KR20230160202A - Compound, coating composition comprising same, organic light emitting device comprising same and method of manufacturing same - Google Patents

Abstract

This specification relates to a compound of Formula 1, a coating composition containing the same, an organic light-emitting device containing the same, and a method of manufacturing the same.

Description

Compound, coating composition containing the same, organic light emitting device containing the same, and method for manufacturing the same {COMPOUND, COATING COMPOSITION COMPRISING SAME, ORGANIC LIGHT EMITTING DEVICE COMPRISING SAME AND METHOD OF MANUFACTURING SAME}

This application claims the benefit of Korean Patent Application No. 10-2022-0059685 filed with the Korea Intellectual Property Office on May 16, 2022, the entire contents of which are incorporated herein by reference.

This specification relates to a compound, a coating composition containing the same, an organic light-emitting device containing the same, and a method of manufacturing the same.

The organic luminescence phenomenon is an example of an electric current being converted into visible light by an internal process of a specific organic molecule. The principle of organic luminescence phenomenon is as follows. When an organic layer is placed between an anode and a cathode and an electric current is applied between the two electrodes, electrons and holes are injected into the organic layer from the cathode and anode, respectively. The electrons and holes injected into the organic layer recombine to form excitons, and when these excitons fall back to the ground state, they emit light. An organic light-emitting device using this principle may generally be composed of a cathode, an anode, and an organic material layer located between them, such as a hole injection layer, a hole transport layer, a light-emitting layer, an electron injection layer, and an electron transport layer.

Conventionally, a deposition process has been mainly used to manufacture organic light-emitting devices. However, when manufacturing an organic light-emitting device using a deposition process, there are problems that a lot of material loss occurs and that it is difficult to manufacture a large-area device. To solve these problems, devices using a solution process are being developed.

Therefore, there is a need for development of materials for solution processing.

Korean Patent Publication No. 10-2000-0051826

The present specification provides a compound, a coating composition containing the same, an organic light emitting device containing the same, and a method for manufacturing the same.

An exemplary embodiment of the present specification provides a compound of Formula 1 below.

[Formula 1]

In Formula 1,

X1 to

X11 to X14 are the same as or different from each other, and are each independently hydrogen; heavy hydrogen; halogen group; Substituted or unsubstituted alkyl group; Substituted or unsubstituted cycloalkyl group; Substituted or unsubstituted aryl group; Or it is a substituted or unsubstituted heteroaryl group, or combines with an adjacent group to form a substituted or unsubstituted ring,

a1 to a4 are each an integer of 0 or 1, and a1+a2+a3+a4 are an integer of 2 to 4,

a11 to a14 are each an integer of 0 to 4, and when a11 to a14 are each an integer of 2 or more, the substituents in parentheses are the same or different from each other,

[Formula 2]

In Formula 2,

Y1 is 0, S or Se,

L1 is direct bonding; Substituted or unsubstituted alkylene group; Substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group,

R1 and R2 are the same or different from each other, and are each independently a photocurable group or a thermosetting group.

Another embodiment of the present specification provides a coating composition containing the above-described compound.

Another embodiment of the present specification includes a first electrode; second electrode; and one or more organic material layers provided between the first electrode and the second electrode, wherein at least one layer of the organic material layers includes the above-described coating composition or a cured product thereof.

Another embodiment of the present specification includes preparing a first electrode; Forming one or more organic layers on the first electrode; And forming a second electrode on the organic material layer, wherein the step of forming the organic material layer includes forming one or more organic material layers using the above-described coating composition. to provide.

Since the compound according to an exemplary embodiment of the present specification has excellent solubility, there is an advantage that various solvents can be selected when manufacturing the coating composition.

In addition, the compound according to an exemplary embodiment of the present specification has the advantage of forming a stable thin film that is not damaged in the next solution process by forming a completely cured thin film through heat treatment or light treatment.

In addition, the compound according to an exemplary embodiment of the present specification exhibits resistance to a specific solvent after curing, so a solution process is possible when manufacturing the device, thereby enabling a larger area of the device, and improving performance through the lamination process. possible.

In addition, the compound according to an embodiment of the present specification can be used as a material for the organic material layer of an organic light-emitting device, and when applied to an organic light-emitting device, a device having low driving voltage, excellent efficiency characteristics, and/or excellent lifespan characteristics can be obtained. .

1 and 2 show examples of organic light-emitting devices according to some embodiments of the present invention.
Figure 3 is a diagram showing the results of a film retention rate test of a thin film formed with coating composition 1 prepared in Experimental Example 1-1.
Figure 4 is a diagram showing the results of a film retention rate test of a thin film formed with coating composition 2 prepared in Comparative Example 1-1.

Hereinafter, the present invention will be described in detail.

An exemplary embodiment of the present specification provides a compound of Formula 1 below.

[Formula 1]

In Formula 1,

X1 to

X11 to X14 are the same as or different from each other, and are each independently hydrogen; heavy hydrogen; halogen group; Substituted or unsubstituted alkyl group; Substituted or unsubstituted cycloalkyl group; Substituted or unsubstituted aryl group; Or it is a substituted or unsubstituted heteroaryl group, or combines with an adjacent group to form a substituted or unsubstituted ring,

a1 to a4 are each an integer of 0 or 1, and a1+a2+a3+a4 are an integer of 2 to 4,

a11 to a14 are each an integer of 0 to 4, and when a11 to a14 are each an integer of 2 or more, the substituents in parentheses are the same or different from each other,

[Formula 2]

In Formula 2,

Y1 is 0, S or Se,

L1 is direct bonding; Substituted or unsubstituted alkylene group; Substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group,

R1 and R2 are the same or different from each other, and are each independently a photocurable group or a thermosetting group.

In an exemplary embodiment of the present specification, at least two of X1 to X4 are of Formula 2. That is, the compound of Formula 1 includes two or more photocurable groups or thermosetting groups.

When the compound contains a photo-curable group or a thermo-curable group, there is an advantage in forming a stable thin film that is not damaged during the next solution process by forming a completely cured thin film through heat treatment or light treatment. Therefore, since a solution process is possible when manufacturing a device, it is possible to increase the area of the device and also improve performance through a stacking process.

In this specification, when a member is said to be located “on” another member, this includes not only the case where a member is in contact with another member, but also the case where another member exists between the two members.

In this specification, when a part “includes” a certain component, this means that it does not exclude other components but may further include other components, unless specifically stated to the contrary.

In this specification, the term “substitution” means changing a hydrogen atom bonded to a carbon atom of a compound to another substituent, and the position to be substituted is not limited as long as it is the position where the hydrogen atom is substituted, that is, a position where the substituent can be substituted, When two or more substituents are substituted, the two or more substituents may be the same or different from each other.

As used herein, the term “substituted or unsubstituted” refers to deuterium; halogen group; Alkyl group; Cycloalkyl group; Alkoxy group; Aryloxy group; Amine group; Aryl group; It means that it is substituted with one or two or more substituents selected from the group consisting of heteroaryl groups, or is substituted with a substituent in which two or more of the above-exemplified substituents are linked, or does not have any substituents. For example, “a substituent group in which two or more substituents are connected” may be a biphenyl group. That is, the biphenyl group may be an aryl group, or it may be interpreted as a substituent in which two phenyl groups are connected.

As used herein, “photocurable group or thermosetting group” may refer to a reactive substituent that crosslinks compounds or polymers by exposure to light and/or heat. A photocurable group or a thermosetting group can be created by connecting radicals generated when a carbon-carbon multiple bond or cyclic structure is decomposed by light irradiation or heat treatment.

In an exemplary embodiment of the present specification, the photo-curable group or the thermo-curable group has any of the following structures.

In the above structure,

L50 to L56 are the same or different from each other and are each independently directly bonded; -O-; Substituted or unsubstituted alkylene group; Or a substituted or unsubstituted arylene group,

is a site bound to Formula 2 above.

