KR20220028356A - Novel compound, coating composition comprising same, organic light emitting device using same and method of manufacturing same - Google Patents

Abstract

The present specification relates to a compound represented by chemical formula 1, a coating composition including the compound represented by chemical formula 1, an organic light emitting element using the same, and a method for manufacturing the same. According to the present invention, the compound can be used as a material for a solution process, thereby enlarging the element.

Description

Novel compound, coating composition comprising same, organic light emitting device using same, and manufacturing method thereof {NOVEL COMPOUND, COATING COMPOSITION COMPRISING SAME, ORGANIC LIGHT EMITTING DEVICE USING SAME AND METHOD OF MANUFACTURING SAME}

The present specification relates to a novel compound, a coating composition including the compound, an organic light emitting device formed using the coating composition, and a method for manufacturing the same.

The organic light emitting phenomenon is one example in which electric current is converted into visible light by an internal process of a specific organic molecule. The principle of the organic light emitting phenomenon is as follows. When an organic material layer is placed between the anode and the cathode, when a current is applied between the two electrodes, electrons and holes are respectively injected into the organic material layer from the cathode and the anode. Electrons and holes injected into the organic layer recombine to form excitons, and the excitons fall back to the ground state and emit light. An organic light emitting device using this principle may generally include a cathode, an anode, and an organic material layer disposed therebetween, for example, 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 an organic light emitting device. However, there is a problem that a lot of material loss occurs and it is difficult to manufacture a device having a large area when manufacturing an organic light emitting device through the deposition process. To solve these problems, a device using a solution process is being developed.

Accordingly, there is a demand for development of materials for solution processing.

Korean Patent Publication No. 10-2005-015902

An object of the present specification is to provide a novel compound and an organic light emitting device including the same.

A compound represented by the following formula (1) is provided.

[Formula 1]

In Formula 1,

R1 to R4 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; or an alkyl group,

R11 to R13 are the same as or different from each other, and each independently represents an aryl group unsubstituted or substituted with one or more substituents selected from the group consisting of an alkyl group, an alkoxy group, and an aryloxy group,

Ar1 to Ar6 are the same as or different from each other, and each independently an aryl group unsubstituted or substituted with one or more substituents selected from the group consisting of an alkyl group, an alkoxy group, and an aryloxy group; Or an aryl group substituted with a curable group,

Ar11 to Ar13 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; an alkyl group; an aryl group unsubstituted or substituted with one or more substituents selected from the group consisting of an alkyl group, an alkoxy group, and an aryloxy group; alkoxy group; aryloxy group; Or an aryl group substituted with a curable group,

At least one of Ar1, Ar2, and Ar11 is an aryl group substituted with a curable group, at least one of Ar3, Ar4, and Ar12 is an aryl group substituted with a curable group, and at least one of Ar5, Ar6, and Ar13 is an aryl group substituted with a curable group ,

n1, n3 and n4 are each an integer of 1 to 4, n2 is an integer of 1 to 3, and when n1 to n4 are each 2 or more, two or more substituents in parentheses are the same as or different from each other,

Each of m1 to m3 is an integer of 1 to 7, and when m1 to m3 are each 2 or more, two or more substituents in parentheses are the same as or different from each other.

The present specification provides a coating composition comprising the compound.

The present specification also includes a first electrode; a second electrode; and one or more organic material layers provided between the first electrode and the second electrode, wherein one or more of the one or more organic material layers provides an organic light emitting device including the above-described coating composition or a cured product thereof.

Finally, the present specification includes the steps of preparing a first electrode; forming one or more organic material layers on the first electrode; and forming a second electrode on the one or more organic material layers, wherein the forming of the one or more organic material layers includes forming one or more organic material layers using the coating composition. A method of manufacturing a device is provided.

The compound of Formula 1 of the present invention can be used as a material for an organic material layer of an organic light emitting device, and when applied to a device, a device having a low driving voltage and excellent efficiency and lifespan characteristics can be obtained, and it can be used as a material for a solution process. It is possible to increase the area of the device.

