WO2019004764A1

WO2019004764A1 - Composition for encapsulating organic light emitting diode, and organic light emitting display device comprising same

Info

Publication number: WO2019004764A1
Application number: PCT/KR2018/007385
Authority: WO
Inventors: 박용욱; 이제우; 강문성; 박윤석; 문성윤
Original assignee: 덕산네오룩스 주식회사
Priority date: 2017-06-30
Filing date: 2018-06-29
Publication date: 2019-01-03

Abstract

The present invention provides: an encapsulation composition for an organic electroluminescence element, capable of improving the reliability of a member for a device by blocking moisture and oxygen permeating from the outside; and an encapsulated device comprising the same.

Description

Composition for encapsulating organic light emitting devices and organic light emitting display comprising the same

The present invention relates to a UV-blocking resin composition, and a flexible sealing technique for protecting an organic light-emitting device from external stimuli including moisture, oxygen and light.

In an organic light emitting diode (OLED), electrons injected from a cathode and holes injected from an anode are combined in an emission layer of an organic light emitting portion to form an electron-hole pair And a self-emitting flat panel display device in a process of recombination thereof. The organic light emitting device exhibits high luminous efficiency in the three primary colors of red, green, blue and white, low driving voltage and power consumption, wide viewing angle, and high response speed of pixels, Have.

In addition, the organic light emitting device is being actively studied in the field of flexible display, since it can realize an ultra-thin and lightweight display capable of being manufactured with a thickness of 1 mm or less on a glass or plastic substrate. However, in the organic light emitting device, the light emitting material and the electrode material are oxidized by oxygen or moisture, thereby causing problems such as a dark spot and a pixel shrinkage, resulting in a decrease in lifetime and efficiency. In addition, the lifetime and efficiency of the OLED device are reduced due to external light including sunlight. The sunlight has a light amount ratio of 2.5% of ultraviolet rays, 51.5% of visible rays, and 40.6% of ultraviolet rays. Among them, ultraviolet ray has a small amount of light but it is energetically high and causes decomposition and deterioration of organic light emitting material, Is destroyed. At this time, there is no general route in which the organic material and the organic-metal material by UV are decomposed. Generally, the organic and organic-metal materials of the organic light emitting device emit light when the light absorption occurs from the ground state to the singly excited state under the optical excitation and returns to the ground state. At this time, the binding energy in the organic or organic-metal molecule may be similar to or lower than the energy of singlet excited state, and dissociation may occur at the binding site. In addition, by the radical generated at this time, an addition reaction is carried out to form a neutral saturated decomposition product, which can act as an impurity.

As a result, when the organic light emitting device receives external light (sunlight) for a long time, the organic material or the organic-metal material of the organic light emitting device receives a continuous stress due to the ultraviolet rays flowing into the device, , The coupling of the destroyed molecules causes a change in the color coordinates of the organic light emitting device, a driving voltage rise, and a reduction in the lifetime, so that the ultraviolet rays should be prevented from flowing into the organic light emitting device.

Development of encapsulation technology for blocking oxygen, moisture, and ultraviolet rays introduced into the organic light emitting device is one of key technologies.

These encapsulation techniques can be largely classified into three ways: Can (glass encapsulation), TFE (thin film encapsulation), and Hybrid. Each method can be performed by using a metal or glass cover plate having a gas barrier property and a Can Method and a TEF method called a face sealing method which implements a barrier property by organic or inorganic multilayer thin film on the upper layer and a plastic barrier film as a cover plate, It can be explained by the hybrid method of positioning the adhesive layer. A sealing method is disclosed in Korean Patent Publication No. 2011-0071039.

Can (Glass encap) method widely used until now is a technology to seal the glass powder by melting with laser or to seal it with UV glue by placing organic light emitting element between two glass composed of substrate and lid, However, it is disadvantageous in that the heat conduction characteristic is poor due to the inert gas in the device, the cost due to the glass processing is increased due to the large surface area, and it is difficult to apply it to the production of the flexible OLED panel requiring flexibility.

In order to overcome the disadvantage of such a glass encapsulation technique, an inorganic layer such as Al ₂ O ₃ having a high barrier property to oxygen or moisture and a polymer organic layer are alternately laminated on the entire surface of the organic light emitting element, Thin film encapsulation (TFE), which is a multi-layer thin film encapsulation technique, has been actively studied.

The inorganic barrier layer may be a metal oxide / nitride such as AlxOy, SiOx, SiNy, SiOxNy, etc., and the inorganic barrier layer may be formed by sputtering (sputtering) on the organic barrier layer, deposition or plasma enhanced chemical vapor deposition (PECVD).

U.S. Patent No. 7767498 discloses that the barrier properties of moisture and oxygen are more advantageous as the number of pairs of the organic barrier layer and the inorganic barrier layer is larger. However, the barrier properties of the barrier layer due to the foreign material incorporation And a decrease in the yield along with the decrease is reported as disadvantage.

In recent studies, in order to overcome the yield deterioration while maintaining the barrier properties, research has been conducted in the direction of increasing the thickness of the organic / inorganic barrier layer and decreasing the number of layers in the thin film multilayer structure, As the number of processes is reduced, the number of process steps is reduced, and the manufacturing cost can be reduced by overcoming the deterioration of the characteristics and the yield reduction due to the inclusion of the foreign material.

Accordingly, the present invention provides an encapsulating material composition capable of protecting the organic light emitting element from ultraviolet light while having flexibility in film formation so as to be compatible with the development direction of a display which is converted from a rigid display to a flexible OLED.

It is an object of the present invention to provide a sealing composition having an ultraviolet shielding ability and suitable for an inkjet process.

Another object of the present invention is to provide a sealing composition capable of forming a thick film and having flexibility.

It is another object of the present invention to provide a sealing composition capable of forming a barrier layer for encapsulation of a member for an environmentally sensitive device.

The encapsulant used in the present invention is intended to block ultraviolet rays of 400 nm or less and transmit light in a visible light region of 440 nm or more to protect the organic light emitting device from ultraviolet rays and not to lower the efficiency of the organic light emitting device.

Therefore, the ultraviolet blocking agent included in the encapsulant used in the present invention absorbs ultraviolet rays of 400 nm or less and prevents ultraviolet rays from penetrating into the organic light emitting device, and must transmit visible light. This is calculated as the energy bandgap, which is a characteristic characteristic of organic materials.

The relationship between the wavelength of light and the energy is expressed by the following equation (1).

Equation 1)

? E = hv = hc /? [EV]

? [nm] = hc /? E = 1240 [eVnm] /? E [eV]

hc = (4.13566733 X 10 ^-15 [eVs]) (3 X 10 ⁸ [m / s])? 1240 [eVnm]

ΔE: energy difference between the base state of the electrons and the excited state

h: Plank's constant (= 6.626 X 10 ^-34 [JS] = 4.13566733 X 10 ^-15 [eVS])

v: Frequency of electromagnetic waves

λ: wavelength of electromagnetic wave

c: luminous flux (= 3.00 X 10 ⁸ [m / s])

According to the above formula (1), the ultraviolet ray corresponds to an electron energy level of 3.1 [eV] or more, which corresponds to the energy bandgap of the material. However, the ultraviolet screening agent included in the encapsulating composition of the present invention has an electron energy level of 2.95 to 3.1 [ev] since ultraviolet rays blocking 400 nm or less of ultraviolet rays should be blocked to 5% or less and visible light of 440 nm must be transmitted by 90% or more.

In addition, the sealing composition of the present invention may contain an ultraviolet screening agent of the following formula (1).

By using an ultraviolet absorber having an aromatic derivative bonded to nitrogen of the present invention, water, oxygen and ultraviolet rays penetrating from the outside after curing of the sealing composition can be blocked, thereby improving the reliability of the organic light emitting device.

1 is an exemplary view illustrating an organic electroluminescent device according to an embodiment of the present invention.

2 is a view schematically showing an example of the structure of an electronic device including an organic electroluminescent device.

3 is a graph of transmittance according to embodiments of the present invention.

4 is a graph of transmittance according to comparative examples.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings.

It should be noted that, in adding reference numerals to the constituent elements of the drawings, the same constituent elements are denoted by the same reference numerals even though they are shown in different drawings. In the following description of the present invention, a detailed description of known functions and configurations incorporated herein will be omitted when it may make the subject matter of the present invention rather unclear.

In describing the components of the present invention, terms such as first, second, A, B, (a), and (b) may be used. These terms are intended to distinguish the constituent elements from other constituent elements, and the terms do not limit the nature, order or order of the constituent elements. When a component is described as being "connected", "coupled", or "connected" to another component, the component may be directly connected to or connected to the other component, It should be understood that an element may be "connected," "coupled," or "connected."

As used in this specification and the appended claims, unless stated otherwise, the following terms have the following meanings:

The term " halo " or " halogen ", as used herein, unless otherwise indicated, is fluorine (F), bromine (Br), chlorine (Cl) or iodine (I).

As used herein, the term " alkyl " or " alkyl group " refers to a straight or branched Alkyl " means a radical of a saturated aliphatic group, including alkyl, cycloalkyl-substituted alkyl groups.

The term " haloalkyl group " or " halogenalkyl group " as used in the present invention means an alkyl group substituted with halogen unless otherwise stated.

The term " heteroalkyl group " as used herein means that at least one of the carbon atoms constituting the alkyl group is replaced by a heteroatom.

The term " alkenyl group " or " alkynyl group ", as used herein, unless otherwise indicated, each have a double bond or triple bond of from 2 to 60 carbon atoms and include straight chain or branched chain groups, It is not.

The term " cycloalkyl " as used herein, unless otherwise specified, means alkyl which forms a ring having from 3 to 60 carbon atoms, but is not limited thereto.

The term " alkoxy group ", " alkoxy group ", or " alkyloxy group " used in the present invention means an alkyl group to which an oxygen radical is attached and, unless otherwise stated, has 1 to 60 carbon atoms, It is not.

The term " alkenoyl group ", " alkenoyl group ", " alkenyloxy group ", or " alkenyloxy group " as used in the present invention means an alkenyl group to which an oxygen radical is attached, , But is not limited thereto.

As used herein, the term " aryloxyl group " or " aryloxy group " refers to an aryl group attached to an oxygen radical and, unless otherwise stated, has a carbon number of 6 to 60, but is not limited thereto.

The terms " aryl group " and " arylene group ", as used herein, unless otherwise specified, each have 6 to 60 carbon atoms, but are not limited thereto. In the present invention, an aryl group or an arylene group means a single ring or a multicyclic aromatic group, and neighboring substituents include aromatic rings formed by bonding or participating in the reaction. For example, the aryl group may be a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, an anthracenyl group, a fluorene group, a spirobifluorene group, or a spirobifluorene group.

The prefix " aryl " or " ar " means a radical substituted with an aryl group. For example, the arylalkyl group is an alkyl group substituted with an aryl group, the arylalkenyl group is an alkenyl group substituted with an aryl group, and the radical substituted with an aryl group has the carbon number described in the present specification.

Also, if prefixes are named consecutively, it means that the substituents are listed in the order listed first. Means, for example, an alkoxy group substituted with an aryl group in the case of an arylalkoxy group, a carbonyl group substituted with an alkoxy group in the case of an alkoxycarbonyl group, and an alkenyl group substituted with an arylcarbonyl group in the case of an arylcarbonylalkenyl group Wherein the arylcarbonyl group is a carbonyl group substituted with an aryl group.

The term " heteroalkyl ", as used herein, unless otherwise indicated, means an alkyl comprising one or more heteroatoms. The term " heteroaryl group " or " heteroarylene group " as used in the present invention means an aryl or arylene group having 2 to 60 carbon atoms each containing at least one heteroatom unless otherwise specified, And includes at least one of a single ring and a multi-ring, and neighboring functional devices may be formed in combination.

The term " heterocyclic group ", as used herein, unless otherwise indicated, includes one or more heteroatoms, has from 2 to 60 carbon atoms, includes at least one of a single ring and multiple rings and includes a heteroaliphatic ring and hetero Aromatic rings. Adjacent functional groups may be combined and formed.

As used herein, the term " heteroatom " refers to N, O, S, P or Si unless otherwise stated.

The " heterocyclic group " may also include a ring containing SO ₂ in place of the carbon forming the ring. For example, the "heterocyclic group" includes the following compounds.

Unless otherwise stated, the term " aliphatic " as used herein means an aliphatic hydrocarbon having 1 to 60 carbon atoms and an " aliphatic ring " means an aliphatic hydrocarbon ring having 3 to 60 carbon atoms.

Unless otherwise specified, the term "ring" as used herein refers to a fused ring consisting of an aliphatic ring of 3 to 60 carbon atoms or an aromatic ring of 6 to 60 carbon atoms or a heterocycle of 2 to 60 carbon atoms, or combinations thereof, Saturated or unsaturated ring.

Other hetero-compounds or hetero-radicals other than the above-mentioned hetero-compounds include, but are not limited to, one or more heteroatoms.

Unless otherwise specified, the term " carbonyl " as used herein refers to -COR ', wherein R' is hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, A cycloalkyl group of 2 to 20 carbon atoms, an alkenyl group of 2 to 20 carbon atoms, an alkynyl group of 2 to 20 carbon atoms, or a combination thereof.

Unless otherwise indicated, the term " ether " used in the present invention refers to -RO-R 'wherein R or R' are each independently of the other hydrogen, an alkyl group of 1-20 carbon atoms, An aryl group, a cycloalkyl group having 3 to 30 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, or a combination thereof.

One also no explicit description, the terms in the "unsubstituted or substituted", "substituted" is heavy hydrogen, a halogen, an amino group, a nitrile group, a nitro group, C ₁ ~ C ₂₀ alkyl group, C ₁ ~ C for use in the present invention C ₂ -C ₂₀ alkoxy groups, C ₁ -C ₂₀ alkylamine groups, C ₁ -C ₂₀ alkylthiophene groups, C ₆ -C ₂₀ arylthiophene groups, C ₂ -C ₂₀ alkenylene groups, C ₂ -C ₂₀ alkynyl, C ₃ ~ C ₂₀ cycloalkyl group, C ₆ ~ C ₂₀ aryl group, of a C ₆ ~ C ₂₀ substituted by deuterium aryl group, a C ₈ ~ C ₂₀ aryl alkenyl group, a silane group, a boron Means a group substituted with at least one substituent selected from the group consisting of a halogen atom, a halogen atom, a cyano group, a germanium group, and a C ₂ to C ₂₀ heterocyclic group.