As used herein, an “adjacent” group may mean a substituent substituted on an atom directly connected to the atom on which the substituent is substituted, a substituent located closest to the substituent in terms of structure, or another substituent substituted on the atom on which the substituent is substituted. You can. For example, two substituents substituted at ortho positions in a benzene ring and two substituents substituted on the same carbon in an aliphatic ring can be interpreted as “adjacent” groups.

In the present specification, in rings formed by combining adjacent groups, “ring” refers to a substituted or unsubstituted hydrocarbon ring; Or it means a substituted or unsubstituted heterocycle.

In this specification, And * refers to a site bound to another substituent or binding moiety.

Examples of the above substituents are described below, but are not limited thereto.

In this specification, examples of halogen groups include fluorine (F), chlorine (Cl), bromine (Br), or iodine (I).

In the present specification, the alkyl group may be straight chain or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 60. According to one embodiment, the carbon number of the alkyl group is 1 to 30. Specific examples of the alkyl group include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, and octyl groups.

In this specification, an alkylene group refers to an alkyl group having two bonding positions, that is, a bivalent group. The description of the alkyl group described above can be applied except that each of these is a divalent group.

In this specification, the number of carbon atoms in the cycloalkyl group is not particularly limited, but is preferably 3 to 60. According to one embodiment, the carbon number of the cycloalkyl group is 3 to 30. Specific examples of the cycloalkyl group include, but are not limited to, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, and cyclooctyl group.

In the present specification, the alkoxy group may be straight chain, branched chain, or ring chain. The number of carbon atoms of the alkoxy group is not particularly limited, but is preferably 1 to 30 carbon atoms. Specific examples of the alkoxy group include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentyloxy, neopentyloxy, iso It may be pentyloxy, n-hexyloxy, 3,3-dimethylbutyloxy, 2-ethylbutyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, etc., but is not limited thereto.

In the present specification, the amine group is a group represented by -NR200R201, where R200 and R201 are the same or different from each other, and are each independently hydrogen; heavy hydrogen; Substituted or unsubstituted alkyl group; Substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group. Specifically, the amine group is -NH ₂ ; Alkylamine group; Arylalkylamine group; Arylamine group; Arylheteroarylamine group; It may be selected from the group consisting of alkylheteroarylamine group and heteroarylamine group, but is not limited thereto. The number of carbon atoms of the amine group is not particularly limited, but is preferably 1 to 60.

In the present specification, the aryl group is not particularly limited, but may have 6 to 60 carbon atoms and may be a monocyclic aryl group or a polycyclic aryl group. According to one embodiment, the aryl group has 6 to 30 carbon atoms. According to one embodiment, the aryl group has 6 to 20 carbon atoms. The aryl group may be a monocyclic aryl group, such as a phenyl group, a biphenyl group, or a terphenyl group, but is not limited thereto. The polycyclic aryl group may be a naphthyl group, anthracenyl group, phenanthrenyl group, pyrenyl group, perylenyl group, triphenylenyl group, chrysenyl group, fluorenyl group, etc., but is not limited thereto.

In the present specification, the fluorenyl group may be substituted, and two substituents may be combined with each other to form a spiro structure.

When the fluorenyl group is substituted, , , and etc., and the exemplified structures may be substituted with additional substituents. However, the structure is not limited to this.

In the present specification, an arylene group refers to an aryl group having two bonding positions, that is, a bivalent group. The description of the aryl group described above can be applied, except that each of these is a divalent group.

In the present specification, the heteroaryl group is a heteroaryl group containing one or more of N, O, P, S, Si, and Se as heteroatoms, and the number of carbon atoms is not particularly limited, but may have 2 to 60 carbon atoms. According to one embodiment, the heteroaryl group has 2 to 30 carbon atoms. According to another exemplary embodiment, the heteroaryl group has 2 to 20 carbon atoms. Examples of heteroaryl groups include pyridyl group, pyrrole group, pyrimidyl group, pyridazinyl group, furanyl group, thiophene group, benzothiophene group, benzofuran group, dibenzothiophene group, dibenzofuran group, etc. However, it is not limited to these.

In the present specification, a heteroarylene group refers to a heteroaryl group having two bonding positions, that is, a bivalent group. The description of the heteroaryl group described above can be applied, except that each of these is a divalent group.

Hereinafter, the compound of Formula 1 will be described in detail.

In one embodiment of the present specification, a11 is an integer from 1 to 4.

In one embodiment of the present specification, a12 is an integer of 1 to 4.

In one embodiment of the present specification, a13 is an integer from 1 to 4.

In one embodiment of the present specification, a14 is an integer of 1 to 4.

In one embodiment of the present specification, a1+a11 is an integer from 1 to 4.

In one embodiment of the present specification, a2+a12 is an integer from 1 to 4.

In one embodiment of the present specification, a3+a13 is an integer from 1 to 4.

In one embodiment of the present specification, a4+a14 is an integer from 1 to 4.

In an exemplary embodiment of the present specification, a1 to a4 are each integers of 0 or 1, and a1+a2+a3+a4 are integers of 2 to 4.

In one embodiment of the present specification, a1 to a4 are each integers of 0 or 1, and a1+a2+a3+a4 is 2.

In an exemplary embodiment of the present specification, a1 and a2 are 0, and a3 and a4 are 1.

In an exemplary embodiment of the present specification, a1 and a3 are 1, and a2 and a4 are 0.

In an exemplary embodiment of the present specification, Formula 1 is the following Formula 1-1 or 1-2.

[Formula 1-1]

[Formula 1-2]

In Formulas 1-1 and 1-2,

X1, X3, X4, X11 to X14, a11, a12 and a14 are the same as defined in Formula 1,

a11', a13', and a14' are each integers of 1 to 3, and when a11', a13', and a14' are each integers of 2 or more, the substituents in parentheses are the same as or different from each other.

In an exemplary embodiment of the present specification, Formula 1 is the following Formula 1-1-1 or 1-2-1.

[Formula 1-1-1]

[Formula 1-2-1]

In the above formulas 1-1-1 and 1-2-1,

X11 to X14 and a11, a12 and a14 are the same as defined in Formula 1 above,

Y1 and Y2 are the same or different from each other and are each independently O, S or Se,

L1 and L2 are the same or different from each other and are each independently directly bonded; Substituted or unsubstituted alkylene group; Substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group,

R1 to R4 are the same or different from each other and are each independently a photocurable group or a thermosetting group,

a11', a13', and a14' are each integers of 1 to 3, and when a11', a13', and a14' are each integers of 2 or more, the substituents in parentheses are the same as or different from each other.

In an exemplary embodiment of the present specification, X11 to X14 are the same or different from each other, and are each independently hydrogen; heavy hydrogen; Or, it is a substituted or unsubstituted alkyl group, or combines with an adjacent group to form a substituted or unsubstituted ring.

In an exemplary embodiment of the present specification, when a12 is 2 or more, Formula 1 can be expressed as Formula 1-a below.

[Formula 1-a]

In Formula 1-a,

X1, X3, X4, X11, X13,

X12a to X12d are the same or different from each other and are each independently hydrogen; heavy hydrogen; halogen group; Substituted or unsubstituted alkyl group; Substituted or unsubstituted cycloalkyl group; Substituted or unsubstituted aryl group; It is a substituted or unsubstituted heteroaryl group, or a group (X2) represented by Formula 2, or is combined with an adjacent group to form a substituted or unsubstituted ring.

In one embodiment of the present specification, X12 is hydrogen; heavy hydrogen; Or it is a group (X2) represented by Formula 2, or it combines with an adjacent group to form a substituted or unsubstituted ring.

In one embodiment of the present specification, a12 is 2 or more, and adjacent X12s combine with each other to form a substituted or unsubstituted ring. Specifically, X12a and X12b combine to form a substituted or unsubstituted ring, X12b and X12c combine to form a substituted or unsubstituted ring, and/or X12c and do. For example, in this case, they may be represented by the following formulas 1-3 to 1-5, respectively.

In an exemplary embodiment of the present specification, Formula 1 is any one of the following Formulas 1-3 to 1-5.