In addition, when the organic material layer containing the compound of Formula 1 of the present invention is formed through a solution process and then the organic material layer of the upper layer is formed through a solution process, the organic layer including the compound of Formula 1 does not dissolve in the solution process solvent of the upper layer, so the device It has the advantage that the performance does not deteriorate.

1 illustrates an example of an organic light emitting device according to an exemplary embodiment of the present specification.

Hereinafter, the present specification will be described in detail.

In the present specification, when a member (layer) is said to be located “on” another member (layer), this is not only when a member (layer) is in contact with another member but also between two members (layers). (layer) is also included.

In the present specification, when a part "includes" a certain component, this means that other components may be further included, rather than excluding other components, unless otherwise stated.

As used herein, the term “curable group” may refer to a reactive substituent that cross-links compounds between compounds by exposure to heat and/or light. Crosslinking may be generated while radicals generated while decomposing carbon-carbon multiple bonds or cyclic structures are connected by heat treatment or light irradiation.

Hereinafter, the substituents of the present specification will be described in detail.

In the present specification, “-----” refers to a site bonded to another substituent or a bonding group.

In the present specification, the term "substitution" means that a hydrogen atom bonded to a carbon atom of a compound is changed to another substituent, and the position to be substituted is not limited as long as the position at which the hydrogen atom is substituted, that is, a position where the substituent is substitutable, is not limited, When two or more substituents are substituted, two or more substituents may be the same as or different from each other.

As used herein, the term "substituted or unsubstituted" is substituted or unsubstituted with one or more substituents selected from the group consisting of deuterium, an alkyl group, a cycloalkyl group, an alkoxy group, an aryloxy group, an aryl group, and a heteroaryl group, or It means that it is unsubstituted or substituted with a substituent to which two or more substituents are connected among the substituents. For example, "a substituent in which two or more substituents are connected" may be a biphenyl group. That is, the biphenyl group may be an aryl group, and may be interpreted as a substituent in which two phenyl groups are connected.

In addition, as used herein, the term “substituted or unsubstituted” refers to deuterium, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 60 carbon atoms, and carbon atoms. It means unsubstituted or substituted with one or more substituents selected from the group consisting of an aryl group having 6 to 60 carbon atoms and a heteroaryl group having 2 to 60 carbon atoms, or substituted or unsubstituted by a substituent to which two or more substituents are connected among the exemplified substituents do.

In the present specification, the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but may be 1 to 20. According to another exemplary embodiment, the number of carbon atoms in the alkyl group is 1 to 10. Specific examples of the alkyl group include a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, etc. , but not limited to these.

In the present specification, the cycloalkyl group is not particularly limited, but may have 3 to 60 carbon atoms, and according to an exemplary embodiment, the cycloalkyl group may have 3 to 30 carbon atoms. According to another exemplary embodiment, the carbon number of the cycloalkyl group is 3 to 20. Specific examples of the cycloalkyl group include, but are not limited to, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and the like.

In the present specification, the alkoxy group may be linear or branched. The number of carbon atoms of the alkoxy group is not particularly limited, but may be 1 to 20 carbon atoms. Specific examples of the alkoxy group include a methoxy group, an ethoxy group, n-propoxy group, n-butoxy group, tert-butoxy group, n-pentyloxy group, n-hexyloxy group, n-octyloxy group, n-no It may be a nyloxy group, an n-decyloxy group, and the like, but is not limited thereto.

In the present specification, the number of carbon atoms of the aryloxy group is not particularly limited, but may be 6 to 60. Specific examples of the aryloxy group include, but are not limited to, a phenoxy group, a biphenyloxy group, and a naphthyloxy group.

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 an exemplary embodiment, the carbon number of the aryl group is 6 to 30. According to an exemplary embodiment, the carbon number of the aryl group is 6 to 20. 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 include, but is not limited to, a naphthyl group, an anthracenyl group, a phenanthrenyl group, a pyrenyl group, a perylenyl group, a triphenylenyl group, a chrysenyl group, a fluorenyl group, and the like.

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

,

등의 스피로플루오레닐기,

(9,9-디메틸플루오레닐기), 및

(9,9-디페닐플루오레닐기) 등의 치환된 플루오레닐기가 될 수 있다. 다만, 이에 한정되는 것은 아니다.When the fluorenyl group is substituted,

,

spirofluorenyl groups such as

(9,9-dimethyl fluorenyl group), and

a substituted fluorenyl group such as (9,9-diphenylfluorenyl group). However, the present invention is not limited thereto.