Unless otherwise expressly stated, the formula used in the present invention is applied in the same manner as the definition of the substituent by the definition of the index of the following formula.

When a is an integer of 0, substituent R ¹ is absent. When a is an integer of 1, one substituent R ¹ is bonded to any one of carbon atoms forming a benzene ring, and when a is an integer of 2 or 3 each coupled as follows: and wherein R ¹ may be the same or different from each other, a is the case of 4 to 6 integer, and bonded to the carbon of the benzene ring in a similar way, while the display of the hydrogen bonded to the carbon to form a benzene ring Is omitted.

1 is an illustration of an encapsulated device in accordance with an embodiment of the present invention.

Referring to FIG. 1, a first electrode 120, a second electrode 180, and a second electrode 180 formed on a substrate 110 are formed between the first electrode 110 and the second electrode 180, And an organic material layer. In this case, the first electrode 120 may be an anode and the second electrode 180 may be a cathode (cathode). In case of an inverting type, the first electrode may be a cathode and the second electrode may be an anode.

The organic material layer may include a hole injecting layer 130, a hole transporting layer 140, a light emitting layer 150, an electron transporting layer 160, and an electron injecting layer 170 sequentially on the first electrode 120. At this time, the remaining layers except the light emitting layer 150 may not be formed. An electron blocking layer, a light emitting auxiliary layer 151, a buffer layer 141, and the like, and the electron transport layer 160 may serve as a hole blocking layer.

In addition, although not shown, the organic EL device 200 according to the present invention may include a protective layer or a light-efficiency-improvement layer (not shown) formed on one surface of the first electrode 120 and the second electrode 180, Capping layer).

The organic electroluminescent device 200 according to an embodiment of the present invention can be manufactured using a physical vapor deposition (PVD) method. For example, a first electrode 120 is formed by depositing a metal or a conductive metal oxide or an alloy thereof on a substrate, and a hole injecting layer 130, a hole transporting layer 140, a light emitting layer 150, A transport layer 160 and an electron injection layer 170, and then depositing a material usable as the second electrode 180 on the organic layer.

In addition, the organic material layer may be formed using a variety of polymer materials, not a vapor deposition method, or a solution process or a solvent process such as a spin coating process, a nozzle printing process, an inkjet printing process, a slot coating process, a dip coating process, It is possible to produce a smaller number of layers by a method such as a dipping process, a screen printing process, or a thermal transfer process. Since the organic material layer according to the present invention can be formed by various methods, the scope of the present invention is not limited by the forming method.

The organic electroluminescent device 200 according to the present invention may be a front emission type, a back emission type, or a both-sided emission type, depending on the material used.

WOLED (White Organic Light Emitting Device) has advantages of high resolution realization and fairness, and can be manufactured using existing color filter technology of LCD. Various structures for a white organic light emitting device mainly used as a backlight device have been proposed and patented. Typically, a stacking method in which R (Red), G (Green) and B (Blue) light emitting parts are arranged side by side, and R, G and B light emitting layers are stacked up and down , And a color conversion material (CCM) method using photo-luminescence of an inorganic phosphor by using electroluminescence by a blue (B) organic light emitting layer and light from the electroluminescence material. Can be applied to such WOLED.

The organic electroluminescent device 200 according to the present invention may be one of an organic light emitting diode (OLED), an organic solar cell, an organic photoconductor (OPC), an organic transistor (organic TFT), and a monochromatic or white illumination device.

Another embodiment of the present invention may include an electronic device including a display device including the above-described organic electroluminescent device 200 of the present invention and a control unit for controlling the display device. The electronic device may be a current or future wired or wireless communication terminal and includes all electronic devices such as a mobile communication terminal such as a mobile phone, a PDA, an electronic dictionary, a PMP, a remote controller, a navigation device, a game machine, various TVs, and various computers.

In addition, the present invention may further include a sealing layer 300 for protecting the organic EL device 200. 1, the sealing layer 300 is a single layer. However, the present invention is not limited thereto, and the sealing layer 300 may be formed of multiple layers. This configuration will be described with reference to FIG.

2 is a view schematically showing an example of the structure of an electronic device including an organic electroluminescent device. 2 includes a substrate 110, an organic electroluminescent device 200 disposed on the substrate 110, and an encapsulant layer 300 disposed on the organic electroluminescent device 200.

2, an embodiment in which the sealing layer 300 according to the present invention is composed of multiple layers composed of a first sealing layer 310 and a second sealing layer 320 is disclosed. 2, the sealing layer 300 has three layers. However, the sealing layer 300 may include two or more layers. When the sealing layer 300 is composed of three or more layers, it may include an inorganic barrier layer and an organic barrier layer. For example, when the first sealing layer 310 is an inorganic barrier layer, the second sealing layer 320 may be an organic barrier layer and the third sealing layer 330 may be an inorganic barrier layer. However, The stacking order of the

layers

310, 320, and 330 is not limited to this. For example, the organic barrier layer and the inorganic barrier layer may be alternately deposited to one layer or more and ten layers or less, preferably one layer or more and three layers or less.

The encapsulant layer 300 according to the present invention may form an organic barrier layer between the inorganic barrier layers for encapsulation or encapsulation of a flexible display device which is capable of curing the encapsulant composition . The sealing composition (organic barrier layer material) can be applied by a method such as vapor deposition, spin coating, or slit coating, and an initiator can be used for photo-curing.

The initiator may include, without limitation, conventional photopolymerization initiators capable of carrying out photo-curable reactions. Examples of the photopolymerization initiator include triazine; Cetophenone system; Benzophenone type; Thioxanthone system; Benzoin; taking over; Oxime based or mixtures thereof.

Examples of triazines include 2,4,6-trichloro-s-triazine; 2-phenyl-4,6-bis (trichloromethyl) -s-triazine; 2- (3 ', 4'-dimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine; 2- (4'-methoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine; 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine; 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine; 2-biphenyl-4,6-bis (trichloromethyl) -s-triazine; Bis (trichloromethyl) -6-styryl-s-triazine; 2- (naphtho-1-yl) -4,6-bis (trichloromethyl) -s-triazine; 2- (4-methoxynaphtho-1-yl) -4,6-bis (trichloromethyl) -s-triazine; 2,4-trichloromethyl (piperonyl) -6-triazine; 2,4- (trichloromethyl (4 ' -methoxystyryl) -6-triazine or mixtures thereof.

Examples of the acetophenone-based compound include 2,2'-diethoxyacetophenone; 2,2'-dibutoxyacetophenone; 2-hydroxy-2-methylpropiophenone; p-tert-butyltrichloroacetophenone; p-t-butyldichloroacetophenone; 4-chloroacetophenone; 2,2'-dichloro-4-phenoxyacetophenone; 2-methyl-1- (4- (methylthio) phenyl) -2 -morpholinopropan-1-one; Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one or mixtures thereof.

Examples of benzophenone include benzophenone; Benzoyl benzoic acid; Benzoyl benzoate; 4-phenylbenzophenone; Hydroxybenzophenone; Acrylated benzophenone; 4,4'-bis (dimethylamino) benzophenone; 4,4'-dichlorobenzophenone; 3,3'-dimethyl-2-methoxybenzophenone, or a mixture thereof.

Thioxanthone is thioxanthone; 2-methyl thioxanthone; Isopropyl thioxanthone; 2,4-diethyl thioxanthone; 2,4-diisopropylthioxanthone; 2-chlorothioxanthone, or a mixture thereof.

Examples of the benzoin group include benzoin; Benzoin methyl ether; Benzoin ethyl ether; Benzoin isopropyl ether; Benzoin isobutyl ether; Benzyl dimethyl ketal, or mixtures thereof.

Examples of phosphorus compounds include bisbenzoylphenylphosphine oxide; Benzoyldiphenylphosphine oxide, or a mixture thereof.

The oxime system was prepared by reacting 2- (o-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione and 1- (o-acetyloxime) 2-methylbenzoyl) -9H-carbazol-3-yl] ethanone, or mixtures thereof.

On the other hand, the initiator may be contained in an amount of 0.1 to 20% by weight, preferably 0.5 to 20% by weight, more preferably 0.5 to 10% by weight, and most preferably 0.5 to 7% by weight, based on the solid content. In the above range, photopolymerization can sufficiently take place at the time of exposure, and the transmittance can be prevented from being lowered due to the unreacted initiator remaining after the photopolymerization.

In the present invention, the light stabilizer itself does not have an ability to absorb ultraviolet light, but it is a light stabilizer having a photostabilizing effect in coexistence with a substance that absorbs ultraviolet light, and may include a conventional light stabilizer. For example, the light stabilizer may be a cyanoacrylate-based; Hindered amine series (HALS); A metal complex salt system or a mixture thereof.

The cyanoacrylate system is ethyl 2-cyano-3,3-diphenylacrylate; 2-ethylhexyl 2-cyano-3, 3-diphenylacrylate; Hexyl 2-cyano-3, 3-diphenylacrylate; Octyl 2-cyano-3- (4-methoxyphenyl) -3-phenyl acrylate; Pentaerythritol tetrakis (2-cyano-3,3-diphenylacrylate); Ethane-1,2-diylbis (2-cyano-3,3-diphenylacrylate); 2- (acryloyloxy) ethyl 2-cyano-3, 3-diphenylacrylate; 2- (methacryloyloxy) ethyl 2-cyano-3, 3-diphenylacrylate; Propane-1,2,3-triyltris (2-cyano-3,3-diphenylacrylate) or mixtures thereof.

Hindered amine systems (HALS) include tetrakis [methylene 3- (3,5-di-tert-butyl-4-hvdroxyphenyl) propionate] methane; Thiodiethylene bis [3 (3,5-di-tert-butyl-4-hvdroxyphenyl) propionate]; Octadecyl-3- (3,5-di-tert-butyl-4-hindoxyphenyl) propionate; Isotridecyl-3- (3,5-di-t-butyl-4-hindoxyphenyl) propionate; Hexamethyl (3,5-di-tert-butyl-4-hydroxydrosinamide); Iso-octyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate or mixtures thereof.

The metal complex salt system is 2,2'-thiobis (4-tert-octylphenolate)] -n-butylamine nickel (II); Nickel bis [monoethyl (3,5-di-tert-butyl-4-hydroxybenzyl) phosphonate] or a mixture thereof.

In addition, the light stabilizer may be contained in the composition in an amount of 0.1 to 10% by weight, preferably 0.1 to 5% by weight, more preferably 0.1 to 3% by weight. When the composition for encapsulating an organic light emitting element is exposed to ultraviolet rays for a long time in the above range, the function of the ultraviolet absorber can be maintained for a long time.

On the other hand, the formation of the organic barrier layer using photo-curing is performed by coating the sealing composition at 0.1 to 20 탆, preferably 1 to 15 탆, most preferably 1 to 10 탆, at 10 to 500 mW / cm 2 for 1 to 60 seconds Irradiation and curing. At this time, the curing rate may be 90% or more, preferably 93% or more. At this time, the composition and the initiator not participating in the photo-curing reaction in the organic barrier layer are minimized and the pass-way of moisture and / or oxygen is suppressed, so that good barrier properties can be obtained.

Also, when the sealing composition is cured (when an organic barrier layer is formed), the coated sealing composition may shrink, and the shrinkage may be about 1 to 20%, more preferably 1 to 15 %. &Lt; / RTI > When the shrinkage ratio of the organic barrier layer is 20% or more, dark spots and pixel shrinkage occur due to oxygen and / or moisture penetration in the inorganic barrier layer. In addition, The occurrence of warpage in the formation of the multi-layered barrier layer may lead to bonding of the light emitting device.

Specifically, the organic barrier layer of the sealing layer 300 according to the present invention comprises (A) 1 to 10% by weight of an ultraviolet screening agent represented by the following formula (1), (B) 20 to 70% (C) 5 to 40% by weight of mono (meth) acrylate and (D) 1 to 10% by weight of an initiator.

In Formula 1,

1) Ar ₁ , Ar ₂ and Ar ₃ are each independently the same or different and are C ₆ -C ₆₀ aryl; A fluorenyl group; A C ₂ to C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si and P; A fused ring group of a C ₃ to C ₃₀ aliphatic ring and a C ₆ to C ₃₀ aromatic ring; An alkyl group having ₁ to ₆₀ carbon atoms; An alkenyl group having ₂ to ₆₀ carbon atoms; An alkynyl group of C ₂ to C ₆₀ ; A C ₁ to C ₃₀ alkoxy group; An aryloxy group of C ₆ to C ₃₀ ; L'-N (Ar ₄ ) (Ar ₅ )

2) L 'is a single bond; An arylene group having ₆ to ₆₀ carbon atoms; A heterocyclic group of C ₂ ~ C _60; A fluorenylene group; A fused ring group of an aliphatic ring of C ₃ to C ₃₀ and an aromatic ring of C ₆ to C ₃₀ ,

3) Ar ₄ and Ar ₅ are each independently the same or different and are C ₆ -C ₆₀ aryl; A fluorenyl group; A C ₂ to C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si and P; A fused ring group of a C ₃ to C ₃₀ aliphatic ring and a C ₆ to C ₃₀ aromatic ring; An alkyl group having ₁ to ₆₀ carbon atoms; An alkenyl group having ₂ to ₆₀ carbon atoms; An alkynyl group of C ₂ to C ₆₀ ; A C ₁ to C ₆₀ alkoxy group; And an aryloxy group having ₆ to ₆₀ carbon atoms.

The Ar ₁ To Ar ₅ And when L 'is an aryl group, a fluorenyl group, an arylene group, a heterocyclic group, a fused ring group, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryloxy group or a fluorenylene group; heavy hydrogen; A silane group substituted or unsubstituted with an aryl group having ₆ to ₂₀ carbon atoms; Siloxyl group; Cyano; A nitro group; An alkyl thio group of C ₁ to C ₃₀ ; A C ₁ to C ₃₀ alkoxy group; An alkyl group having ₁ to ₃₀ carbon atoms; An alkenyl group having ₂ to ₃₀ carbon atoms; An alkynyl group of C ₂ to C ₃₀ ; A C ₆ to C ₃₀ aryl group; A C ₆ -C ₃₀ aryl group substituted with deuterium; A fluorenyl group; A heterocyclic group of C ₂ ~ C _30; A C ₃ to C ₃₀ cycloalkyl group; An arylalkyl group having ₇ to ₃₀ carbon atoms, and an arylalkenyl group having ₈ to ₃₀ carbon atoms, and these substituents may be further bonded to each other to form a ring, Refers to a fused ring consisting of an aliphatic ring having 3 to 20 carbon atoms or an aromatic ring having 6 to 20 carbon atoms or a heterocyclic ring having 2 to 20 carbon atoms, or a combination thereof, and includes a saturated or unsaturated ring.