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

In Formulas 1-3 to 1-5,

X1 to X4, X11,

X15 is hydrogen; heavy hydrogen; halogen group; Substituted or unsubstituted alkyl group; Substituted or unsubstituted cycloalkyl group; Substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

a15 is an integer of 1 to 6, and when a15 is an integer of 2 or more, the substituents in parentheses are the same or different from each other.

In one embodiment of the present specification, a15+a2 is an integer of 6 or less.

In one actual state of the present specification, a15+a2 is an integer from 1 to 6.

The above example of a12 being 2 or more is equally applicable to a11 being 2 or more, a13 being 2 or more, and a14 being 2 or more.

In an exemplary embodiment of the present specification, a1 to a4 of Formulas 1-3 to 1-5 are each an integer of 0 or 1, and a1+a2+a3+a4 are an integer of 2 to 4.

In an exemplary embodiment of the present specification, a1 to a4 of Formulas 1-3 to 1-5 are each an integer of 0 or 1, and a1+a2+a3+a4 is 2.

In an exemplary embodiment of the present specification, a1 and a2 of Formulas 1-3 to 1-5 are 1, and a3 and a4 are 0.

In an exemplary embodiment of the present specification, a1 and a2 of Formulas 1-3 to 1-5 are 0, and a3 and a4 are 1.

In an exemplary embodiment of the present specification, a2 and a4 in Formulas 1-3 to 1-5 are 1, and a1 and a3 are 0.

In an exemplary embodiment of the present specification, a2 and a4 in Formulas 1-3 to 1-5 are 0, and a1 and a3 are 1.

In an exemplary embodiment of the present specification, X11, X13, X14, and heavy hydrogen; Or it is a substituted or unsubstituted alkyl group.

In an exemplary embodiment of the present specification, X11, X13, X14, and Or deuterium.

In the present specification, * in Formula 2 is a site bonded to Formula 1.

In one embodiment of the present specification, L1 is a direct bond; Or it is a substituted or unsubstituted arylene group.

In one embodiment of the present specification, L1 is a direct bond; Or it is a substituted or unsubstituted arylene group having 6 to 30 carbon atoms.

In one embodiment of the present specification, L1 is a direct bond; phenylene group; biphenylene group; Or it is a naphthylene group.

In one embodiment of the present specification, L1 is a direct bond; Or it is a phenylene group.

In one embodiment of the present specification, Y1 is O.

In an exemplary embodiment of the present specification, R1 and R2 are the same as or different from each other, and each independently has one of the following structures.

In the above structure,

L50 to L56 are the same or different from each other and are each independently directly bonded; -O-; Substituted or unsubstituted alkylene group; Or a substituted or unsubstituted arylene group,

은 상기 화학식 2에 결합되는 부위이다.

is a site bound to Formula 2 above.

In an exemplary embodiment of the present specification, R1 and R2 are the same or different from each other, and each independently has one of the following structures.

In the above structure,

L54 and L55 are the same or different from each other and are each independently directly bonded; -O-; Substituted or unsubstituted alkylene group; Or a substituted or unsubstituted arylene group,

은 상기 화학식 2에 결합되는 부위이다.

is a site bound to Formula 2 above.

In an exemplary embodiment of the present specification, R1 and R2 are the same or different from each other, and each independently has one of the following structures.

In an exemplary embodiment of the present specification, the compound of Formula 1 has any one of the following structures.

The compound of Formula 1 according to an exemplary embodiment of the present specification can be prepared by a method known in the art, such as a palladium-catalyzed coupling reaction of two aryl groups each having bromine and boronic acid functional groups, or hydrogen and bromine functional groups of phosphine oxide. It can be combined by, and the type, position, or number of substituents can be changed according to techniques known in the art.

Cargo according to an exemplary embodiment of the present specification may be manufactured by the manufacturing method described later.

For example, the compound of Formula 1 may have a core structure prepared as shown in the following reaction scheme. Substituents may be combined by methods known in the art, and the type, position, or number of substituents may be changed according to techniques known in the art.

<Reaction formula>

In the above reaction formula, Ar, L and A can be changed depending on the structure of the compound to be prepared.

Hereinafter, the coating composition containing the above-mentioned compounds will be described in detail.

An exemplary embodiment of the present specification provides a coating composition containing the compound of Formula 1 described above.

In one embodiment of the present specification, the coating composition further includes a solvent. In one embodiment of the present specification, the coating composition includes the compound of Formula 1 and a solvent.

In one embodiment of the present specification, the coating composition may be in a liquid form. The “liquid phase” means that it is in a liquid state at room temperature and pressure.

In one embodiment of the present specification, when the coating composition is applied to the organic material layer, a solvent that does not dissolve the material in the lower layer is used. Accordingly, there is an advantage that the organic layer can be introduced through a solution process.

In an exemplary embodiment of the present specification, the compound includes a photocurable group or a thermocurable group, so solvent resistance is improved during heat treatment or light treatment after coating. That is, the compound is crosslinked after coating and therefore does not dissolve in a specific solvent.

For example, even if the coating composition is prepared using a solvent that dissolves the compound and the layer is prepared through a solution process, it may be resistant to the same solvent when cured through heat treatment or light treatment.

Therefore, after forming the organic layer using the above compound, it is cured through heat treatment or light treatment, so it is possible to introduce the upper layer through a solution process.

For example, when the coating composition is applied to a hole injection layer, the advantage is that the upper layer can be introduced through a solution process by using a specific solvent to which the cured coating composition is resistant when manufacturing the upper layer (hole transport layer, etc.). there is.

In one embodiment of the present specification, the solvent included in the coating composition is a solvent that dissolves the compound. Examples of solvents include chlorine-based solvents such as chloroform, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, chlorobenzene, and o-dichlorobenzene; Ether-based solvents such as tetrahydrofuran and dioxane; Aromatic hydrocarbon solvents such as toluene, xylene, trimethylbenzene, and mesitylene; Ketone-based solvents such as acetone, methyl ethyl ketone, and cyclohexanone; Ester solvents such as ethyl acetate, butyl acetate, and ethyl cellosolve acetate; Polyhydric acids such as ethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, dimethoxyethane, propylene glycol, diethoxymethane, triethylene glycol monoethyl ether, glycerin, 1,2-hexanediol, etc. alcohol and its derivatives; Alcohol-based solvents such as methanol, ethanol, propanol, isopropanol, and cyclohexanol; Sulfoxide-based solvents such as dimethyl sulfoxide; Amide-based solvents such as N-methyl-2-pyrrolidone and N,N-dimethylformamide; Benzoate-based solvents such as methyl benzoate, butyl benzoate, and 3-phenoxy benzoate; and tetralin. The solvent may be any solvent capable of dissolving or dispersing the compound according to an exemplary embodiment of the present specification, but is not limited thereto.

In one embodiment of the present specification, one type of solvent may be used alone, or two or more types of solvent may be mixed.

In one embodiment of the present specification, the coating composition does not further include a p-doping material.

In one embodiment of the present specification, the coating composition further includes a p-doping material.

In this specification, the p-doping material refers to a material that causes the host material to have p-semiconductor characteristics. The p semiconductor characteristic refers to the characteristic of injecting or transporting holes at the HOMO (highest occupied molecular orbital) energy level, that is, the characteristic of a material with high hole conductivity.

In an exemplary embodiment of the present specification, the p-doping material may be represented by any of the following structures, but is not limited thereto.

In this specification, the p-doping material is sufficient as long as it has p-semiconductor properties, and one type or two or more types can be used, and the type is not limited.

In one embodiment of the present specification, the content of the p-doping material is 0% by weight to 500% by weight based on the compound of the present invention. Specifically, the content of the p-doping material is 10% to 400% by weight based on the compound of the present invention.

In one embodiment of the present specification, the p-doping material is contained in an amount of 0 to 50% by weight based on the total solid content of the coating composition. In one embodiment of the present specification, the p-doping material preferably contains 1 to 50% by weight based on the total solids content of the coating composition, and 10 to 30% by weight based on the total solids content of the coating composition. It is more preferable to include %.

