4 - - - 80 - - 45 - - - - - - - B B1 - 50 - 20 - 20 - 50 - - - - - 100 B2 - 30 - - 55 - 20 30 - - - - - - B3 45 - 30 - - 30 35 - - - - - - - C C1 - - - - - - - - - 100 - 50 - - C2 - - - - - - - - - - 100 - 50 - D D1 3 3 3 3 3 3 3 - 3 - - - - 3 D2 - - - - - - - - - 0.2 0.2 0.2 0.2 - D3 - - - - - - - 3 - - - - - -

The following physical properties were measured for the compositions prepared in Examples and Comparative Examples, and the results are shown in Table 2.

(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) Inkjet jetting property: Inkjet jetting was performed at a drop rate of 2.5 μm/sec and an inkjet head temperature of 25 to 35° C. for the sealing compositions of Examples and Comparative Examples. When inkjet jetting was performed, if the shape of the drop was accurately spherical, it was evaluated as OK, and if it was not spherical, it was evaluated as NG.

(4) Pencil hardness: Coating the composition for encapsulation on a glass substrate and UV curing by UV 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.

(5) 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 One 2 3 4 5 6 viscosity 14.3 8.9 37.3 42.8 20.9 18.8 21.4 9.3 137 1.7 3.5 12 21 10.2 permittivity 2.95 3.48 2.92 2.65 3.12 3.24 3.11 3.28 2.31 4.6 5.5 not hardenable not hardenable not hardenable Inkjet jetting property OK OK OK OK OK OK OK OK NG NG NG OK OK OK pencil hardness 6H 5H 6H 5H 6H 5H 4H 5H 4H 2B 1B - - - plasma etch rate 5.9 6.2 5.6 5.7 6.1 5.8 6.2 6.0 5.2 8.9 9.4 - - -

* In Table 2, "-" means that Comparative Examples 4 to 6 were not cured and the results were not measured.

As shown in Table 2, the composition for encapsulating an organic light emitting device of the present invention formed an organic layer having a low dielectric constant, excellent plasma resistance, and excellent hardness after curing. In addition, the composition of the present invention was excellent in 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 (10)

A composition for encapsulating an organic light emitting device comprising an allyl or methallyl compound having a nitrogen-containing cyclic structure, a thiol group-containing compound consisting only of carbon, hydrogen, sulfur and oxygen, and an initiator.
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 thiol group-containing 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-based or metaallyl-based compound having the nitrogen-containing cyclic structure and the thiol group-containing compound, the composition for encapsulating an organic light emitting device.
The composition for encapsulating an organic light emitting diode according to claim 1, wherein the thiol group-containing compound comprises a compound represented by Formula 4 below:
[Formula 4]

(In Chemical Formula 4,
A is a substituted or unsubstituted aliphatic hydrocarbon group having 1 to 10 carbon atoms or a substituted or unsubstituted aromatic hydrocarbon group having 6 to 10 carbon atoms;
R ⁷ , R ⁸ , and R ⁹ are each independently a thiol group, Formula 4-1, Formula 4-2, or Formula 4-3 below;
[Formula 4-1]

(In Chemical Formula 4-1, * is a linking site of an element,
R ¹¹ is a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms)
[Formula 4-2]

(In Chemical Formula 4-2, * is a linking site of an element,
R ¹² and R ¹³ are each independently a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms;
e is 0 or 1)
[Formula 4-3]

(In Chemical Formula 4-3, * is a linking site of an element,
R ¹⁴ and R ¹⁵ are each independently a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms;
f is 0 or 1)
R ¹⁰ is hydrogen, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms;
a, b, c are each an integer from 0 to 5, a+b+c is an integer of 1 or greater,
d is an integer from 0 to 5).
The composition for encapsulating an organic light emitting diode according to claim 1, wherein the thiol group-containing compound includes at least one of the following Chemical Formulas 5-1 to 5-9:
[Formula 5-1]

[Formula 5-2]

[Formula 5-3]

[Formula 5-4]

[Formula 5-5]

[Formula 5-6]

[Formula 5-7]

[Formula 5-8]

[Formula 5-9]

.
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 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).
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]

.
The composition for encapsulating an organic light emitting device according to claim 1, wherein the initiator includes at least one of a phosphorus-based initiator and a ketone-based initiator having a photoreaction initiation wavelength of 200 nm to 400 nm.
According to claim 1, wherein the composition is a non-solvent type, organic light emitting device sealing composition.
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.
An organic light emitting diode display comprising an organic layer formed of the composition for encapsulating an organic light emitting diode according to any one of claims 1 to 9.

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