The aryl group may be an aryl group having 6 to 60 carbon atoms, preferably 6 to 40 carbon atoms, more preferably 6 to 30 carbon atoms, and the heterocyclic group may have 2 to 60 carbon atoms, preferably 2 carbon atoms More preferably 1 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and in the case of the alkyl group, the number of carbon atoms is 1 to 50, preferably 1 to 30, more preferably 1 to 20, May be an alkyl group of 1 to 10 carbon atoms.

Specifically, when the aryl group or the arylene group is the aryl group or the arylene group, the aryl group or the arylene group may be independently selected from the group consisting of a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, a phenanthryl group or a phenylene group, a biphenylene group, Phenylene, phenylene, phenylene, phenylene, phenylene, phenylene, phenylene, phenylene, phenylene or phenylene.

In particular, Ar ₁ , Ar ₂ and Ar _{3 in the} above formula (1) May be a substituted or unsubstituted fluorenyl derivative.

L 'in the above formula (1) may be any one of the following formulas (a-1) to (a-4).

In the above formulas (a-1) to (a-4)

1) R ¹ and R ² are each independently the same or different and independently of one another are halogen; Hydrogen; heavy hydrogen; A silane group substituted or unsubstituted with an aryl group having ₆ to ₂₀ carbon atoms; Siloxyl group; Cyano; A nitro group; An alkyl thio group of C ₁ to C ₃₀ ; A C ₁ to C ₃₀ alkoxy group; An alkyl group having ₁ to ₃₀ carbon atoms; An alkenyl group having ₂ to ₃₀ carbon atoms; An alkynyl group of C ₂ to C ₃₀ ; A C ₆ to C ₃₀ aryl group; A C ₆ -C ₃₀ aryl group substituted with deuterium; A fluorenyl group; A heterocyclic group of C ₂ ~ C _30; A C ₃ to C ₃₀ cycloalkyl group; An arylalkyl group having ₇ to ₃₀ carbon atoms and an arylalkenyl group having ₈ to ₃₀ carbon atoms,

2) a, c and d are each an integer of 0 to 4, b is an integer of 0 to 6, e and f are integers of 0 to 3,

When a, b, c, d, e, and f are two or more, they are the same or different, and a plurality of R ^{1 s} or a plurality of R ^{2 s} or adjacent R ^{1 s} and R ^{2 s} are bonded to each other to form a ring In addition,

3) X is any one of NR ', O, S and CR'R "

4) R 'and R " are each independently selected from the group consisting of hydrogen, C ₆ -C ₂₀ aryl, C ₂ -C ₂₀ heterocycle, and C ₁ -C ₂₀ alkyl, R 'and R " may combine with each other to form a ring with a spy.

Wherein R ¹ , R ² , R 'and R "are the same as or different from each other selected from the group consisting of aryl, silane, siloxane, alkylthio, alkoxy, alkyl, alkenyl, If an alkyl group, an aryl alkenyl group is, each of halogen; deuterium; siloxane group;; C ₆ ~ aryl group a substituted or unsubstituted silane group of the C ₂₀ a cyano group; a nitro group; C ₁ ~ Import alkylthio of C _30; an alkoxy group of _{_{_{C 1 ~ C 30; C 1}}} ~ alkyl group of C _30; C ₂ ~ of the C ₃₀ alkenyl; C ₂ ~ alkynyl of C _30; a C ₆ substituted with heavy hydrogen; C ₆ ~ aryl group of C ₃₀ aryl group ~ C _30; fluorene group; C ₂ ~ heterocyclic group of C _30; C ₃ ~ C ₃₀ cycloalkyl group; C ₇ ~ C ₃₀ aryl group and a C ₈ ~ consisting of aryl alkenyl group of C ₃₀ And these substituents may be bonded to each other to form a ring, wherein the " ring " means a ring having 3 to 2 carbon atoms An aliphatic ring of 0 to 6 carbon atoms or an aromatic ring of 6 to 20 carbon atoms or a heterocyclic ring of 2 to 20 carbon atoms, or a combination thereof, and includes a saturated or unsaturated ring.

In addition, Ar ₄ of Formula 1 And Ar ₅ may be any one of the following formulas (b-1) to (b-4).

In the above formulas (b-1) to (b-4)

1) R ³ and R ⁴ are each independently the same or different and are halogen; Hydrogen; heavy hydrogen; A silane group substituted or unsubstituted with an aryl group having ₆ to ₂₀ carbon atoms; Siloxyl group; Cyano; A nitro group; An alkyl thio group of C ₁ to C ₃₀ ; A C ₁ to C ₃₀ alkoxy group; An alkyl group having ₁ to ₃₀ carbon atoms; An alkenyl group having ₂ to ₃₀ carbon atoms; An alkynyl group of C ₂ to C ₃₀ ; A C ₆ to C ₃₀ aryl group; A C ₆ -C ₃₀ aryl group substituted with deuterium; A fluorenyl group; A heterocyclic group of C ₂ ~ C _30; A C ₃ to C ₃₀ cycloalkyl group; An arylalkyl group having ₇ to ₃₀ carbon atoms and an arylalkenyl group having ₈ to ₃₀ carbon atoms,

2) a ', d', e 'are integers of 0-5, b' is an integer of 0-9, c 'is an integer of 0-4, f'

In the case where a, b ', c', d ', e' and f 'are two or more, a plurality of R ^{3 s} or a plurality of R ^{4 s} or adjacent R ^{3 s} and R ^{4 s} May be bonded to each other to form an aromatic ring or a heteroaromatic ring,

3) X is any one of NR ', O, S and CR'R "

4) R 'and R "are C ₆ -C ₂₀ aryl groups; A fluorenyl group; A heterocyclic group of C ₂ ~ C _20; C ₁ to C ₂₀ alkyl group, R 'and R "may combine with each other to form a ring with a spy,

5) Each of A ring and B ring is independently selected from the group consisting of an aryl group having ₆ to ₃₀ carbon atoms and a heterocyclic group having ₂ to ₃₀ carbon atoms.

Wherein R ³ , R ⁴ , R 'and R "are the same as or different from the above-mentioned aryl group, silane group, siloxane group, cyano group, nitro group, alkylthio group, alkoxy group, alkyl group, alkenyl group, alkynyl group, fluorenyl group, A substituted or unsubstituted C ₆ -C ₂₀ aryl group, a siloxane group, a cyano group, a nitro group, a C ₁ -C ₆ alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted aryloxy group, _A C ₁ to C ₃₀ alkyl group, a C ₁ to C ₃₀ alkoxy group, a C ₁ to C ₃₀ alkyl group, a C ₂ to C ₃₀ alkenyl group, a C ₂ to C ₃₀ alkynyl group, a C ₆ to C ₃₀ aryl group, an aryl group of a C ₆ ~ C ₃₀ substituted with heavy hydrogen; fluorene group; C ₂ ~ heterocyclic group of C _30; C ₃ ~ cycloalkyl group of C _{_30;} C ₇ ~ C ₃₀ aryl group and a C ₈ ~ C ₃₀ And the aryl group may be further substituted with one or more substituents selected from the group consisting of a halogen atom, Refers to a fused ring consisting of an aliphatic ring having 3 to 20 carbon atoms or an aromatic ring having 6 to 20 carbon atoms or a heterocyclic ring having 2 to 20 carbon atoms, or a combination thereof, and includes saturated or unsaturated rings.

Meanwhile, the composition for encapsulating an organic light emitting diode according to the present invention may contain at least two compounds different from each other among the compounds represented by the formula (1).

The (B) di (meth) acrylate contained in the composition for encapsulating an organic light emitting diode according to the present invention may be represented by the following formula (2).

In Formula 2,

1) R ⁵ and R ⁶ are hydrogen; heavy hydrogen; Tritium; An alkyl group having ₁ to ₆₀ carbon atoms; An alkenyl group having ₂ to ₆₀ carbon atoms; A C ₁ -C ₆₀ alkoxy group; A hydroxy group,

2) R ⁷ is a C ₁ to C ₆₀ alkylene group; A C ₆ -C ₆₀ arylene group; A fluorenylene group; It is selected by any one of the heterocyclic group of C ₂ ~ C _60.

When each of R ⁵ to R ⁷ is an alkyl group, an alkenyl group, an alkoxy group, a hydroxyl group, an alkylene group, an arylene group, a fluorenylene group, or a heterocyclic group, heavy hydrogen; A silane group substituted or unsubstituted with an aryl group having ₆ to ₂₀ carbon atoms; Siloxyl group; Cyano; A nitro group; An alkyl thio group of C ₁ to C ₃₀ ; A C ₁ to C ₃₀ alkoxy group; An alkyl group having ₁ to ₃₀ carbon atoms; An alkenyl group having ₂ to ₃₀ carbon atoms; An alkynyl group of C ₂ to C ₃₀ ; A C ₆ to C ₃₀ aryl group; A C ₆ -C ₃₀ aryl group substituted with deuterium; A fluorenyl group; A heterocyclic group of C ₂ ~ C _30; A C ₃ to C ₃₀ cycloalkyl group; An arylalkyl group having ₇ to ₃₀ carbon atoms, and an arylalkenyl group having ₈ to ₃₀ carbon atoms, and these substituents may be further bonded to each other to form a ring, Refers to a fused ring consisting of an aliphatic ring having 3 to 20 carbon atoms or an aromatic ring having 6 to 20 carbon atoms or a heterocyclic ring having 2 to 20 carbon atoms, or a combination thereof, and includes a saturated or unsaturated ring.

The composition for encapsulating an organic luminescent element of the present invention can further increase the photo-curability and the viscosity of the composition because the di (meth) acrylate represented by the above-mentioned formula (2) is contained. For example, in Formula 2, R ⁷ is a substituted or unsubstituted C ₁ -C ₆₀ alkylene group, a substituted or unsubstituted C ₆ -C ₆₀ arylene group, a substituted or unsubstituted fluorenylene group, a substituted Or an unsubstituted C ₂ to C ₆₀ heterocyclic group, preferably a substituted or unsubstituted C ₁ to C ₆₀ alkylene group, a substituted or unsubstituted C ₆ to C ₆₀ arylene group, Preferably a substituted or unsubstituted C ₁ to C ₃₀ alkylene group.

More specifically, the di (meth) acrylate is selected from the group consisting of octanediol di (meth) acrylate; Nonanediol (meth) acrylate; Decanediol di (meth) acrylate; Undecanediol (meth) acrylate; Dodecanediol (meth) acrylate; Decyl (meth) acrylate; Undecyl (meth) acrylate; Lauryl di (meth) acrylate; Tridecyl (meth) acrylate; Tetradecyl (meth) acrylate; Pentadecyldi (meth) acrylate; Hexadecyl (meth) acrylate; Heptadecyl (meth) acrylate; Octadecyl (meth) acrylate; Nonadecyldi (meth) acrylate; (Meth) acrylate, and the like, but are not limited thereto.

The mono (meth) acrylate (C) contained in the composition for encapsulating an organic luminescent element according to the present invention may be represented by the following formula (3).

In Formula 3,

1) L ₁ is a single bond; An alkylene group of C ₁ to C ₂₆ ; A C ₂ -C ₂₆ alkenyl group; A C ₁ to C ₂₆ alkoxy group; An arylene group having ₆ to ₆₀ carbon atoms; A C ₆ to C ₆₀ aryloxy group,

2) R ⁵ is hydrogen; heavy hydrogen; Tritium; An alkyl group having ₁ to ₆₀ carbon atoms; A C ₃ to C ₃₀ cycloalkyl group; An alkenyl group having ₂ to ₆₀ carbon atoms; A C ₁ to C ₆₀ alkoxy group; A hydroxyl group,

3) R ⁷ is a C ₆ to C ₆₀ aryl group; An aryloxy group of C ₆ to C ₆₀ ; A fluorenyl group; C ₂ to C ₆₀ heteroatoms.

When each of L ₁ , R ⁵ and R ⁷ is an alkyl group, an alkenyl group, an alkoxy group, an arylene group, an aryloxy group, a cycloalkyl group, a hydroxyl group, an aryl group, a fluorenyl group or a heterocyclic ring, heavy hydrogen; A silane group substituted or unsubstituted with an aryl group having ₆ to ₂₀ carbon atoms; Siloxyl group; Cyano; A nitro group; An alkyl thio group of C ₁ to C ₃₀ ; A C ₁ to C ₃₀ alkoxy group; An alkyl group having ₁ to ₃₀ carbon atoms; An alkenyl group having ₂ to ₃₀ carbon atoms; An alkynyl group of C ₂ to C ₃₀ ; A C ₆ to C ₃₀ aryl group; A C ₆ -C ₃₀ aryl group substituted with deuterium; A fluorenyl group; A heterocyclic group of C ₂ ~ C _30; A C ₃ to C ₃₀ cycloalkyl group; An arylalkyl group having ₇ to ₃₀ carbon atoms, and an arylalkenyl group having ₈ to ₃₀ carbon atoms, and these substituents may be further bonded to each other to form a ring, Refers to a fused ring consisting of an aliphatic ring having 3 to 20 carbon atoms or an aromatic ring having 6 to 20 carbon atoms or a heterocyclic ring having 2 to 20 carbon atoms, or a combination thereof, and includes a saturated or unsaturated ring.

For example, R ⁷ is a phenylphenoxyethyl group; A phenoxyethyl group; Benzyl group; A phenyl group; Phenylphenoxy group; Phenoxy group; A phenylethyl group; Phenylpropyl group; A phenylbutyl group; Methylphenylethyl; Propylphenylethyl; A methoxyphenylethyl group; Cyclohexylphenylethyl group; Chlorophenylethyl; Bromophenylethyl group; A methylphenyl group; Methylethylphenyl group; A methoxyphenyl group; A propyl group; A cyclohexylphenyl group; Chlorophenyl group; Bromophenyl group; A phenyl phenyl group; A biphenyl group; A terphenyl group; A quaterphenyl group; Anthracenyl group; A naphthalene group; A triphenylrenyl group; Methylphenoxy group; Ethylphenoxy group; Methylethylphenoxy group; A methoxyphenyloxy group; Propylphenoxy group; Cyclohexylphenoxy group; Chlorophenoxy group; Bromophenoxy group; A biphenyloxy group; A terphenyloxy group; A quaterphenyloxy group; Anthracenyloxy group; Naphthalenyloxy group; And may be a triphenylenyloxy group.