In another embodiment, the coating composition is a single molecule containing a functional group that can be crosslinked by heat or light; Or, it further includes a single molecule containing a terminal group capable of forming a polymer by heat.

In an exemplary embodiment of the present specification, a single molecule containing a functional group that can be crosslinked by heat or light; Alternatively, a single molecule containing a terminal group capable of forming a polymer by heat may be a compound with a molecular weight of 3,000 g/mol or less.

In an exemplary embodiment of the present specification, a single molecule containing a functional group that can be crosslinked by heat or light; Alternatively, single molecules containing terminal groups capable of forming polymers by heat include aryl such as phenyl, biphenyl, fluorene, and naphthalene; Arylamine; Alternatively, it may be a single molecule in which fluorene is substituted with a functional group that can be crosslinked by heat or light or a terminal group that can form a polymer by heat.

In one embodiment of the present specification, the viscosity of the coating composition at room temperature is 2 cP to 15 cP. Specifically, the viscosity of the coating composition is 2 cP to 10 cP. If the above viscosity is satisfied, it is easy to manufacture a device.

Hereinafter, an organic light emitting device formed using the above-described coating composition will be described in detail.

One embodiment of the present specification provides an organic light-emitting device formed using the coating composition.

An exemplary embodiment of the present specification includes a first electrode; second electrode; and at least one organic material layer provided between the first electrode and the second electrode, wherein at least one layer of the organic material layer includes the coating composition or a cured product thereof. At this time, the cured product of the coating composition is in a state in which the coating composition has been cured by heat treatment or light treatment.

In one embodiment of the present specification, the organic material layer containing the coating composition or a cured product thereof is a hole transport layer, a hole injection layer, or a hole injection and transport layer.

In one embodiment of the present specification, the organic material layer containing the coating composition or a cured product thereof is an electron transport layer, an electron injection layer, or an electron transport and injection layer.

In one embodiment of the present specification, the organic material layer containing the coating composition or a cured product thereof is a charge generation layer.

In one embodiment of the present specification, the organic layer containing the coating composition or a cured product thereof is a light-emitting layer.

In one embodiment of the present specification, the organic layer containing the coating composition or a cured product thereof is a light-emitting layer, and the light-emitting layer includes the compound of the present invention as a host of the light-emitting layer.

In one embodiment of the present specification, the organic material layer containing the coating composition or a cured product thereof is a light-emitting layer, and the light-emitting layer includes the compound of the present invention as a dopant of the light-emitting layer.

In one embodiment of the present specification, the organic material layer is a hole injection layer or a hole transport layer. A layer selected from the group consisting of an electron transport layer, an electron injection layer, an electron blocking layer, a hole blocking layer, a charge generation layer, a light emitting layer, a layer that simultaneously performs hole injection and hole transport, and a layer that performs both electron transport and electron injection, or Includes two or more floors.

In one embodiment of the present specification, the organic material layer includes a light emitting layer; and a common layer provided between the light emitting layer and the second electrode, wherein the common layer includes the coating composition or a cured product thereof.

In this specification, the 'common layer' is a layer excluding the light-emitting layer among examples of the above-mentioned organic layer. For example, the common layer may be one or more of a hole injection layer, a hole transport layer, an electron transport layer, an electron injection layer, a charge generation layer, a layer that simultaneously performs hole injection and hole transport, and a layer that simultaneously performs electron transport and electron injection.

In one embodiment of the present specification, the common layer includes an electron injection layer; electron transport layer; electron injection and transport layer; and at least one of a charge generation layer.

In one embodiment of the present specification, the organic light emitting device may be provided with one set of organic material layers between the first electrode and the second electrode.

In one embodiment of the present specification, the organic light emitting device may be provided with two or more sets of organic material layers between the first electrode and the second electrode.

In this specification, 'one set of organic layers' is a structure including a common layer and a light-emitting layer.

In one embodiment of the present specification, '1 set' may be expressed as '1 stack'.

In one embodiment of the present specification, the organic material layer includes a first laminate including a first common layer and a first light-emitting layer; and a second laminate including a second common layer and a second light-emitting layer.

In one embodiment of the present specification, the organic light emitting device includes a set of organic material layers between the first electrode and the second electrode. For example, the organic light emitting device may include a first electrode; first light emitting layer; first common layer; and a second electrode.

In one embodiment of the present specification, the organic light emitting device includes two sets of organic material layers between the first electrode and the second electrode. For example, the organic light emitting device may include a first electrode; first light emitting layer; first common layer; second light emitting layer; It is a structure including a second common layer and a second electrode.

In one embodiment of the present specification, the first common layer may be replaced with a first organic layer, and the second common layer may be replaced with a second organic layer.

In one embodiment of the present specification, a charge generation layer may be provided between the first stack and the second stack.

In one embodiment of the present specification, the organic material layer includes: a first laminate provided on a first electrode and including a first common layer and a first light-emitting layer; A charge generation layer provided on the first laminate; and a second laminate provided on the charge generation layer and including a second common layer and a second light-emitting layer.

In one embodiment of the present specification, the first common layer and the second common layer each include an electron injection layer; electron transport layer; and at least one of an electron injection and transport layer.

In an exemplary embodiment of the present specification, two or more layers among the first common layer, the charge generation layer, and the second common layer include the coating composition or a cured product thereof.

In one embodiment of the present specification, the first electrode is an anode and the second electrode is a cathode.

According to another exemplary embodiment, the first electrode is a cathode, and the second electrode is an anode.

In another embodiment, the organic light emitting device may be a normal type organic light emitting device in which an anode, one or more organic material layers, and a cathode are sequentially stacked on a substrate.

In another embodiment, the organic light emitting device may be an inverted type organic light emitting device in which a cathode, one or more organic material layers, and an anode are sequentially stacked on a substrate.

For example, the structure of an organic light emitting device according to an exemplary embodiment of the present specification is illustrated in FIGS. 1 and 2.

In Figure 1, a first electrode 201, a hole injection layer 301, a hole transport layer 401, a light emitting layer 501, an electron injection and transport layer 601, and a second electrode 701 are provided on the substrate 101. The structure of sequentially stacked organic light emitting devices is illustrated.

2 shows a first electrode 201, a first hole injection layer 1301, a first hole transport layer 1401, a first light emitting layer 1501, a first electron injection and transport layer 1601, on a substrate 101. The charge generation layer 2001, the second hole injection layer 2301, the second hole transport layer 2401, the second light emitting layer 2501, the second electron injection and transport layer 2601, and the second electrode 701 are sequentially formed. The structure of a stacked organic light emitting device is illustrated.

1 and 2 illustrate an organic light emitting device, and the structure of the organic light emitting device of the present invention is not limited thereto.

When the organic light emitting device includes a plurality of organic material layers, the organic material layers may be formed of the same material or different materials.

The organic light emitting devices of the present specification may be stacked in a structure as shown in the example below.