On the other hand, the above-mentioned formula (3) is preferably an aromatic mono (meth) acrylate, and is specifically as follows.

3-phenoxybenzyl (meth) acrylate; 2-phenylphenoxyethyl (meth) acrylate; Phenoxyethyl (meth) acrylate; Phenyl (meth) acrylate; Phenoxy (meth) acrylate; 2-ethylphenoxy (meth) acrylate; Benzyl (meth) acrylate; 2-phenylethyl (meth) acrylate; 3-phenylpropyl (meth) acrylate, 4-phenylbutyl (meth) acrylate; 2- (2-methylphenyl) ethyl (meth) acrylate; 2- (3-methylphenyl) ethyl (meth) acrylate; 2- (4-methylphenyl) ethyl (meth) acrylate; 2- (4-propylphenyl) ethyl (meth) acrylate; 2- (4- (1-methylethyl) phenyl) ethyl (meth) acrylate; 2- (4-methoxyphenyl) ethyl (meth) acrylate; 2- (4-cyclohexylphenyl) ethyl (meth) acrylate; 2- (2-chlorophenyl) ethyl (meth) acrylate; 2- (3-chlorophenyl) ethyl (meth) acrylate; 2- (4-chlorophenyl) ethyl (meth) acrylate; 2- (4-bromophenyl) ethyl (meth) acrylate; 2- (3-phenylphenyl) ethyl (meth) acrylate; 4- (biphenyl-2-yloxy) butyl (meth) acrylate; 3- (biphenyl-2-yloxy) butyl (meth) acrylate; 2- (biphenyl-2-yloxy) butyl (meth) acrylate; 1- (biphenyl-2-yloxy) butyl (meth) acrylate; 4- (biphenyl-2-yloxy) propyl (meth) acrylate; 3- (biphenyl-2-yloxy) propyl (meth) acrylate; 2- (biphenyl-2-yloxy) propyl (meth) acrylate; 1- (biphenyl-2-yloxy) propyl (meth) acrylate; 4- (biphenyl-2-yloxy) ethyl (meth) acrylate; 3- (biphenyl-2-yloxy) ethyl (meth) acrylate; 2- (biphenyl-2-yloxy) ethyl (meth) acrylate; 1- (biphenyl-2-yloxy) ethyl (meth) acrylate; 2- (4-benzylphenyl) ethyl (meth) acrylate; 1- (4-benzylphenyl) ethyl (meth) acrylate, or structural isomers thereof.

In addition, the (meth) acrylate referred to in the present invention is not limited to only one example, and the present invention includes all acrylates having a structural isomer relationship. For example, although only 2-phenylethyl (meth) acrylate is mentioned as an example of the present invention, the present invention includes at least one of 3-phenylethyl (meth) acrylate and 4-phenyl But is not limited thereto.

The composition for encapsulating an organic light emitting diode according to the present invention may further comprise a light stabilizer. The light stabilizer may be selected from the group consisting of (A) an ultraviolet light blocking agent, (B) di (meth) acrylate, (C) mono And 0.1 to 10% by weight based on the total amount of (D) initiator.

The compound represented by Formula 1 may be any one of the following compounds, and the compound represented by Formula 1 is not limited to the following compounds.

The composition for encapsulating an organic light emitting diode according to the present invention may have a viscosity of 5 cps to 40 cps at 25 ° C.

In addition, the composition for encapsulating an organic luminescent element according to the present invention may further comprise a photo-curable initiator.

In addition, the barrier layer formed on the organic light emitting device may include an inorganic barrier layer and an organic barrier layer, and the organic barrier layer may be a composition for encapsulating an organic luminescent element according to any one of claims 1 to 11 .

In addition, the organic barrier layer may be formed by inkjet, vacuum deposition, spin coating, or slit coating.

The light transmittance of the composition for encapsulating an organic light emitting diode according to the present invention may be less than 10% at 400 nm and at least 90% at 440 nm. Preferably, the composition for encapsulating an organic light emitting diode according to the present invention has a light transmittance of less than 5% at 400 nm and at least 90% at 430 nm, more preferably a light transmittance of the composition for encapsulating an organic light emitting element according to the present invention The light transmittance at 405 nm is less than 10% and the light transmittance at 430 nm is at least 90%. More preferably, the light transmittance of the composition for encapsulating an organic light emitting device according to the present invention is less than 5% at 405 nm and 90% More preferably, the light transmittance of the composition for encapsulating an organic light emitting diode according to the present invention may be less than 5% at 410 nm and greater than 90% at 430 nm.

Hereinafter, the synthesis examples and preparation examples of the compound represented by the formula (1) according to the present invention will be specifically described with reference to examples, but the present invention is not limited to the following examples.

[합성예 1][Synthesis Example 1]

The compound represented by Formula 1 according to the present invention (Final Product 1) is prepared by reacting Sub 1 and Sub 2 as shown in Reaction Scheme 1 below.

The compound of formula (1) according to the present invention is prepared by reacting Sub 1 and Sub 3 as shown in Reaction Scheme 2 below.

In addition, the compound of formula (1) according to the present invention is prepared by reacting Core 1 'and Sub 3' as shown in Reaction Scheme 3 below.

Sub 1 합성 예시Sub 1 synthesis example

Sub 1 of Scheme 1 may be synthesized by the reaction path of Scheme 4 below, but is not limited thereto.

Sub 1(1)의 합성예시Example of synthesis of Sub 1 (1)

The starting material, 2-bromo-9,9-dimethyl-9H-fluorene (112.50 g, 411.83 mmol) and naphthalen-2-amine (64.87 g, 453.01 mmol) were dissolved in toluene (2000 ml) Pd ₂ (dba) ₃ (18.86 g, 20.59 mmol), 50% P (t-Bu) ₃ (16.66 ml, 41.18 mmol) and NaOt-Bu (119.47 g, 1235.49 mmol) were added and stirred at room temperature. When the reaction was completed, water was added to complete the reaction. The organic layer was extracted, dried over MgSO ₄ and concentrated. The resulting compound was subjected to silicagel column to obtain 100.5 g (yield: 73%) of the product.

Sub 1(2)의 합성예시Example of synthesis of Sub 1 (2)

2-bromo-9,9-diphenyl-9H-fluorene (95.0 g, 239.10 mmol), naphthalen-2-amine (37.66 g, 263.01 mmol), toluene (1200 mL), Pd ₂ (dba) ₃ 10.95 g, 11.96 mmol), 50 % P (t-Bu) 3 (9.675 ml, 23.91 mmol), NaOt-Bu (69.36 g, 717.31 mmol) and the product proceeds in the same manner as in experiment method of Sub 1 (1) 83.73 g (Yield: 76%) was obtained.

Sub 1(3)의 합성예시 Example of synthesis of Sub 1 (3)

(80.0 g, 201.35 mmol), 9,9-dimethyl-9H-fluoren-2-amine (46.35 g, 221.48 mmol), toluene (1000 ml) , of _{_{Pd 2 (dba) 3 (9.22}} g, 10.07 mmol), 50% P (t-Bu) 3 (8.14 ml, 20.13 mmol), NaOt-Bu (58.41 g, 604.05 mmol) to the Sub 1 (1) The reaction proceeded in the same manner as in Experimental procedure to obtain 81.29 g (yield: 77%) of the product.

Sub 1(4)의 합성예시Example of synthesis of Sub 1 (4)

9,9-dimethyl-9H-fluoren-2-amine (93.82 g, 448.29 mmol), toluene (2000 ml), Pd ₂ _{(dba) 3 (18.66 g,} 20.38 mmol), 50% P (t-Bu) 3 to (16.49 ml, 40.75 mmol), NaOt-Bu (118.23 g, 1222.60 mmol) and the experimental method of the Sub 1 (1) The same procedure was followed to obtain 114.76 g (yield: 78%) of the product.

Sub 1(5)의 합성예시Example of synthesis of Sub 1 (5)

9-dimethyl-9H-fluoren-2-amine (71.54 g, 341.84 mmol), toluene (1500 mL), Pd ₂ (dBA ) in the same manner as in test method _{3 (14.23 g, 15.54 mmol)} , 50% P (t-Bu) 3 (12.57 ml, 31.08 mmol), NaOt-Bu (90.15 g, 932.30 mmol) to the Sub 1 (1) To obtain 93.62 g (yield: 73%) of the product.

Sub 1(6)의 합성예시Example of synthesis of Sub 1 (6)

9-diphenyl-9H-fluoren-2-amine (84.19 g, 252.50 mmol), toluene (1100 mL), Pd ₂ (dba (3-bromophenyl) naphthalene (65.0 g, 229.54 mmol) ) in the same manner as in test method _{3 (10.51 g, 11.48 mmol)} , 50% P (t-Bu) 3 (9.28 ml, 22.95 mmol), NaOt-Bu (66.59 g, 688.63 mmol) to the Sub 1 (1) To obtain 94.80 g (yield: 77%) of the product.

Sub 1(7)의 합성예시Example of synthesis of Sub 1 (7)

The starting material, 2-bromo-9,9-diphenyl-9H-fluorene (88.0 g, 221.48 mmol), [1,1'- biphenyl] -3 -amine (41.23 g, 243.63 mmol) Bu (64.25 g, 664.45 mmol) was added to a solution of Pd ₂ (dba) ₃ (10.14 g, 11.07 mmol), 50% P (t- Bu) ₃ (8.96 ml, 22.15 mmol) (77.55 g, yield: 72%) was obtained.

Sub 1(8)의 합성예시Example of synthesis of Sub 1 (8)

(75.0 g, 188.76 mmol), [1,1'-biphenyl] -2-amine (35.14 g, 207.64 mmol), toluene (1000 mL), and a mixture of 2-bromo-9,9-diphenyl-9H- Bu of Pd ₂ (dba) ₃ (8.64 g, 9.44 mmol), 50% P (t-Bu) ₃ (7.63 ml, 18.88 mmol) and NaOt-Bu (54.76 g, 566.29 mmol) (63.36 g, yield: 71%) was obtained.

Sub 1(9)의 합성예시Example of synthesis of Sub 1 (9)

2-bromo-9,9-diphenyl-9H-fluorene (80.0 g, 201.35 mmol), [1,1'- biphenyl] -4- Bu (584.1 g, 604.05 mmol) was added to a solution of Pd ₂ (dba) ₃ (9.22 g, 10.07 mmol), 50% P (t- Bu) ₃ (8.14 ml, 20.13 mmol) (71.38 g, yield: 73%) was obtained.

Sub 1(10)의 합성예시Example of synthesis of Sub 1 (10)

9-diphenyl-9H-fluoren-2-amine (57.23 g, 171.65 mmol) and toluene (800 ml) were added to a solution of the starting material, 2-bromo- Bu (45.27 g, 468.14 mmol), Pd ₂ (dba) ₃ (7.14 g, 7.80 mmol), 50% P (t- Bu) ₃ (6.31 ml, The reaction proceeded in the same manner as in Experimental procedure to obtain 73.01 g (yield: 72%) of the product.

Sub 1(11)의 합성예시Example of synthesis of Sub 1 (11)

The starting material, 4-bromo-4 '- (tert-butyl) -1,1'-biphenyl (35.00 g, 121.02 mmol), 9,9-dimethyl-9H- fluoren- 2 -amine (27.82 g, 133.12 mmol) (50 ml), toluene (600 ml), Pd ₂ (dba) ₃ (5.54 g, 6.05 mmol), 50% P (t- Bu) ₃ (4.89 ml, 12.10 mmol) and NaOt- Subsequently, the same procedure as in Sub 1 (1) was conducted to obtain 35.22 g (yield: 70%) of the product.

Sub 1(12)의 합성예시Example of synthesis of Sub 1 (12)

4-bromo-4 '- (tert-butyl) -1,1'-biphenyl (32.00 g, 110.64 mmol) and 9,9- diphenyl- 9H- fluoren- 2 -amine (40.58 g, 121.71 mmol) (32.10 g, 331.93 mmol), 50% P (t-Bu) ₃ (4.47 ml, 11.06 mmol) and Pd ₂ (dba) ₃ (5.07 g, 5.53 mmol) Subsequently, 42.01 g (yield: 70%) of the product was obtained in the same manner as in Sub 1 (1).

Sub 1(13)의 합성예시Example of synthesis of Sub 1 (13)

(30.0 g, 103.73 mmol), 9,9-diphenyl-9H-fluoren-2-amine (38.04 g, 114.10 mmol), which is the starting material, 3-bromo-4 ' a, toluene (550 ml), Pd 2 (dba) 3 (4.75 g, 5.19 mmol), 50% P (t-Bu) 3 (4.19 ml, 10.37 mmol), NaOt-Bu (30.09 g, 311.18 mmol) the Subsequently, 38.71 g (yield: 69%) of the product was obtained in the same manner as in Sub 1 (1).

Sub 1(14)의 합성예시Example of synthesis of Sub 1 (14)

(25.00 g, 82.99 mmol), [1,1'-biphenyl] -3-amine (15.45 g, 91.29 mmol), toluene (450 ml) _{_{Pd 2 (dba) 3 (3.80}} g, 4.15 mmol), 50% P (t-Bu) 3 (3.35 ml, 8.30 mmol), NaOt-Bu (24.08 g, 248.98 mmol) experiments of said Sub 1 (1) (Yield: 68%) of the product.

Sub 1(15)의 합성예시Example of synthesis of Sub 1 (15)

2-bromo-9,9-diethyl-9H-fluorene (25.00 g, 82.99 mmol), naphthalen-2-amine (13.07 g, 91.29 mmol), toluene (420 mL), Pd ₂ (dba) ₃ (3,80 g, 4.15 mmol), 50% P (t-Bu) ₃ (3.35 ml, 8.30 mmol) and NaOt-Bu (24.08 g, 248.98 mmol) 21.20 g (Yield: 70%) was obtained.

Sub 1(16)의 합성예시Example of synthesis of Sub 1 (16)

The starting material, 2-bromo-9,9-diethyl- 9H-fluorene (25.00 g, 82.99 mmol), aniline (8.50 g, 91.29 mmol), toluene (420 ml), Pd 2 (dba) 3 (3.80 g, 4.15 (24.08 g, 248.98 mmol) was treated in the same manner as in Sub 1 (1) to obtain 17.93 g of the product (yield: 50%), P (t- Bu) ₃ (3.35 ml, 8.30 mmol) and NaOt- : 68%).

Sub 1(17)의 합성예시Example of synthesis of Sub 1 (17)

The starting material, 2-bromo-9,9-diethyl- 9H-fluorene (25.00 g, 82.99 mmol), 4-aminobiphenyl (15.45 g, 91.29 mmol), toluene (420 ml), Pd 2 (dba) 3 (3.80 g , 4.15 mmol), 50% P (t-Bu) 3 (3.35 ml, 8.30 mmol), NaOt-Bu (24.08 g, 248.98 mmol) the process proceeds in the same manner as in experiment method of Sub 1 (1) product was 23.05 g (Yield: 71%).

Sub 1(18)의 합성예시Example of synthesis of Sub 1 (18)

(25.0 g, 82.99 mmol), 4- (naphthalen-1-yl) aniline (20.02 g, 91.29 mmol), toluene (420 mL), Pd ₂ _{(dba) 3 (3.80 g,} 4.15 mmol), 50% P (t-Bu) 3 (3.35 ml, 8.30 mmol), NaOt-Bu (24.08 g, 248.98 mmol) to the test method of the Sub 1 (1) The same procedure was followed to obtain 26.30 g (yield: 72%) of the product.

Sub 1(19)의 합성예시Example of synthesis of Sub 1 (19)

(25.00 g, 82.99 mmol), [1,1'-biphenyl] -3-amine (15.45 g, 91.29 mmol), toluene (420 mL) _{_{Pd 2 (dba) 3 (3.80}} g, 4.15 mmol), 50% P (t-Bu) 3 (3.35 ml, 8.30 mmol), NaOt-Bu (24.08 g, 248.98 mmol) experiments of said Sub 1 (1) (Yield: 70%) of the product.

Sub 1(20)의 합성예시Example of synthesis of Sub 1 (20)

A mixture of 2-bromo-9,9-dimethyl-9H-fluorene (100.00 g, 366.07 mmol), aniline (37.50 g, 402.68 mmol), toluene (1800 mL), Pd ₂ (dba) ₃ (16.76 g, (106.20 g, 1098.22 mmol) was treated in the same manner as in Sub 1 (1) to give 75.84 g of product (Yield: 80%), 50% P (t- Bu) ₃ (14.81 ml, 36.61 mmol) and NaOt- : 73%).

Sub 1(21)의 합성예시Example of synthesis of Sub 1 (21)

The starting material, 3-bromo-1,1'-biphenyl ( 82.50 g, 353.91 mmol), 9,9-dimethyl-9H-fluoren-2-amine (91.48 g, 389.30 mmol), toluene (1750 ml), Pd 2 (dba) ₃ (16.20 g, 17.70 mmol), 50% P (t-Bu) ₃ (14.32 ml, 35.39 mmol) and NaOt-Bu (102.67 g, 1061.73 mmol) The same procedure was followed to obtain 99.02 g (yield: 77%) of the product.

Sub 1(22)의 합성예시Example of synthesis of Sub 1 (22)

2-bromo-9,9-dimethyl-9H-fluorene (100.00 g, 366.07 mmol) and [1,1'-biphenyl] -2- amine (68.15 g, 402.68 mmol) Bu (106.20 g, 1098.22 mmol) was added to a mixture of Pd ₂ (dba) ₃ (16.76 g, 18.30 mmol), 50% P (t- Bu) ₃ (14.81 ml, 36.61 mmol) (96.07 g, yield: 73%) was obtained.

Sub 1(23)의 합성예시Example of synthesis of Sub 1 (23)

2-bromo-9,9-diphenyl-9H-fluorene (100.00 g, 251.69 mmol), naphthalen-2-amine (39.64 g, 276.85 mmol), toluene (1300 mL), Pd ₂ (dba) ₃ (73.01 g, 755.06 mmol) was treated in the same manner as in Sub 1 (1) to obtain the product (11.52 g, 12.58 mmol), 50% P (t- Bu) ₃ (10.18 ml, 25.17 mmol) and NaOt- 88.60 g (Yield: 77%) was obtained.

Sub 1(24)의 합성예시Example of synthesis of Sub 1 (24)

A mixture of 2-bromo-9,9-diphenyl-9H-fluorene (100.00 g, 251.69 mmol), aniline (25.78 g, 276.85 mmol), toluene (1250 mL), Pd ₂ (dba) ₃ (11.52 g, 12.58 (73.01 g, 755.06 mmol) was treated in the same manner as in Sub 1 (1) to obtain 78.23 g of the product (yield: 78%), 50% P (t- Bu) ₃ (10.18 ml, 25.17 mmol) and NaOt- : 76%).

Sub 1(25)의 합성예시Example of synthesis of Sub 1 (25)

(100.8 g, 251.69 mmol), [1,1'-biphenyl] -4-amine (46.85 g, 276.85 mmol), toluene (1250 mL), and 2-bromo-9,9- diphenyl-9H- Bu (73.01 g, 755.06 mmol) was added to a solution of Pd ₂ (dba) ₃ (11.52 g, 12.58 mmol), 50% P (t- Bu) ₃ (10.18 ml, 25.17 mmol) (Yield: 79%) of the product.

Sub 1(26)의 합성예시Example of synthesis of Sub 1 (26)

(60.03 g, 644.54 mmol), toluene (2000 ml), Pd ₂ (dba) ₃ (26.83 g, 29.30 mmol), 50% P (t-Bu) ₃ (23.71 ml, 58.59 mmol) and NaOt-Bu (169.98 g, 1757.85 mmol) were treated in the same manner as in Sub 1 (1) to obtain 72.28 g of the product (yield: 73%).

Sub 1(27)의 합성예시Example of synthesis of Sub 1 (27)

The starting material, 2-bromonaphthalene (85.00 g, 410.49 mmol), aniline (42.05 g, 451.54 mmol), toluene (2000 ml), Pd 2 (dba) 3 (18.79 g, 20.52 mmol), 50% P (t-Bu _{) 3 (16.61 ml, 41.05 mmol} ), NaOt-Bu (119.08 g, 1231.47 mmol) the process proceeds in the same manner as in experiment method of Sub 1 (1) product was 66.70 g (yield: was obtained in 74%).

Sub 1(28)의 합성예시Example of synthesis of Sub 1 (28)

The starting material, 2-bromonaphthalene (87.00 g, 420.15 mmol), [1,1'-biphenyl] -4-amine (78.21 g, 462.16 mmol), toluene (2000 ml), Pd 2 (dba) 3 (19.24 g, 21.01 mmol), 50% P ( t-Bu) 3 (17.00 ml, 42.01 mmol), NaOt-Bu (121.88 g, 1260.44 mmol) the process proceeds in the same manner as in experiment method of Sub 1 (1) product was 93.82 g ( Yield: 76%) was obtained

Sub 1(29)의 합성예시Example of synthesis of Sub 1 (29)

(100.0 g, 336.07 mmol), 9,9-dimethyl-9H-fluoren-2-amine (84.28 g, 402.68 mmol), toluene (1800 mL), and 2-bromo-9,9- Bu (106.20 g, 1098.22 mmol), Pd ₂ (dba) ₃ (16.76 g, 18.30 mmol), 50% P (t- Bu) ₃ (14.81 ml, 36.61 mmol) The procedure proceeded in the same manner as the experimental method to obtain 108.92 g (yield: 74%) of the product.

Sub 1(30)의 합성예시Example of synthesis of Sub 1 (30)

9,9-diethyl-9H-fluorene (25.00 g, 82.99 mmol), 9,9-dimethyl-9H-fluoren-2-amine (19.11 g, 91.29 mmol) , of _{_{Pd 2 (dba) 3 (3.80}} g, 4.15 mmol), 50% P (t-Bu) 3 (3.35 ml, 8.30 mmol), NaOt-Bu (24.08 g, 248.98 mmol) to the Sub 1 (1) 25.06 g (Yield: 70%) of the product was obtained.

Sub 1(31)의 합성예시Example of synthesis of Sub 1 (31)

(25.00 g, 117.30 mmol), 9,9-dimethyl-9H-fluoren-2-amine (27.01 g, 129.04 mmol), toluene (600 mL), and 1-bromo- _{_{Pd 2 (dba) 3 (5.37}} g, 5.87 mmol), 50% P (t-Bu) 3 (4.74 ml, 11.73 mmol), NaOt-Bu (34.03 g, 351.91 mmol) experiments of said Sub 1 (1) (27.52 g, yield: 69%) was obtained.

Sub 1(32)의 합성예시Example of synthesis of Sub 1 (32)

(25.6 g, 86.44 mmol), naphthalen-2-amine (13.61 g, 95.08 mmol), toluene (450 mL), Pd ₂ test method _{(dba) 3 (3.96 g,} 4.32 mmol), 50% P (t-Bu) 3 (3.49 ml, 8.64 mmol), NaOt-Bu (25.08 g, 259.32 mmol) to the Sub 1 (1) To obtain 21.66 g (yield: 71%) of the product.

Sub 1(33)의 합성예시Example of synthesis of Sub 1 (33)

A mixture of 4-bromo-1,1'-biphenyl (50.00 g, 214.49 mmol), aniline (21.97 g, 235.94 mmol), toluene (1000 mL), Pd ₂ (dba) ₃ (9.82 g, 10.72 mmol) 41.20 g (Yield: 78%) was obtained by proceeding in the same manner as in Sub 1 (1) except that 50% P (t-Bu) ₃ (8.67 ml, 21.45 mmol) and NaOt-Bu (62.22 g, 643.47 mmol) ).

Sub 1(34)의 합성예시Example of synthesis of Sub 1 (34)

The starting material, 2-bromo-9,9-dimethyl- 9H-fluorene (50.00 g, 183.04 mmol), naphthalen-1-amine (33.78 g, 235.94 mmol), toluene (900 ml), Pd 2 (dba) 3 ( 9.82 g, 10.72 mmol), 50% P (t-Bu) ₃ (8.67 ml, 21.45 mmol) and NaOt-Bu (62.22 g, 643.47 mmol) 47.33 g (Yield: 77%) was obtained.

The compound belonging to Sub 1 may be, but not limited to, the following compounds, and Table 1 shows FD-MS (Field Desorption-Mass Spectrometry) values of some compounds belonging to Sub 1.

Sub 3 합성 예시Example of Sub 3 synthesis

Sub 3 of Scheme 2 can be synthesized by the reaction path of Scheme 5 below, but is not limited thereto.

Sub 3(21)의 합성예시Example of synthesis of Sub 3 (21)

The starting material Sub 1 (1) (15.00 g, 44.72 mmol) and 2,7-dibromo-9,9-dimethyl-9H-fluorene (16.53 g, 46.95 mmol) were dissolved in toluene (250 ml) in a round bottom flask after addition of _{_{Pd 2 (dba) 3 (2.05}} g, 2.24 mmol), 50% P (t-Bu) 3 (1.80 ml, 4.47 mmol), NaOt-Bu (12.97 g, 134.15 mmol) and stirred at 80 ℃ Respectively. When the reaction was completed, water was added to complete the reaction. The organic layer was extracted, dried over MgSO ₄ and concentrated. The resulting compound was subjected to silicagel column to obtain 17.71 g (yield: 65%) of the product.

Sub 3(24)의 합성예시Example of synthesis of Sub 3 (24)

9,7-dibromo-9,9-diphenyl-9H-fluorene (47.88 g, 100.55 mmol), toluene (500 ml), Pd ₂ (dba) ₃ (4.38 g, 4.79 mmol), 50% P (t-Bu) ₃ (3.87 ml, 9.58 mmol) and NaOt-Bu (27.78 g, 287.29 mmol) 38.90 g of the product (yield: 66%) was obtained.

Sub 3(37)의 합성예시Example of synthesis of Sub 3 (37)

9-diphenyl-9H-fluorene (47.88 g, 100.55 mmol), toluene (400 ml), Pd ₂ (dba) ₃ (4.38 g, 4.79 mmol), 50% P (t-Bu) ₃ (3.87 ml, 9.58 mmol) and NaOt-Bu (27.78 g, 287.29 mmol) To obtain 36.97 g (yield: 67%) of the product.

The compound belonging to Sub 2 may be, but not limited to, the following compounds, and Table 2 shows FD-MS (Field Desorption-Mass Spectrometry) values of some compounds belonging to Sub 2.

Core 1' 합성 예시Core 1 'synthesis example

Core 1 'of Scheme 3 can be synthesized by the reaction path of Scheme 6 below, but is not limited thereto.

Sub 1' 합성 예시Sub 1 'Synthetic example

Sub 1 'of Scheme 6 can be synthesized by the reaction path of Scheme 7 below, but is not limited thereto.

Sub 1'(Sub 1 '( 1)의1) of 합성예시 Synthetic example

The starting material, 3-amino-1,1'-biphenyl (16.92 g, 100 mmol) and 2-chlorospiro [benzo [b] fluorene-11,9'-fluorene] (40.09 g, 100 mmol) was dissolved in _{toluene (330 ml), Pd 2} (dba) 3 (2.74 g, 3 mmol), 50% P (t-Bu) 3 (3.2 ml, 8 mmol), NaOt-Bu (28.83 g, 300 mmol) And the mixture was stirred under reflux. When the reaction was completed, water was added to complete the reaction. The organic layer was extracted with MgSO ₄ and concentrated. The resulting compound was subjected to silicagel column to obtain 27.21 g (yield: 51%) of the product.

Sub 1'(Sub 1 '( 2)의2) of 합성예시 Synthetic example

The starting material, 4- (naphthalen-1-yl) aniline (21.92 g, 100 mmol) and 9-chlorospiro [benzo [c] fluorene-7,9'- fluorene] (40.09 g, 100 mmol) was dissolved in _{toluene (330 ml), Pd 2} (dba) 3 (2.74 g, 3 mmol), 50% P (t-Bu) 3 (3.2 ml, 8 mmol), NaOt-Bu (28.83 g, 300 mmol) And the mixture was stirred under reflux. When the reaction was completed, water was added to complete the reaction. The organic layer was extracted, dried over MgSO ₄ and concentrated. The resulting compound was subjected to silica gel column chromatography to obtain 29.76 g (yield: 51%) of the product.

Sub 1'(Sub 1 '( 3)의3) of 합성예시 Synthetic example

The starting material, 4- (naphthalen-1-yl) aniline (21.92 g, 100 mmol) and 2-chlorospiro [benzo [b] fluorene-11,9'- fluorene] (40.09 g, 100 mmol) was dissolved in _{toluene (330 ml), Pd 2} (dba) 3 (2.74 g, 3 mmol), 50% P (t-Bu) 3 (3.2 ml, 8 mmol), NaOt-Bu (28.83 g, 300 mmol) And the mixture was stirred under reflux. When the reaction was completed, water was added to complete the reaction. The organic layer was extracted, dried over MgSO ₄ and concentrated. The resulting compound was subjected to silica gel column chromatography to obtain 28.01 g (yield: 48%) of the product.