(1) Anode/hole transport layer/light emitting layer/cathode

(2) Anode/hole injection layer/hole transport layer/light emitting layer/cathode

(3) Anode/hole injection layer/hole buffer layer/hole transport layer/light emitting layer/cathode

(4) Anode/hole transport layer/light emitting layer/electron transport layer/cathode

(5) Anode/hole transport layer/light emitting layer/electron transport layer/electron injection layer/cathode

(6) Anode/hole injection layer/hole transport layer/light-emitting layer/electron transport layer/cathode

(7) Anode/hole injection layer/hole transport layer/light-emitting layer/electron transport layer/electron injection layer/cathode

(8) Anode/hole injection layer/hole buffer layer/hole transport layer/light-emitting layer/electron transport layer/cathode

(9) Anode/hole injection layer/hole buffer layer/hole transport layer/light-emitting layer/electron transport layer/electron injection layer/cathode

(10) Anode/hole transport layer/electron blocking layer/light emitting layer/electron transport layer/cathode

(11) Anode/hole transport layer/electron blocking layer/light emitting layer/electron transport layer/electron injection layer/cathode

(12) Anode/hole injection layer/hole transport layer/electron blocking layer/light emitting layer/electron transport layer/cathode

(13) Anode/hole injection layer/hole transport layer/electron blocking layer/light-emitting layer/electron transport layer/electron injection layer/cathode

(14) Anode/hole transport layer/light emitting layer/hole blocking layer/electron transport layer/cathode

(15) Anode/hole transport layer/light-emitting layer/hole blocking layer/electron transport layer/electron injection layer/cathode

(16) Anode/hole injection layer/hole transport layer/light-emitting layer/hole blocking layer/electron transport layer/cathode

(17) Anode/hole injection layer/hole transport layer/light-emitting layer/hole blocking layer/electron transport layer/electron injection layer/cathode

(18) Anode/hole injection layer/hole transport layer/electron blocking layer/light emitting layer/hole blocking layer/electron injection layer and transport layer/cathode

Additionally, the organic light emitting device may have a structure in which two or more layers each play the same role. At this time, layers playing the same role may be provided adjacent to each other, and may be provided at the top and bottom, respectively, based on the charge generation layer.

When the organic light emitting device of the present specification includes two sets of organic material layers, they may be stacked in a structure as shown in the example below.

(1) Anode/first hole transport layer/first light-emitting layer/charge generation layer/second hole transport layer/second light-emitting layer/cathode

(2) Anode / first hole injection layer / first hole transport layer / first light-emitting layer / charge generation layer / second hole injection layer / second hole transport layer / second light-emitting layer / cathode

(3) Anode / first hole injection layer / first hole buffer layer / first hole transport layer / first light-emitting layer / charge generation layer / second hole injection layer / second hole buffer layer / second hole transport layer / second light-emitting layer / cathode

(4) Anode / first hole transport layer / first light-emitting layer / first electron transport layer / charge generation layer / second hole transport layer / second light-emitting layer / second electron transport layer / cathode

(5) Anode / first hole transport layer / first light-emitting layer / first electron transport layer / first electron injection layer / charge generation layer / second hole transport layer / second light-emitting layer / second electron transport layer / second electron injection layer / cathode

(6) Anode / first hole injection layer / first hole transport layer / first light-emitting layer / first electron transport layer / charge generation layer / second hole injection layer / second hole transport layer / second light-emitting layer / second electron transport layer / cathode

(7) Anode / first hole injection layer / first hole transport layer / first light-emitting layer / first electron transport layer / first electron injection layer / charge generation layer / second hole injection layer / second hole transport layer / second light-emitting layer / Second electron transport layer/second electron injection layer/cathode

(8) Anode / first hole injection layer / first hole buffer layer / first hole transport layer / first light emitting layer / first electron transport layer / charge generation layer / second hole injection layer / second hole buffer layer / second hole transport layer / Second light emitting layer/second electron transport layer/cathode

(9) Anode / first hole injection layer / first hole buffer layer / first hole transport layer / first light emitting layer / first electron transport layer / first electron injection layer / charge generation layer / second hole injection layer / second hole buffer layer /2nd hole transport layer/2nd light emitting layer/2nd electron transport layer/2nd electron injection layer /cathode

(10) Anode / first hole transport layer / first electron blocking layer / first light-emitting layer / first electron transport layer / charge generation layer / second hole transport layer / second electron blocking layer / second light-emitting layer / second electron transport layer / cathode

(11) Anode / first hole transport layer / first electron blocking layer / first light-emitting layer / first electron transport layer / first electron injection layer / charge generation layer / second hole transport layer / second electron blocking layer / second light-emitting layer / Second electron transport layer/second electron injection layer/cathode

(12) Anode / first hole injection layer / first hole transport layer / first electron blocking layer / first light emitting layer / first electron transport layer / charge generation layer / second hole injection layer / second hole transport layer / second electron blocking layer layer/second emitting layer/second electron transport layer/cathode

(13) Anode / first hole injection layer / first hole transport layer / first electron blocking layer / first light emitting layer / first electron transport layer / first electron injection layer / charge generation layer / second hole injection layer / second hole Transport layer/second electron blocking layer/second light emitting layer/second electron transport layer/second electron injection layer/cathode

(14) Anode / first hole transport layer / first emitting layer / first hole blocking layer / first electron transport layer / charge generation layer / second hole transport layer / second emitting layer / second hole blocking layer / second electron transport layer / cathode

(15) Anode / first hole transport layer / first light-emitting layer / first hole blocking layer / first electron transport layer / first electron injection layer / charge generation layer / second hole transport layer / second light-emitting layer / second hole blocking layer / Second electron transport layer/second electron injection layer/cathode

(16) Anode / first hole injection layer / first hole transport layer / first light-emitting layer / first hole blocking layer / first electron transport layer / charge generation layer / second hole injection layer / second hole transport layer / second light-emitting layer / Second hole blocking layer/second electron transport layer/cathode

(17) Anode / first hole injection layer / first hole transport layer / first light emitting layer / first hole blocking layer / first electron transport layer / first electron injection layer / charge generation layer / second hole injection layer / second hole Transport layer/second light emitting layer/second hole blocking layer/second electron transport layer/second electron injection layer/cathode

(18) Anode / first hole injection layer / first hole transport layer / first electron blocking layer / first light emitting layer / first hole blocking layer / first electron injection layer and transport layer / charge generation layer / second hole injection layer / Second hole transport layer/second electron blocking layer/second light emitting layer/second hole blocking layer/second electron injection layer and transport layer/cathode

In the above structure, 'electron transport layer/electron injection layer' can be replaced with 'electron injection and transport layer' or 'layer that performs electron injection and electron transport simultaneously'.

Additionally, in the above structure, 'hole injection layer/hole transport layer' can be replaced with 'hole injection and transport layer' or 'layer that performs hole injection and hole transport simultaneously'.

The organic light emitting device of the present specification can be manufactured using materials and methods known in the art, except that at least one organic layer is formed using a coating composition containing the compound of the present invention.

For example, the organic light emitting device of the present specification can be manufactured by sequentially stacking an anode, an organic material layer, and a cathode on a substrate. At this time, a PVD (physical vapor deposition) method such as sputtering or e-beam evaporation is used to deposit a metal or a conductive metal oxide or an alloy thereof on the substrate to form an anode. and forming an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, and a layer that simultaneously transports and injects electrons through a solution process, a deposition process, etc., and then depositing a material that can be used as a cathode on it. It can be. In addition to this method, an organic light-emitting device can be made by sequentially depositing a cathode material, an organic material layer, and an anode material on a substrate.

This specification also provides a method of manufacturing an organic light-emitting device formed using the coating composition.

Specifically, one embodiment of the present specification includes preparing a first electrode; Forming one or more organic layers on the first electrode; and forming a second electrode on the organic layer, wherein forming the organic layer includes forming one or more organic layers using the coating composition.

In one embodiment of the present specification, the step of forming one or more organic layers using the coating composition uses a spin coating method.

In another embodiment, the step of forming one or more organic layers using the coating composition uses a printing method.

In one embodiment of the present specification, the printing method includes, for example, inkjet printing, nozzle printing, offset printing, transfer printing, or screen printing, but is not limited thereto.

The coating composition according to an exemplary embodiment of the present specification is suitable for a solution process due to its structural characteristics and can be formed by a printing method, so it is economical in terms of time and cost when manufacturing a device.

In one embodiment of the present specification, forming one or more organic layers using the coating composition includes coating the coating composition on the first electrode; and heat-treating or light-treating the coated coating composition.

In one embodiment of the present specification, the heat treatment step may be performed through heat treatment. The heat treatment temperature in the heat treatment step is 85°C to 250°C. Specifically, it may be 100°C to 250°C, and more specifically, it may be 150°C to 250°C.