Sub 1'(Sub 1 '( 4)의4) of 합성예시 Synthetic example

2,7-dibromo-9,9-dimethyl-9H-fluorene (35.20 g, 100 mmol) and naphthalen-2-amine (31.50 g, 220 mmol) were dissolved in toluene (330 ml) in a round bottom flask then, was added _{_{Pd 2 (dba) 3 (2.74}} g, 3 mmol), 50% P (t-Bu) 3 (3.2 ml, 8 mmol), NaOt-Bu (28.83 g, 300 mmol) and stirred at room temperature . When the reaction was completed, water was added to complete the reaction. The organic layer was extracted, dried over MgSO ₄ and concentrated. The resulting compound was subjected to silica gel column chromatography to obtain 33.36 g (yield: 70%) of the product.

Sub 1'(Sub 1 '( 5)의5) of 합성예시 Synthetic example

The starting material 2,7-dibromo-9,9-dipheyl- 9H-fluorene (47.62 g, 100 mmol) and aniline was dissolved in toluene (330 ml) in a (20.48 g, 220 mmol) round bottom flask, Pd ₂ (dba) ₃ (2.74 g, 3 mmol), 50% P (t-Bu) ₃ (3.2 ml, 8 mmol) and NaOt-Bu (28.83 g, 300 mmol) were added and stirred at room temperature. When the reaction was completed, water was added to complete the reaction. The organic layer was extracted, dried over MgSO ₄ and concentrated. The resulting compound was subjected to silica gel column chromatography to obtain 34.54 g (yield: 69%) of the product.

Examples of Sub 1 'are as follows, but not limited thereto, and Table 3 shows FD-MS (Field Desorption-Mass Spectrometry) values of Sub1' (1) to Sub1 '(5).

Sub 2' 합성 예시Sub 2 'Synthetic example

Sub 2 'of Scheme 6 can be synthesized by the reaction path of Scheme 8 below, but is not limited thereto.

Sub 2'(Sub 2 '( 2)의2) of 합성예시 Synthetic example

The starting material, 7-bromo-9,9-dimethyl- 9H-fluoren-2-ol (28.91 g, 100 mmol) and ethylenecarbonate (9.68 g, 110 mmol) , K 2 CO 3 (41.46 g, 300 mmol) and DMF (330 ml) were placed in a round bottom flask and stirred at 130 ° C. When the reaction was completed, water was added to complete the reaction. The organic layer was extracted, dried over MgSO ₄ and concentrated. The resulting compound was subjected to silicagel column to obtain 30.98 g (yield: 93%) of the product.

(33.32 g, 100 mmol) and PPh ₃ (31.47 g, 120 mmol), which was the starting material, 2 - ((7-bromo-9,9-dimethyl-9H- fluoren-2-yl) oxy) ACN (330 ml) was added to a round bottom flask and CBr ₄ (39.79 g, 120 mmol) was slowly added at 0 ° C and stirred. After 20 minutes, the temperature was again raised to room temperature and stirred. After the reaction was completed, the reaction solvent was concentrated and the organic layer was extracted with water and an organic solvent. The organic layer was dried over MgSO ₄ and concentrated. The resulting compound was subjected to silicagel column to obtain 35.64 g (yield: 90%) of the product.

Sub 2'(Sub 2 '( 3)의3) of 합성예시 Synthetic example

The starting material, 7-bromo-9,9-diphenyl- 9H-fluoren-2-ol (41.33 g, 100 mmol) and ethylenecarbonate (9.68 g, 110 mmol) , K 2 CO 3 (41.46 g, 300 mmol) and DMF (330 ml) were placed in a round bottom flask and stirred at 130 ° C. When the reaction was completed, water was added to complete the reaction. The organic layer was extracted, dried over MgSO ₄ and concentrated. The resulting compound was subjected to silica gel column chromatography to obtain 42.52 g (yield: 93%) of the product.

1-ol (45.73 g, 100 mmol) and PPh ₃ (31.47 g, 120 mmol), the starting material, 2 - ACN (330 ml) was added to a round bottom flask and CBr ₄ (39.79 g, 120 mmol) was slowly added at 0 ° C and stirred. After 20 minutes, the temperature was again raised to room temperature and stirred. After completion of the reaction, the reaction solvent was concentrated, and the organic layer was extracted with water and an organic solvent. The organic layer was dried over MgSO ₄ and concentrated. The resulting compound was subjected to silicagel column chromatography to obtain 46.81 g of the product (yield: 90%).

Examples of Sub 2 'are as follows, but not limited thereto, and Table 4 shows FD-MS (Field Desorption-Mass Spectrometry) values of Sub 2' (1) to Sub 2 '(3).

Core 1'(Core 1 '( 1)의1) of 합성예시 Synthetic example

The starting material, Sub1 '(1) (53.36 g , 100 mmol) and Sub2' (2) was dissolved in toluene (330 ml) in a (39.61 g, 100 mmol) round bottom flask was _{_{added, Pd 2 (dba) 3 (}} 2.74 g, 3 mmol), 50% P (t-Bu) ₃ (3.2 ml, 8 mmol) and NaOt-Bu (28.83 g, 300 mmol) were added and refluxed with stirring. When the reaction was completed, water was added to complete the reaction. The organic layer was extracted with MgSO ₄ and concentrated. The resulting compound was subjected to silicagel column to obtain 38.19 g (yield: 45%) of the product.

Core 1'(Core 1 '( 2)의2) of 합성예시 Synthetic example

The starting material, Sub1 '(2) (58.37 g , 100 mmol) and Sub2' (2) was dissolved in toluene (330 ml) in a (39.61 g, 100 mmol) round bottom flask was _{_{added, Pd 2 (dba) 3 (}} 2.74 g, 3 mmol), 50% P (t-Bu) ₃ (3.2 ml, 8 mmol) and NaOt-Bu (28.83 g, 300 mmol) were added and refluxed with stirring. When the reaction was completed, water was added to complete the reaction. The organic layer was extracted, dried over MgSO ₄ and concentrated. The resulting compound was subjected to silicagel column to obtain 43.14 g (yield: 48%) of the product.

Core 1'(Core 1 '( 3)의3) of 합성예시 Synthetic example

The starting material, Sub1 '(3) (58.37 g , 100 mmol) and Sub2' (3) was dissolved in toluene (330 ml) in a (52.02 g, 100 mmol) round bottom flask was _{_{added, Pd 2 (dba) 3 (}} 2.74 g, 3 mmol), 50% P (t-Bu) ₃ (3.2 ml, 8 mmol) and NaOt-Bu (28.83 g, 300 mmol) were added and refluxed with stirring. When the reaction was completed, water was added to complete the reaction. The organic layer was extracted, dried over MgSO ₄ and concentrated. The resulting compound was subjected to silicagel column to obtain 45.01 g (yield: 44%) of the product.

Core 1'(Core 1 '( 4)의4) of 합성예시 Synthetic example

The starting material, Sub1 '(4) (47.66 g , 100 mmol) and Sub2' (2) (79.22 g , 200 mmol) to a round bottom flask was dissolved in _{toluene (330 ml), Pd 2} (dba) 3 (2.74 g, 3 mmol), 50% P (t-Bu) ₃ (3.2 ml, 8 mmol) and NaOt-Bu (28.83 g, 300 mmol) were added and refluxed with stirring. When the reaction was completed, water was added to complete the reaction. The organic layer was extracted, dried over MgSO ₄ and concentrated. The resulting compound was silicagel column to obtain 67.52 g (yield: 61%) of the product.

Core 1'(Core 1 '( 5)의5) of 합성예시 Synthetic example

The starting material, Sub1 '(5) (50.06 g , 100 mmol) and Sub2' (2) (79.22 g , 200 mmol) to a round bottom flask was dissolved in _{toluene (330 ml), Pd 2} (dba) 3 (2.74 g, 3 mmol), 50% P (t-Bu) ₃ (3.2 ml, 8 mmol) and NaOt-Bu (28.83 g, 300 mmol) were added and refluxed with stirring. When the reaction was completed, water was added to complete the reaction. The organic layer was extracted, dried over MgSO ₄ and concentrated. The resultant compound was subjected to silica gel column chromatography to obtain 62.20 g (yield: 55%) of the product.

Examples of Core 1 'are as follows, but not limited thereto, and Table 5 shows FD-MS (Field Desorption-Mass Spectrometry) values of the compounds for Core 1' (1) to Core 1 '(5) .

In addition, the compound represented by the formula (1) according to the present invention (Final Product P3) is prepared by reacting Core 1 'and Sub 3' as shown in the following reaction formula (3).

Final product 1 합성 예시Final product 1 Synthetic example

P-3 합성예시Example of P-3 synthesis

Subsequently, 2-bromo-9,9'-spirobi [fluorene] (12.00 g, 30.36 mmol) and Sub 1 (2) (10.18 g, 30.36 mmol) were dissolved in toluene (150 ml) (1.22 g, 91.07 mmol), Pd ₂ (dba) ₃ (1.39 g, 1.52 mmol), 50% P (t-Bu) ₃ (1.22 ml, 3.04 mmol) and the mixture was stirred at 80 ° C. When the reaction was completed, water was added to complete the reaction. The organic layer was extracted, dried over MgSO ₄ and concentrated. The resulting compound was subjected to silicagel column to obtain 16.41 g (yield: 83%) of the product.

P-30 합성예시P-30 Synthetic Example

A mixture of 2-chlorospiro [benzo [b] fluorene-11,9'-fluorene] (14.00 g, 34.92 mmol), Sub 1 (21) (12.62 g, 34.92 mmol), toluene (180 mL), Pd ₂ a _{dba) 3 (1.60 g, 1.75} mmol), 50% P (t-Bu) 3 (1.41 ml, 3.49 mmol), NaOt-Bu (10.13 g, 104.76 mmol) proceeds in the same manner as in experiment way of the P-3 To obtain 20.73 g (yield: 82%) of the product.

P-33 합성예시P-33 Synthetic Example

The starting material 9-chlorospiro [benzo [c] fluorene-7,9'-fluorene] (11.50 g, 28.68 mmol), Sub 1 (5) (11.81 g, 28.68 mmol), toluene (150 ml), Pd ₂ a _{dba) 3 (1.31 g, 1.43} mmol), 50% P (t-Bu) 3 (1.16 ml, 2.87 mmol), NaOt-Bu (8.32 g, 86.05 mmol) proceeds in the same manner as in experiment way of the P-3 To obtain 18.72 g (yield: 84%) of the product.

Final product 2 합성 예시Final product 2 Synthetic example

P-73 합성예시Example of P-73 synthesis

(1.30 g, 21.76 mmol), Sub 1 (1.30 g, 21.76 mmol), toluene (110 mL), Pd ₂ (dba) ₃ (1.00 g, 1.09 mmol), 50 15.88 g (Yield: 85%) of the product was obtained by proceeding in the same manner as in the above-mentioned P-3, by using the same procedure as in the above-mentioned P-3, except that P (t-Bu) ₃ (0.88 ml, 2.18 mmol) and NaOt-Bu (6.31 g, 65.28 mmol) .

P-76 합성예시P-76 Synthetic examples

Pd ₂ (dba) ₃ (0.85 g, 0.93 mmol), 50 (0.13 g, 18.52 mmol), Sub 1 (27) (4.06 g, 18.52 mmol) (P-t-Bu) ₃ (0.74 ml, 1.85 mmol) and NaOt-Bu (5.37 g, 55.55 mmol) were processed in the same manner as in the above P-3 to obtain 11.96 g .

P-80 합성예시Example of P-80 synthesis

Sub1 (20) (7.01 g, 24.56 mmol), toluene (120 ml), Pd ₂ (dba) ₃ (1.12 g, 1.23 mmol), Sub 50 (16.72 g, 24.56 mmol) 18.19 g (Yield: 84%) of the product was obtained by proceeding in the same manner as in the above-mentioned P-3 except that% P (t-Bu) ₃ (0.99 ml, 2.46 mmol) and NaOt-Bu (7.13 g, 73.69 mmol) .

Final product 3 합성 예시Final product 3 Synthetic example

P-115 합성예시P-115 Synthetic example

(1) (84.88 g, 100 mmol) and DMF (2 mL) were added to a round-bottomed flask equipped with a reflux condenser, a stirrer, a reflux condenser, (100 ml) was added and stirred at 100 占 폚. When the reaction was completed, water was added to complete the reaction. The organic layer was extracted, dried over MgSO ₄ and concentrated. The resulting compound was silicagel column to obtain 42.00 g (yield: 50%) of the product.

P-116 합성예시P-116 Synthetic Example

(2) (89.89 g, 100 mmol) and DMF (2 mL) were added to a round-bottom flask equipped with a reflux condenser, a stirrer, a reflux condenser, (100 ml) was added and stirred at 100 占 폚. When the reaction was completed, water was added to complete the reaction. The organic layer was extracted with MgSO ₄ and concentrated. The resulting compound was subjected to silica gel column chromatography to obtain 47.17 g (yield: 53%) of the product.

P-117 합성예시Example of P-117 synthesis

3 (102.30 g, 100 mmol) and DMF (10 mL) were added to a round-bottomed flask equipped with a reflux condenser, a stirrer, a reflux condenser, (100 ml) was added and stirred at 100 占 폚. When the reaction was completed, water was added to complete the reaction. The organic layer was extracted, dried over MgSO ₄ and concentrated. The resulting compound was subjected to silica gel column chromatography to obtain 51.67 g (yield: 51%) of the product.

P-118 합성예시Example of P-118 synthesis

(110.70 g, 100 mmol) and DMF (10 mL) were added to a round-bottomed flask equipped with a reflux condenser, a stirrer, a reflux condenser, and a mixture of acrylic acid (7.2 g, (100 ml) was added and stirred at 100 占 폚. When the reaction was completed, water was added to complete the reaction. The organic layer was extracted, dried over MgSO ₄ and concentrated. The resulting compound was subjected to silicagel column to obtain 43.57 g (yield: 40%) of the product.

P-119 합성예시Example of P-119 synthesis

(113.10 g, 100 mmol) and DMF (10 mL) were added to a round bottom flask equipped with a reflux condenser, a stirrer, a reflux condenser, a reflux condenser, and a mixture of acrylic acid (7.2 g, (100 ml) was added and stirred at 100 占 폚. When the reaction was completed, water was added to complete the reaction. The organic layer was extracted, dried over MgSO ₄ and concentrated. The resulting compound was subjected to silica gel column chromatography to obtain 44.53 g (yield: 40%) of the product.

Table 6 shows FD-MS (Field Desorption-Mass Spectrometry) values of the compounds for P-1 to P-114. Table 7 shows FD-MS (Field Desorption-Mass Spectrometry).

유기발광소자 봉지용 조성물의 제조평가Evaluation of Manufacture of Composition for Encapsulating Organic Light Emitting Device

[실시예 1] [Example 1]

In Example 1, (A) 5.6 parts by weight of P-30 of the present invention as an ultraviolet screening agent, (B) 55.0 parts by weight of 1,10-decanediol diacrylate (TCI) as di (meth) 36.7 parts by weight of 3-phenoxybenzyl acrylate (KPX) as mono (meth) acrylate, 1.8 parts by weight of Darocur TPO (BASF) as an initiator (D), CHISORB 336 DBC) were placed in a 20 ml brown vial and mixed at room temperature for 2 hours using a shaker to prepare a sealing composition (viscosity of 18.5 cps at 25 캜).

[실시예 2] [Example 2]

In Example 2, 5.6 parts by weight of P-34 of the present invention as an ultraviolet screening agent (A2), 55.0 parts by weight of 1,10-decanediol diacrylate (TCI) as di (meth) acrylate (B) 36.7 parts by weight of 3-phenoxybenzyl acrylate (KPX) as mono (meth) acrylate, 1.8 parts by weight of Darocur TPO (BASF) as an initiator (D), CHISORB 336 DBC) were placed in a 20 ml brown vial and mixed at room temperature for 2 hours using a shaker to prepare a sealing composition (viscosity of 18.8 cps at 25 캜).

[실시예 3] [Example 3]

In Example 3, (A3) 5.6 parts by weight of P-73 of the present invention as an ultraviolet screening agent, (B) 55.0 parts by weight of 1,10-decanediol diacrylate (TCI) as di (meth) acrylate, 36.7 parts by weight of 3-phenoxybenzyl acrylate (KPX) as mono (meth) acrylate, 1.8 parts by weight of Darocur TPO (BASF) as an initiator (D), CHISORB 336 DBC) were placed in a 20 ml brown vial and mixed at room temperature for 2 hours using a shaker to prepare a sealing composition (viscosity of 18.1 cps at 25 캜).

[실시예 4] [Example 4]

In Example 4, 5.6 parts by weight of P-76 of the present invention as an ultraviolet screening agent, (B) 55.0 parts by weight of 1,10-decanediol diacrylate (TCI) as di (meth) acrylate, 36.7 parts by weight of 3-phenoxybenzyl acrylate (KPX) as mono (meth) acrylate, 1.8 parts by weight of Darocur TPO (BASF) as an initiator (D), CHISORB 336 DBC Co., Ltd.) were put into a 20 ml brown vial and mixed at room temperature for 2 hours using a shaker to prepare a sealing composition (viscosity of 18.0 cps at 25 캜).

[실시예 5] [Example 5]

In Example 5, (A5) 5.6 parts by weight of P-80 of the present invention as an ultraviolet screening agent, (B) 55.0 parts by weight of 1,10-decanediol diacrylate (TCI) as di (meth) acrylate, 36.7 parts by weight of 3-phenoxybenzyl acrylate (KPX) as mono (meth) acrylate, 1.8 parts by weight of Darocur TPO (BASF) as an initiator (D), CHISORB 336 DBC) were placed in a 20 ml brown vial and mixed at room temperature for 2 hours using a shaker to prepare a sealing composition (viscosity of 17.8 cps at 25 캜).

[실시예 6] [Example 6]

In Example 6, (A6) 5.6 parts by weight of P-115 of the present invention as an ultraviolet screening agent, (B) 55.0 parts by weight of 1,10-decanediol diacrylate (TCI) as di (meth) acrylate, 36.7 parts by weight of 3-phenoxybenzyl acrylate (KPX) as mono (meth) acrylate, 1.8 parts by weight of Darocur TPO (BASF) as an initiator (D), CHISORB 336 DBC) were placed in a 20 ml brown vial and mixed at room temperature for 2 hours using a shaker to prepare a sealing composition (viscosity of 18.5 cps at 25 캜).

[실시예 7] [Example 7]

In Example 7, 5.6 parts by weight of P-116 of the present invention as a (A7) ultraviolet screening agent, (B) 55.0 parts by weight of 1,10-decanediol diacrylate (TCI) as di (meth) acrylate, 36.7 parts by weight of 3-phenoxybenzyl acrylate (KPX) as mono (meth) acrylate, 1.8 parts by weight of Darocur TPO (BASF) as an initiator (D), CHISORB 336 DBC) were put into 20 ml brown vials and mixed at room temperature for 2 hours using a shaker to prepare a bag composition (viscosity at 25 캜, viscosity 19.4 cps).

[실시예 8] [Example 8]

In Example 8, (A8) 5.6 parts by weight of P-117 of the present invention as an ultraviolet screening agent, (B) 55.0 parts by weight of 1,10-decanediol diacrylate (TCI) as di (meth) acrylate, 36.7 parts by weight of 3-phenoxybenzyl acrylate (KPX) as mono (meth) acrylate, 1.8 parts by weight of Darocur TPO (BASF) as an initiator (D), CHISORB 336 DBC) were placed in a 20 ml brown vial and mixed at room temperature for 2 hours using a shaker to prepare a sealing composition (viscosity of 19.2 cps at 25 캜).

[실시예 9] [Example 9]

In Example 9, 5.6 parts by weight of P-118 of the present invention as the ultraviolet screening agent, (B) 55.0 parts by weight of 1,10-decanediol diacrylate (TCI) as di (meth) acrylate, 36.7 parts by weight of 3-phenoxybenzyl acrylate (KPX) as mono (meth) acrylate, 1.8 parts by weight of Darocur TPO (BASF) as an initiator (D), CHISORB 336 DBC) were put into a 20 ml brown vial and mixed at room temperature for 2 hours using a shaker to prepare a sealing composition (viscosity of 16.8 cps at 25 캜).

[실시예 10] [Example 10]

In Example 1, 5.6 parts by weight of P-119 of the present invention as a (A10) ultraviolet screening agent, (B) 55.0 parts by weight of 1,10-decanediol diacrylate (TCI) as di (meth) acrylate, 36.7 parts by weight of 3-phenoxybenzyl acrylate (KPX) as mono (meth) acrylate, 1.8 parts by weight of Darocur TPO (BASF) as an initiator (D), CHISORB 336 DBC) were placed in a 20 ml brown vial and mixed at room temperature for 2 hours using a shaker to prepare a sealing composition (viscosity of 16.6 cps at 25 캜).

[비교예 1] [Comparative Example 1]

In Comparative Example 1, 8.8 parts by weight of TINUVIN 328 (Basf) as an ultraviolet screening agent (F1), 53.1 parts by weight of 1,10-decanediol diacrylate (TCI) as di (meth) acrylate (B) 35.4 parts by weight of 3-phenoxybenzyl acrylate (KPX) as mono (meth) acrylate, 1.8 parts by weight of Darocur TPO (BASF) as an initiator (D), and CHISORB 336 DBC) were placed in a 20 ml brown vial and mixed at room temperature for 2 hours using a shaker to prepare a sealing composition (viscosity at 25 캜 of 21.8 cps).

[비교예 2] [Comparative Example 2]

In Comparative Example 2, 8.8 parts by weight of (F2) ZIKO-460 (ZIKO) as an ultraviolet screening agent, (B) 53.1 parts by weight of 1,10-decanediol diacrylate (TCI) 35.4 parts by weight of 3-phenoxybenzyl acrylate (KPX Corp.) as (C) mono (meth) acrylate, 1.8 parts by weight of Darocur TPO (BASF) as an initiator (D), and CHISORB 336 (DBC) were placed in a 20 ml brown vial and mixed at room temperature for 2 hours using a shaker to prepare a sealing composition (viscosity at 25 캜 of 21.8 cps).

[비교예 3] [Comparative Example 3]

In Comparative Example 3, 8.8 parts by weight of (F3) Tinosorb M (Basf) as an ultraviolet screening agent, 53.1 parts by weight of 1,10-decanediol diacrylate (TCI) as di (meth) 35.4 parts by weight of 3-phenoxybenzyl acrylate (KPX) as mono (meth) acrylate, 1.8 parts by weight of Darocur TPO (BASF) as an initiator (D), and CHISORB 336 DBC) were placed in a 20 ml brown vial and mixed at room temperature for 2 hours using a shaker to prepare a sealing composition (viscosity at 25 캜 of 21.8 cps).

[비교예 4] [Comparative Example 4]

In Comparative Example 4, 8.8 parts by weight of (F4) CYASORB UV-24 (CYTEC) as an ultraviolet screening agent, 53.1 parts by weight of 1,10-decanediol diacrylate (TCI) as di (meth) , 35.4 parts by weight of 3-phenoxybenzyl acrylate (KPX Corp.) as the mono (meth) acrylate (C), 1.8 parts by weight of Darocur TPO (BASF) as the initiator (D), and CHISORB (DBC) were placed in a 20 ml brown vial and mixed at room temperature for 2 hours using a shaker to prepare a sealing composition (viscosity at 25 캜 of 21.8 cps).

필름형성방법Method of film formation

₂ ml of the sealing compositions of Examples 1 to 6 and Comparative Examples 1 to 4 were applied dropwise to a 50 mm x 50 mm bare glass under N ₂ condition, and the resultant was UV-cured (1800 mJ / cm ² ) Mu m in thickness.

물성평가방법Property evaluation method

1. Transmittance

The coated and cured films were measured for transmittance in the visible light region with Lambda 950 (Perkin Elmer).

2. Outgas

Under N ₂ conditions, 5 ml of the photocurable composition was dropped on a 100 mm X 100 mm glass substrate, spin-coated, and then UV-cured (1800 mJ / cm ² ) to obtain a 4 μm thick organic protective layer specimen. The specimen was cut into 50 mm x 10 mm and used. Measurement equipment was GC / MS (SHIMADZU, GCMS-QP2020). GC / MS used a column of RTX-1 (length: 60 m, diameter: 0.25 mm, fixed bed thickness: 1 μm) as a column, helium gas (flow rate: 1.0 mL / min) 3: 1, the temperature condition is kept at 40 DEG C for 3 minutes, then the temperature is raised at a rate of 7 DEG C / min, and then the temperature is maintained at 300 DEG C for 5 minutes. Outgassing was performed by placing 5 pieces of glass size 50 mm × 10 mm in a collecting container and heating at 100 ° C. for 30 minutes to analyze outgassing. As a standard solution, a calibration curve is prepared with 25 ng, 50 ng, 100 ng and 200 ng of a toluene solution in methanol, and R2 value is obtained as 0.99. The above conditions are summarized in Table 8 below.

3. Light curing rate

Near 1635cm ^-1 (C = C), 1720cm using FT-IR (FT / IR- 6600, Jasco , Inc.) with respect to the photocurable composition ^- the intensity of the absorption peak in the vicinity of ¹ (C = O) was measured. The intensity of the absorption peak near 1635 cm ^-1 (C = C) and around 1720 cm ^-1 (C = O) was measured, and the photo-curability was calculated according to the following formula 2.

(2) Photocuring rate (%) = | 1- (A / B) | x 100

(Wherein, A is the ratio of the intensity of the absorption peak of 1635cm ^-1 in the vicinity of the intensity of the absorption peak in the vicinity of 1720cm ^-1 for the cured film, B is in the vicinity of 1720cm ^-1 for the photocurable composition The ratio of the intensity of the absorption peak at around 1635 cm < ^-1 > to the intensity of the absorption peak)

The measurement results of the sealing composition prepared in Examples and Comparative Examples are shown in Table 9, and the transmittance graphs are shown in Figs. 3 and 4.

As can be seen from the results of Table 9, Examples 1 to 10 using compositions containing A1 to A10, which are the materials of the present invention, as an ultraviolet screening agent, And a transmittance of 81.7% to 97.2% at 430 nm to 440 nm, and a transmittance of 92.9% to 93.9% in the case of the photo-curing ratio and a viscosity of 16.6 cPs to 18.8 cPs I could confirm.

More specifically, the results of Table 8 are compared only in the case of Examples 1 to 10 and Comparative Examples 1 to 4 in which all the compositions and amounts of use are different, 10 showed a transmittance of less than 2% at 400 nm, and Comparative Examples 1 to 4 showed 76.5% to 94.2%. When the transmittance was confirmed at 405 nm, it was confirmed that Examples 1 to 10 were 5% or less, and Comparative Examples 1 to 4 were 85.7% to 95.6%. It was confirmed that when the materials A1 to A10 of the present invention were used as ultraviolet screening agents, they were superior in ultraviolet screening performance to the comparative materials F1 to F4. As a result of measuring the photo-curability for use as the encapsulating material of the present invention, it was confirmed that Examples 1 to 10 and Comparative Examples 1 to 4 exhibited a light curing rate of 90% or more. It was also confirmed that the outgassing amounts of Examples 1 to 10 and Comparative Examples 1 to 4 which are photocurable compositions of the present invention were significantly lower than those of Comparative Examples.

As a result of comparing Examples 1 to 10 using the material of the present invention, it was found that the material having the lowest transmittance at 400 nm is the P-80 material used in Example 5, and the material having the lowest transmittance at 405 nm is also the material of Example 5 The P-80 material used in Examples 6 to 10 showed lower outgassing than Examples 1 to 5. It was confirmed that the heat resistance of the acrylic resin contained in the molecular structure of the ultraviolet screening agents of Examples 6 to 10 was improved by crosslinking with other compositions.

As shown in Table 9, FIG. 3 and FIG. 4, the composition for encapsulating organic light emitting diodes of the present invention has a high photo-curability using a small amount of ultraviolet absorber, and is superior in light to 347 nm to 405 nm The organic light emitting device can be protected from ultraviolet rays.

On the other hand, it was confirmed that the sealing compositions of the comparative examples were inferior in blocking ability against light having a wavelength of 347 nm to 405 nm.

The foregoing description is merely illustrative of the present invention, and various modifications may be made without departing from the essential characteristics of the present invention. Accordingly, the embodiments disclosed herein are for the purpose of limiting the present invention and are not to be construed as limiting the spirit and scope of the present invention. The scope of protection of the present invention should be construed according to the claims, and all the techniques within the scope of the same should be construed as being included in the scope of the present invention.