In one embodiment of the present specification, the heat treatment time in the heat treatment step is 1 minute to 2 hours, according to one embodiment, it may be 1 minute to 1 hour, and in another embodiment, 10 minutes. It may be from 1 hour to 1 hour.

In an exemplary embodiment of the present specification, the light treatment step may be performed through UV irradiation. The light treatment step may be performed for 30 minutes to 5 hours.

In one embodiment of the present specification, the step of coating the coating composition on the first electrode may be a step of coating the coating composition on the first electrode, and applying the coating composition on another organic layer provided on the first electrode. This may be a coating step.

In one embodiment of the present specification, the other organic material layer refers to an organic material layer formed of another material without including a coating composition or a cured product thereof.

In the step of coating the coating composition on the first electrode, a solvent that does not dissolve the material of the lower layer is used. For example, when the coating composition is applied to the hole transport layer, the coating composition includes a solvent that does not dissolve the materials of the lower layer (first electrode, hole injection layer, etc.). Accordingly, there is an advantage that the hole transport layer can be introduced through a solution process.

Through heat treatment or light treatment of the coated coating composition, a plurality of the compounds included in the coating composition may form crosslinks, thereby providing an organic material layer including a thin film structure. In this case, when another layer is laminated on the surface of the organic layer formed using the coating composition, it can be prevented from being dissolved by a solvent, morphologically affected, or decomposed.

Therefore, when the organic material layer formed using the coating composition is formed including a heat treatment or light treatment step, the resistance to solvent increases, so that a multilayer can be formed by repeatedly performing the solution deposition and crosslinking methods, and the stability increases, thereby improving the device's stability. Lifespan characteristics can be increased.

In an exemplary embodiment of the present specification, the anode material is generally preferably a material with a large work function to ensure smooth hole injection into the organic layer. Specific examples of anode materials include metals such as vanadium, chromium, copper, zinc, and gold, or alloys thereof; metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); Combinations of metals and oxides such as ZnO:Al or SnO ₂ :Sb; Conductive polymers such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene](PEDOT), polypyrrole, and polyaniline are included, but are not limited to these.

In one embodiment of the present specification, the cathode material is preferably a material with a small work function to facilitate electron injection into the organic layer. Specific examples of cathode materials include metals such as barium, magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead, or alloys thereof; There are, but are not limited to, multi-layered materials such as LiF/Al or LiO ₂ /Al.

In one embodiment of the present specification, the hole injection layer is a layer that injects holes from an electrode, and the hole injection material has the ability to transport holes and has an excellent hole injection effect at the anode, a light emitting layer, or a light emitting material. A compound that has an injection effect, prevents excitons generated in the light-emitting layer from moving to the electron injection layer or electron injection material, and has excellent thin film forming ability is preferred. Additionally, it is preferable that the highest occupied molecular orbital (HOMO) of the hole injection material is between the work function of the anode material and the HOMO of the surrounding organic material layer. Specific examples of hole injection materials include the above-mentioned metal porphyrin, oligothiophene, arylamine-based organic material, hexanitrilehexaazatriphenylene-based organic material, quinacridone-based organic material, and perylene. ) series of organic materials, anthraquinone and polyaniline and polythiophene series of conductive polymers, etc., but are not limited to these.

In one embodiment of the present specification, the hole transport layer is a layer that receives holes from the hole injection layer and transports holes to the light-emitting layer, and the hole transport material can receive holes from the anode or the hole injection layer and transfer them to the light-emitting layer. A material with high mobility for holes is suitable. Specific examples of hole transport materials include, but are not limited to, arylamine-based organic materials, conductive polymers, and block copolymers having both conjugated and non-conjugated portions. More specifically, the hole transport layer may be a compound containing an arylamine group.

In an exemplary embodiment of the present specification, the light-emitting material included in the light-emitting layer is a material that can emit light in the visible light range by receiving holes and electrons from the hole transport layer and the electron transport layer, respectively, and combining them. Materials with good quantum efficiency are desirable. Specific examples include 8-hydroxy-quinoline aluminum complex (Alq3); Carbazole-based compounds; dimerized styryl compounds; BAlq; 10-hydroxybenzoquinoline-metal compound; Compounds of the benzoxazole, benzthiazole and benzimidazole series; Poly(p-phenylenevinylene) (PPV) series polymer; Spiro compounds; Polyfluorene, rubrene, etc., but are not limited to these.

In one embodiment of the present specification, the light emitting layer may include a host and a dopant. As the host, a condensed aromatic ring derivative or a heterocyclic ring-containing compound may be used. Specifically, condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, and fluoranthene compounds, and heterocycle-containing compounds include carbazole derivatives, dibenzofuran derivatives, and ladder-type compounds. These include, but are not limited to, furan compounds and pyrimidine derivatives. More specifically, an anthracene derivative may be used as the host.

In one embodiment of the present specification, the dopant may be an aromatic amine derivative, a strylamine compound, a boron compound, a fluoranthene compound, a metal complex, etc. Specifically, aromatic amine derivatives are condensed aromatic ring derivatives having a substituted or unsubstituted arylamino group, and include pyrene, anthracene, chrysene, and periplanthene having an arylamino group, and styrylamine compounds are substituted or unsubstituted arylamino groups. Arylamine is a compound in which at least one arylvinyl group is substituted, and is substituted or unsubstituted with one or two or more substituents selected from the group consisting of aryl group, silyl group, alkyl group, cycloalkyl group, and arylamino group. Specifically, styrylamine, styryldiamine, styryltriamine, styryltetraamine, etc. are included, but are not limited thereto. Additionally, metal complexes include, but are not limited to, iridium complexes and platinum complexes. More specifically, a compound containing boron may be used as the dopant.

In one embodiment of the present specification, the electron transport layer is a layer that receives electrons from the electron injection layer and transports the electrons to the light emitting layer. The electron transport material is a material that can easily receive electrons from the cathode and transfer them to the light-emitting layer, and a material with high mobility for electrons is suitable. Specific examples include Al complex of 8-hydroxyquinoline; Complex containing Alq3; organic radical compounds; Hydroxyflavone-metal complexes, etc., but are not limited to these. The electron transport layer can be used with any desired cathode material as used according to the prior art. In particular, examples of suitable cathode materials are conventional materials with a low work function followed by an aluminum or silver layer. Specifically, cesium, barium, calcium, ytterbium and samarium, in each case followed by an aluminum layer or a silver layer.

In one embodiment of the present specification, the electron injection layer is a layer that injects electrons from an electrode. The electron injection material has the ability to transport electrons, has an electron injection effect from the cathode, has an excellent electron injection effect to the light-emitting layer or light-emitting material, prevents movement of excitons generated in the light-emitting layer to the hole injection layer, and forms a thin film. Compounds with excellent forming ability are preferred. Specifically, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, benzoimidazole, perylenetetracarboxylic acid, phenanthroline, and preorenylidene methane. , anthrone, etc. and their derivatives, metal complex compounds, and nitrogen-containing 5-membered ring derivatives, etc., but are not limited thereto.

In an exemplary embodiment of the present specification, the metal complex compound includes 8-hydroxyquinolinato lithium, bis(8-hydroxyquinolinato)zinc, bis(8-hydroxyquinolinato)copper, and bis(8). -Hydroxyquinolinato)manganese, tris(8-hydroxyquinolinato)aluminum, tris(2-methyl-8-hydroxyquinolinato)aluminum, tris(8-hydroxyquinolinato)gallium, bis. (10-hydroxybenzo[h]quinolinato)beryllium, bis(10-hydroxybenzo[h]quinolinato)zinc, bis(2-methyl-8-quinolinato)chlorogallium, bis(2- Methyl-8-quinolinato) (o-cresolato) gallium, bis (2-methyl-8-quinolinato) (1-naphtolato) aluminum, bis (2-methyl-8-quinolinato) (2 -Naphtolato) gallium, etc., but is not limited thereto.