CROSS-REFERENCE TO RELATED APPLICATION

This patent application is related to Korean Patent Application No. 10-2017-0083479 filed on June 30, 2017, and Korean Patent Application No. 10-2018-0034007 filed on March 23, 2018, (a) (35 USC § 119 (a)), the entire contents of which are incorporated herein by reference. In addition, the present patent application is also incorporated in the present patent application as a reference, if the priority is given to the countries other than the US for the same reason as above.

Claims

(A) 1 to 10% by weight of an ultraviolet screening agent represented by the following formula (1), (B) 20 to 70% by weight of di (meth) acrylate, 5 to 40% And (D) 1% to 10% by weight of an initiator.

In Formula 1,

1) Ar 1 , Ar 2 and Ar 3 are each independently the same or different and are C 6 -C 60 aryl; A fluorenyl group; A C 2 to C 60 heterocyclic group containing at least one heteroatom selected from O, N, S, Si and P; A fused ring group of a C 3 to C 30 aliphatic ring and a C 6 to C 30 aromatic ring; An alkyl group having 1 to 60 carbon atoms; An alkenyl group having 2 to 60 carbon atoms; An alkynyl group of C 2 to C 60 ; A C 1 to C 30 alkoxy group; An aryloxy group of C 6 to C 30 ; L'-N (Ar 4 ) (Ar 5 )

2) L 'is a single bond; An arylene group having 6 to 60 carbon atoms; A heterocyclic group of C 2 ~ C 60; A fluorenylene group; A fused ring group of an aliphatic ring of C 3 to C 30 and an aromatic ring of C 6 to C 30 ,

3) Ar 4 and Ar 5 are each independently the same or different and are C 6 -C 60 aryl; A fluorenyl group; A C 2 to C 60 heterocyclic group containing at least one heteroatom selected from O, N, S, Si and P; A fused ring group of a C 3 to C 30 aliphatic ring and a C 6 to C 30 aromatic ring; An alkyl group having 1 to 60 carbon atoms; An alkenyl group having 2 to 60 carbon atoms; An alkynyl group of C 2 to C 60 ; A C 1 to C 60 alkoxy group; And an aryloxy group having 6 to 60 carbon atoms.

The Ar 1 To Ar 5 And when L 'is a fluorenylene group which is an aryl group, a fluorenyl group, an arylene group, a heterocyclic group, a fused ring group, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group or an aryloxy group; heavy hydrogen; A silane group substituted or unsubstituted with an aryl group having 6 to 20 carbon atoms; Siloxyl group; Cyano; A nitro group; An alkyl thio group of C 1 to C 30 ; A C 1 to C 30 alkoxy group; An alkyl group having 1 to 30 carbon atoms; An alkenyl group having 2 to 30 carbon atoms; An alkynyl group of C 2 to C 30 ; A C 6 to C 30 aryl group; A C 6 -C 30 aryl group substituted with deuterium; A fluorenyl group; A heterocyclic group of C 2 ~ C 30; A C 3 to C 30 cycloalkyl group; An arylalkyl group having 7 to 30 carbon atoms, and an arylalkenyl group having 8 to 30 carbon atoms, and these substituents may be further bonded to each other to form a ring, Refers to a fused ring consisting of an aliphatic ring having 3 to 20 carbon atoms or an aromatic ring having 6 to 20 carbon atoms or a heterocyclic ring having 2 to 20 carbon atoms, or a combination thereof, and includes a saturated or unsaturated ring.
The method according to claim 1,

Wherein L 'in the formula (1) is any one of the following formulas (a-1) to (a-4).

In the above formulas (a-1) to (a-4)

1) R 1 and R 2 are each independently the same or different and independently of one another are halogen; Hydrogen; heavy hydrogen; A silane group substituted or unsubstituted with an aryl group having 6 to 20 carbon atoms; Siloxyl group; Cyano; A nitro group; An alkyl thio group of C 1 to C 30 ; A C 1 to C 30 alkoxy group; An alkyl group having 1 to 30 carbon atoms; An alkenyl group having 2 to 30 carbon atoms; An alkynyl group of C 2 to C 30 ; A C 6 to C 30 aryl group; A C 6 -C 30 aryl group substituted with deuterium; A fluorenyl group; A heterocyclic group of C 2 ~ C 30; A C 3 to C 30 cycloalkyl group; An arylalkyl group having 7 to 30 carbon atoms and an arylalkenyl group having 8 to 30 carbon atoms,

2) a, c and d are each an integer of 0 to 4, b is an integer of 0 to 6, e and f are integers of 0 to 3,

When a, b, c, d, e, and f are two or more, they are the same or different, and a plurality of R 1 s or a plurality of R 2 s or adjacent R 1 s and R 2 s are bonded to each other to form a ring In addition,

3) X is any one of NR ', O, S and CR'R "

4) R 'and R " are each independently selected from the group consisting of hydrogen, C 6 -C 20 aryl, C 2 -C 20 heterocycle, and C 1 -C 20 alkyl, R 'and R " may combine with each other to form a ring with a spy.

Wherein R 1 , R 2 , R 'and R "are the same as or different from each other selected from the group consisting of aryl, silane, siloxane, alkylthio, alkoxy, alkyl, alkenyl, If an alkyl group, an aryl alkenyl group is, each of halogen; deuterium; siloxane group;; C 6 ~ aryl group a substituted or unsubstituted silane group of the C 20 a cyano group; a nitro group; C 1 ~ Import alkylthio of C 30; an alkoxy group of C 1 ~ C 30; C 1 ~ alkyl group of C 30; C 2 ~ of the C 30 alkenyl; C 2 ~ alkynyl of C 30; a C 6 substituted with heavy hydrogen; C 6 ~ aryl group of C 30 aryl group ~ C 30; fluorene group; C 2 ~ heterocyclic group of C 30; C 3 ~ C 30 cycloalkyl group; C 7 ~ C 30 aryl group and a C 8 ~ consisting of aryl alkenyl group of C 30 And these substituents may be bonded to each other to form a ring, wherein the " ring " means a ring having 3 to 2 carbon atoms An aliphatic ring of 0 to 6 carbon atoms or an aromatic ring of 6 to 20 carbon atoms or a heterocyclic ring of 2 to 20 carbon atoms, or a combination thereof, and includes a saturated or unsaturated ring.
The method according to claim 1,

The Ar 4 of Formula 1 And Ar 5 is any one of the following formulas (b-1) to (b-4).

In the above formulas (b-1) to (b-4)

1) R 3 and R 4 are each independently the same or different and are halogen; Hydrogen; heavy hydrogen; A silane group substituted or unsubstituted with an aryl group having 6 to 20 carbon atoms; Siloxyl group; Cyano; A nitro group; An alkyl thio group of C 1 to C 30 ; A C 1 to C 30 alkoxy group; An alkyl group having 1 to 30 carbon atoms; An alkenyl group having 2 to 30 carbon atoms; An alkynyl group of C 2 to C 30 ; A C 6 to C 30 aryl group; A C 6 -C 30 aryl group substituted with deuterium; A fluorenyl group; A heterocyclic group of C 2 ~ C 30; A C 3 to C 30 cycloalkyl group; An arylalkyl group having 7 to 30 carbon atoms and an arylalkenyl group having 8 to 30 carbon atoms,

2) a ', d', e 'are integers of 0-5, b' is an integer of 0-9, c 'is an integer of 0-4, f'

In the case where a, b ', c', d ', e' and f 'are two or more, a plurality of R 3 s or a plurality of R 4 s or adjacent R 3 s and R 4 s May be bonded to each other to form an aromatic ring or a heteroaromatic ring,

3) X is any one of NR ', O, S and CR'R "

4) R 'and R "are C 6 -C 20 aryl groups; A fluorenyl group; A heterocyclic group of C 2 ~ C 20; C 1 to C 20 alkyl group, R 'and R "may combine with each other to form a ring with a spy,

5) Each of A ring and B ring is independently selected from the group consisting of an aryl group having 6 to 30 carbon atoms and a heterocyclic group having 2 to 30 carbon atoms.

Wherein R 3 , R 4 , R 'and R "are the same as or different from the above-mentioned aryl group, silane group, siloxane group, cyano group, nitro group, alkylthio group, alkoxy group, alkyl group, alkenyl group, alkynyl group, fluorenyl group, A substituted or unsubstituted C 6 -C 20 aryl group, a siloxane group, a cyano group, a nitro group, a C 1 -C 6 alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted aryloxy group, A C 1 to C 30 alkyl group, a C 1 to C 30 alkoxy group, a C 1 to C 30 alkyl group, a C 2 to C 30 alkenyl group, a C 2 to C 30 alkynyl group, a C 6 to C 30 aryl group, an aryl group of a C 6 ~ C 30 substituted with heavy hydrogen; fluorene group; C 2 ~ heterocyclic group of C 30; C 3 ~ cycloalkyl group of C 30; C 7 ~ C 30 aryl group and a C 8 ~ C 30 And the aryl group may be further substituted with one or more substituents selected from the group consisting of a halogen atom, Refers to a fused ring consisting of an aliphatic ring having 3 to 20 carbon atoms or an aromatic ring having 6 to 20 carbon atoms or a heterocyclic ring having 2 to 20 carbon atoms, or a combination thereof, and includes saturated or unsaturated rings.
The method according to claim 1,

Wherein at least one of Ar 1 , Ar 2 , and Ar 3 in Formula 1 is substituted or unsubstituted fluorenyl group derivative.
The method according to claim 1,

Wherein the composition for encapsulating an organic luminescent element further comprises a photo-curable initiator.
The method according to claim 1,

A composition for encapsulating an organic luminescent element, wherein at least two compounds different from each other among the compounds represented by the formula (1) are mixed.
The method according to claim 1,

(B) di (meth) acrylate is represented by the following formula (2).

In Formula 2,

1) R 5 and R 6 are hydrogen; heavy hydrogen; Tritium; An alkyl group having 1 to 60 carbon atoms; An alkenyl group having 2 to 60 carbon atoms; A C 1 -C 60 alkoxy group; A hydroxy group,

2) R 7 is a C 1 to C 60 alkylene group; A C 6 -C 60 arylene group; A fluorenylene group; It is selected by any one of the heterocyclic group of C 2 ~ C 60.

When each of R 5 to R 7 is an alkyl group, an alkenyl group, an alkoxy group, a hydroxyl group, an alkylene group, an arylene group, a fluorenylene group, or a heterocyclic group, heavy hydrogen; A silane group substituted or unsubstituted with an aryl group having 6 to 20 carbon atoms; Siloxyl group; Cyano; A nitro group; An alkyl thio group of C 1 to C 30 ; A C 1 to C 30 alkoxy group; An alkyl group having 1 to 30 carbon atoms; An alkenyl group having 2 to 30 carbon atoms; An alkynyl group of C 2 to C 30 ; A C 6 to C 30 aryl group; A C 6 -C 30 aryl group substituted with deuterium; A fluorenyl group; A heterocyclic group of C 2 ~ C 30; A C 3 to C 30 cycloalkyl group; An arylalkyl group having 7 to 30 carbon atoms, and an arylalkenyl group having 8 to 30 carbon atoms, and these substituents may be further bonded to each other to form a ring, Refers to a fused ring consisting of an aliphatic ring having 3 to 20 carbon atoms or an aromatic ring having 6 to 20 carbon atoms or a heterocyclic ring having 2 to 20 carbon atoms, or a combination thereof, and includes a saturated or unsaturated ring.
The method according to claim 1,

(C) mono (meth) acrylate is represented by the following formula (3).

In Formula 3,

1) L 1 is a single bond; An alkylene group of C 1 to C 26 ; A C 2 -C 26 alkenyl group; A C 1 to C 26 alkoxy group; An arylene group having 6 to 60 carbon atoms; A C 6 to C 60 aryloxy group,

2) R 5 is hydrogen; heavy hydrogen; Tritium; An alkyl group having 1 to 60 carbon atoms; A C 3 to C 30 cycloalkyl group; An alkenyl group having 2 to 60 carbon atoms; A C 1 to C 60 alkoxy group; A hydroxyl group,

3) R 7 is a C 6 to C 60 aryl group; An aryloxy group of C 6 to C 60 ; A fluorenyl group; C 2 to C 60 heteroatoms.

When each of L 1 , R 5 and R 7 is an alkylene, alkyl, alkenyl, alkoxy, arylene, aryloxy, cycloalkyl, hydroxyl, aryl, halogen; heavy hydrogen; A silane group substituted or unsubstituted with an aryl group having 6 to 20 carbon atoms; Siloxyl group; Cyano; A nitro group; An alkyl thio group of C 1 to C 30 ; A C 1 to C 30 alkoxy group; An alkyl group having 1 to 30 carbon atoms; An alkenyl group having 2 to 30 carbon atoms; An alkynyl group of C 2 to C 30 ; A C 6 to C 30 aryl group; A C 6 -C 30 aryl group substituted with deuterium; A fluorenyl group; A heterocyclic group of C 2 ~ C 30; A C 3 to C 30 cycloalkyl group; An arylalkyl group having 7 to 30 carbon atoms, and an arylalkenyl group having 8 to 30 carbon atoms, and these substituents may be further bonded to each other to form a ring, Refers to a fused ring consisting of an aliphatic ring having 3 to 20 carbon atoms or an aromatic ring having 6 to 20 carbon atoms or a heterocyclic ring having 2 to 20 carbon atoms, or a combination thereof, and includes a saturated or unsaturated ring.
The method according to claim 1,

Wherein the composition for encapsulating an organic light emitting device further comprises a light stabilizer.
10. The method of claim 9,

The light stabilizer is contained in an amount of 0.1 to 10% by weight based on the total amount of the ultraviolet light blocking agent, the (B) di (meth) acrylate, the Cl) mono (meth) acrylate and the (D) Wherein the organic light-emitting element encapsulating composition is a resin composition.
The method according to claim 1,

Wherein the compound represented by Formula 1 is any one of compounds represented by the following formulas.
The method according to claim 1,

Wherein the composition for encapsulating an organic light emitting device has a viscosity of 5 cps to 40 cps at 25 ° C.
The method according to claim 1,

Wherein the composition for encapsulating an organic light emitting device has a light transmittance of less than 10% at 400 nm and a transmittance of 90% or more at 440 nm.
Characterized in that the barrier layer formed on the organic light emitting element comprises an inorganic barrier layer and an organic barrier layer, and the organic barrier layer is formed of the composition for encapsulating an organic light emitting element according to any one of claims 1 to 11. Emitting display device.
15. The method of claim 14,

Wherein the organic barrier layer is formed by inkjet, vacuum deposition, spin coating, or slit coating.