In one embodiment of the present specification, the electron transport layer and the electron injection layer may be formed as a layer that simultaneously performs electron transport and electron injection, and may be expressed as an electron injection and transport layer. At this time, the material applied to the electron injection and transport layer can be both the electron transport material and the electron injection material described above. For example, a benzimidazole-based compound may be used in the electron transport and injection layer.

In one embodiment of the present specification, the hole blocking layer is a layer that prevents holes from reaching the cathode, and can generally be formed under the same conditions as the hole injection layer. Specific examples of hole blocking materials include, but are not limited to, oxadiazole derivatives, triazole derivatives, phenanthroline derivatives, BCP, and aluminum complexes.

In one embodiment of the present specification, the electron blocking layer is a layer that prevents electrons from reaching the anode, and materials known in the art may be used.

The organic light emitting device according to the present specification may be a front emitting type, a back emitting type, or a double-sided emitting type depending on the material used.

Hereinafter, an experimental example will be used to explain the present specification in detail. However, the experimental examples according to the present specification may be modified into various other forms, and the scope of the present specification is not to be construed as being limited to the experimental examples described below. The experimental examples in this specification are provided to more completely explain the present specification to those with average knowledge in the art.

Synthesis example 1. Synthesis of Compound 1

2,7-dibromo-9,9'-spirobi[fluorene] (10.0 g, 1.00 eq) in a round flask equipped with a condenser. , bis(4-vinylphenyl)phosphine oxide (13.4 g, 2.5 eq), cesium carbonate (Cs ₂ CO ₃ ) (17.1 g, 2.5 eq), palladium acetate (Pd( OAc) ₂ ) (0.1 g, 0.02 eq), and 1,1'-Ferrocenediyl-bis(diphenylphosphine), dppf)) (0.46 g, 0.04 eq) ) was added, then 500 mL of dimethylformamide (DMF) was added, the temperature was raised to 120°C, and the mixture was stirred for 6 hours. After terminating the reaction by injecting distilled water, the organic solvent was extracted, concentrated under reduced pressure, purified through column chromatography, and precipitated using dichloromethane and hexane to prepare Compound 1 (10.5 g). (HPLC purity: 99.5%)

Synthesis example 2. Synthesis of Compound 2

In Synthesis Example 1, 5,9-dibromospiro[benzo[c]fluorene-7,9'-fluorene] (5,9) instead of 2,7-dibromo-9,9'-spirobi[fluorene] Compound 2 was prepared in the same manner as Synthesis Example 1, except that -dibromospiro[benzo[c]fluorene-7,9'-fluorene]) was used. (HPLC purity: 99.5%)

Synthesis example 3. Synthesis of Compound 3

In Synthesis Example 1, instead of 2,7-dibromo-9,9'-spirobi[fluorene], 2',7'-dibromospiro[benzo[c]fluorene-7,9'-fluorene] (2 Compound 3 was prepared in the same manner as Synthesis Example 1, except that ',7'-dibromospiro[benzo[c]fluorene-7,9'-fluorene]) was used (purity on HPLC: 99.5%)

Synthesis example 4. Synthesis of Compound 4

In Synthesis Example 1, instead of bis(4-vinylphenyl)phosphine oxide, di(bicyclo[4.2.0]octa-1,3,5-trien-3-yl)phosphine oxide (di(bicyclo[4.2.0) Compound 4 was prepared in the same manner as Synthesis Example 1, except that ]octa-1,3,5-trien-3-yl)phosphine oxide) was used (HPLC purity: 99.5%)

Synthesis example 5. Synthesis of Compound 5

In Synthesis Example 2, the same as Synthesis Example 2 except that di(bicyclo[4.2.0]octa-1,3,5-trien-3-yl)phosphine oxide was used instead of bis(4-vinylphenyl)phosphine oxide. Compound 5 was prepared by this method (purity on HPLC: 99.5%)

Synthesis example 6. Synthesis of Compound 6

In Synthesis Example 3, the same as Synthesis Example 3 except that di(bicyclo[4.2.0]octa-1,3,5-trien-3-yl)phosphine oxide was used instead of bis(4-vinylphenyl)phosphine oxide. Compound 6 was prepared by this method (purity on HPLC: 99.5%)

Synthesis example 7. Synthesis of Compound 7

2,7-dibromo-9,9'-spirobi[fluorene] (10.0 g, 1.00 eq), (4-(4,4,5,5-tetramethyl-1,3,2) in a round flask equipped with a condenser. -dioxaborolan-2-yl)phenyl)bis(4-vinylphenyl)phosphine oxide ((4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl)bis(4-vinylphenyl)phosphine oxide) (24.0 g, 2.5 eq), potassium carbonate (K ₂ CO ₃ ) (7.28 g, 2.5 eq) and tetrakis(triphenylphosphine)palladium(0)(tetrakistriphenylphosphine) After adding palladium(0), Pd(PPh ₃ ) ₄ ) (1.21 g, 0.02 eq), 200 mL of tetrahydrofuran (THF) and 100 mL of distilled water were added, the temperature was raised to 70°C, and the mixture was stirred for 6 hours. After completing the reaction by injecting distilled water, the organic solvent was extracted, concentrated under reduced pressure, purified through column chromatography, and precipitated using dichloromethane and hexane to prepare Compound 7 (10.5 g). (HPLC purity: 99.8%)

Synthesis example 8. Synthesis of Compound 8

In Synthesis Example 7, 5,9-dibromospiro[benzo[c]fluorene-7,9'-fluorene] (5,9) instead of 2,7-dibromo-9,9'-spirobi[fluorene] Compound 8 was prepared in the same manner as Synthesis Example 7, except that -dibromospiro[benzo[c]fluorene-7,9'-fluorene]) was used. (HPLC purity: 99.8%)

Synthesis example 9. Synthesis of Compound 9

In Synthesis Example 7, except that 2',7'-dibromospiro[benzo[c]fluorene-7,9'-fluorene] was used instead of 2,7-dibromo-9,9'-spirobi[fluorene]. Compound 9 was prepared in the same manner as Example 7. (HPLC purity: 99.8%)

Synthesis example 10. Synthesis of Compound 10

In Synthesis Example 7, di(bicyclo[4.2. 0]octa-1,3,5-trien-3-yl)(4-(4,4,5,5-tetramethyl-1,3,2-dioxabororan-2-yl)phenyl) Phosphine oxide (di(bicyclo[4.2.0]octa-1,3,5-trien-3-yl)(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2- Compound 10 was prepared in the same manner as in Synthesis Example 7, except that yl)phenyl)phosphine oxide (HPLC purity: 99.8%)

Synthesis example 11. Synthesis of Compound 11

In Synthesis Example 8, instead of (4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)bis(4-vinylphenyl)phosphine oxide, di(bicyclo[4.2.0 ]Except for using octa-1,3,5-trien-3-yl)(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)phosphine oxide. Compound 11 was prepared in the same manner as Synthesis Example 8 (purity on HPLC: 99.8%)

Synthesis example 12. Synthesis of Compound 12

In Synthesis Example 9, instead of (4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)bis(4-vinylphenyl)phosphine oxide, di(bicyclo[4.2.0 ] Compound 12 was prepared in the same manner as in Synthesis Example 9, except that octa-1,3,5-trien-3-yl)phosphine oxide was used (HPLC purity: 99.8%)

Experiment example 1. Measurement of thin film retention rate

Experiment example 1-1.

Coating composition 1 was prepared by dissolving Compound 1 prepared in Synthesis Example 1 in isopropyl alcohol at a concentration of 2 wt%.

Comparative example 1-1.

Coating composition 2 was prepared by dissolving the following comparative compound Z1 in ispropyl alcohol at a concentration of 2 wt%.

Coating compositions 1 and 2 were spin-coated on glass and heat-treated at 200°C for 10 minutes to form a thin film, and then UV-vis absorption was measured. This thin film was again soaked in cyclohexanone for 3 minutes, dried, and UV-vis absorption was measured. The thin film retention rate was confirmed by comparing the size of the maximum peak of UV absorption before and after immersion.

Figure 3 is a diagram showing the results of a film retention rate test of a thin film formed with coating composition 1.

Figure 4 is a diagram showing the results of a film retention rate test of a thin film formed with coating composition 2.

In Figures 3 and 4, (a) is the UV measurement result immediately after forming the thin film (before immersion in cyclohexanone for 3 minutes), and (b) is the UV measurement result after immersion of the thin film in cyclohexanone for 3 minutes. .

Through Figure 3, it can be seen that in the case of a thin film formed with coating composition 1, the thin film retention rate is 100%. That is, it can be confirmed that the compound according to an exemplary embodiment of the present specification has excellent solvent resistance.

On the other hand, it can be seen from Figure 4 that the thin film loss rate is large in the case of the thin film formed with coating composition 2.

Experiment example 2. Manufacturing of organic light emitting device

Experiment example 2-1.

A glass substrate coated with a thin film of ITO (indium tin oxide) to a thickness of 1,500 Å was placed in distilled water with a detergent dissolved in it and washed ultrasonically. At this time, a detergent from Fischer Co. was used, and distilled water filtered secondarily using a filter from Millipore Co. was used as distilled water. After washing the ITO for 30 minutes, ultrasonic cleaning was repeated twice with distilled water for 10 minutes. After washing with distilled water, the substrate was ultrasonic washed with a solvent such as isopropyl and acetone, dried, and then washed for 5 minutes before transporting the substrate to a glove box.

On the ITO transparent electrode, 2 wt% cyclohexanone ink containing Compound 1 prepared in Synthesis Example 1 and Compound G below at a weight ratio of 8:2 was spin coated on the ITO surface and heat treated at 220°C for 30 minutes to form a 400Å thick layer. A hole injection layer was formed.

2 wt% toluene ink of Compound A below was spin coated on the hole injection layer and heat treated at 120°C for 10 minutes to form a hole transport layer with a thickness of 200 Å. On the hole transport layer, Compound B and Compound C below were vacuum deposited at a weight ratio of 92:8 to form a light emitting layer with a thickness of 200 Å. Compound D below was vacuum deposited on the emitting layer to form an electron transport and injection layer with a thickness of 350 Å. A cathode was formed by sequentially depositing LiF to a thickness of 10 Å and aluminum to a thickness of 1000 Å on the electron transport and injection layer.

In the above process, the deposition rate of organic materials was maintained at 0.4Å/sec to 0.7Å/sec, the lithium fluoride of the cathode was maintained at a deposition rate of 0.3Å/sec, and the deposition rate of aluminum was maintained at 2Å/sec, and the vacuum degree during deposition was 5. x 10 ^-8 torr to 2 x 10 ^-7 torr was maintained.

Experiment example 2-2 to 2-12.

When manufacturing the hole injection layer (HIL), an organic light-emitting device was manufactured in the same manner as in Experimental Example 1, except that the compounds listed in Table 1 below were used instead of Compound 1.

Compounds 1 to 12 listed in Table 1 below are as follows.

compound Experimental Example 2-1 One Experimental Example 2-2 2 Experimental Example 2-3 3 Experimental Example 2-4 4 Experimental Example 2-5 5 Experimental Example 2-6 6 Experimental Example 2-7 7 Experimental Example 2-8 8 Experimental Example 2-9 9 Experimental Example 2-10 10 Experimental Example 2-11 11 Experimental Example 2-12 12

It was confirmed that the organic light emitting devices manufactured in Experimental Examples 2-1 to 2-12 were operated. Through this, it was confirmed that the compound according to the embodiment of the present invention is applicable to organic light-emitting devices.

101: substrate
201: first electrode
301: hole injection layer
401: hole transport layer
501: light emitting layer
601: electron transport layer
701: second electrode
1301: First hole injection layer
1401: first hole transport layer
1501: first emitting layer
1601: first electron transport layer
2001: Charge generation layer
2301: second hole injection layer
2401: second hole transport layer
2501: second light emitting layer
2601: second electron transport layer

Claims (15)

Compound of formula 1:
[Formula 1]

In Formula 1,
X1 to
X11 to X14 are the same as or different from each other, and are each independently hydrogen; heavy hydrogen; halogen group; Substituted or unsubstituted alkyl group; Substituted or unsubstituted cycloalkyl group; Substituted or unsubstituted aryl group; Or it is a substituted or unsubstituted heteroaryl group, or combines with an adjacent group to form a substituted or unsubstituted ring,
a1 to a4 are each an integer of 0 or 1, and a1+a2+a3+a4 are an integer of 2 to 4,
a11 to a14 are each an integer of 0 to 4, and when a11 to a14 are each an integer of 2 or more, the substituents in parentheses are the same or different from each other,
[Formula 2]

In Formula 2,
Y1 is 0, S or Se,
L1 is direct bonding; Substituted or unsubstituted alkylene group; Substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group,
R1 and R2 are the same or different from each other, and are each independently a photocurable group or a thermosetting group. In claim 1,
The compound of Formula 1 is the following Formula 1-1 or 1-2:
[Formula 1-1]

[Formula 1-2]

In Formulas 1-1 and 1-2,
X1, X3, X4, X11 to X14, a11, a12 and a14 are the same as defined in Formula 1,
a11', a13', and a14' are each integers of 1 to 3, and when a11', a13', and a14' are each integers of 2 or more, the substituents in parentheses are the same as or different from each other. In claim 1,
The compound of Formula 1 is any one of the following Formulas 1-3 to 1-5:
[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

In Formulas 1-3 to 1-5,
X1 to X4, X11,
X15 is hydrogen; heavy hydrogen; halogen group; Substituted or unsubstituted alkyl group; Substituted or unsubstituted cycloalkyl group; Substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,
a15 is an integer of 1 to 6, and when a15 is an integer of 2 or more, the substituents in parentheses are the same or different from each other. In claim 1,
A compound in which the photo-curable group or thermo-curable group has any one of the following structures:

In the above structure,
L50 to L56 are the same or different from each other and are each independently directly bonded; -O-; Substituted or unsubstituted alkylene group; Or a substituted or unsubstituted arylene group,

is a site bound to Formula 2 above. In claim 1,
X11 to X14 are the same or different from each other and are each independently hydrogen; heavy hydrogen; Or a compound that is a substituted or unsubstituted alkyl group, or is combined with an adjacent group to form a substituted or unsubstituted ring. In claim 1,
The compound of Formula 1 has any one of the following structures:

. A coating composition comprising the compound according to any one of claims 1 to 6. first electrode;
second electrode; and
Comprising one or more organic material layers provided between the first electrode and the second electrode,
An organic light-emitting device wherein at least one layer of the organic material layers includes the coating composition of claim 7 or a cured product thereof. In claim 8,
The organic material layer includes a light emitting layer; and a common layer provided between the light emitting layer and the second electrode,
An organic light emitting device wherein the common layer includes the coating composition or a cured product thereof. In claim 9,
The common layer is an electron injection layer; electron transport layer; electron injection and transport layer; and an organic light emitting device comprising at least one of a charge generation layer. In claim 8,
The organic material layer includes: a first laminate provided on a first electrode and including a first common layer and a first light-emitting layer;
A charge generation layer provided on the first laminate; and
An organic light emitting device comprising a second laminate provided on the charge generation layer and including a second common layer and a second light emitting layer. In claim 11,
The first common layer and the second common layer each include an electron injection layer; electron transport layer; and an organic light emitting device comprising at least one of an electron injection and transport layer. In claim 11,
An organic light emitting device wherein at least two layers among the first common layer, the charge generation layer, and the second common layer include the coating composition or a cured product thereof. Preparing a first electrode;
Forming one or more organic layers on the first electrode; and
Comprising the step of forming a second electrode on the organic layer,
The step of forming the organic material layer includes forming one or more organic material layers using the coating composition of claim 7. In claim 14,
The step of forming one or more organic layers using the coating composition
coating the coating composition on the first electrode; and
A method of manufacturing an organic light-emitting device comprising the step of heat-treating or light-treating the coated coating composition.