In the present specification, the heteroaryl group is an aromatic ring group including at least one of N, O, S, Si and Se as a heteroatom, and the number of carbon atoms is not particularly limited, but may have 2 to 60 carbon atoms. According to an exemplary embodiment, the heteroaryl group has 2 to 30 carbon atoms. Examples of the heteroaryl group include a pyridine group, a pyrrole group, a pyrimidine group, a pyridazine group, a furan group, a thiophene group, a benzothiophene group, a benzofuran group, a dibenzothiophene group, a dibenzofuran group, and the like. However, the present invention is not limited thereto.

According to an exemplary embodiment of the present specification, there is provided a compound represented by Formula 1 above.

According to an exemplary embodiment of the present specification, when an organic material layer is formed using a coating composition containing the compound of Formula 1, the curable group at the end of the compound of Formula 1 has solvent resistance after curing, so the solution process solvent of the upper layer It does not dissolve in the layer, preventing diffusion to other layers.

In an exemplary embodiment of the present specification, the compound of Formula 1 forms a space between molecules because an amine group having a bulky structure is combined with trisphenylbenzene as the center, and as a result, it has excellent solubility in organic solvents. It can be used as a process material.

In addition, in the compound of Formula 1, since holes can move in three directions centering on trisphenylbenzene, the mobility of holes increases, so that when applied in a device, the effect of improving device performance can be obtained.

According to an exemplary embodiment of the present specification, the compound represented by Formula 1 has a high HOMO energy level value of about 5.1 eV to 5.3 eV, and thus the compound of Formula 1 is included in the hole injection layer in the organic light emitting device. In this case, by facilitating the injection of holes into the hole transport layer, it has a major effect on improving the lifetime of the device.

As used herein, "energy level" means an energy level. Therefore, the energy level is interpreted to mean the absolute value of the corresponding energy value. For example, when the energy level is deep, the absolute value increases in the negative direction from the vacuum level.

In the present specification, the highest occupied molecular orbital (HOMO) refers to a molecular orbital (highest occupied molecular orbital) in the region with the highest energy in the region where electrons can participate in bonding, and the lowest unoccupied molecular orbital (LUMO). is the molecular orbital function (lowest unoccupied molecular orbital) in which electrons are in the lowest energy region among the antibonding regions, and the HOMO energy level means the distance from the vacuum level to the HOMO. In addition, the LUMO energy level means the distance from the vacuum level to the LUMO.

In the present specification, the bandgap means a difference in energy levels between HOMO and LUMO, that is, a HOMO-LUMO gap.

According to an exemplary embodiment of the present specification, the compound of Formula 1 is preferably a compound having solubility in a suitable organic solvent.

In addition, in the case of the compound according to an exemplary embodiment of the present specification, an organic light emitting device can be manufactured by a solution coating method, so that the device can have a large area.

In an exemplary embodiment of the present specification, Chemical Formula 1 is represented by the following Chemical Formula 2 or 3.

[Formula 2]

[Formula 3]

In Formulas 2 and 3,

R1 to R4, R11 to R13, Ar1 to Ar6, Ar11 to Ar13, n1 to n4, and m1 to m3 have the same definitions as in Formula 1.

According to an exemplary embodiment of the present specification, R1 to R4 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; or an alkyl group having 1 to 20 carbon atoms.

According to another exemplary embodiment, R1 to R4 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; or a methyl group.

In another exemplary embodiment, R1 is hydrogen or a methyl group.

In another exemplary embodiment, R2 is hydrogen.

In another exemplary embodiment, R3 is hydrogen or a methyl group.

In another exemplary embodiment, R4 is hydrogen or a methyl group.

According to an exemplary embodiment of the present specification, R11 to R13 are the same as or different from each other, and each independently an aryl having 6 to 60 carbon atoms, unsubstituted or substituted with one or more substituents selected from the group consisting of an alkyl group, an alkoxy group, and an aryloxy group. it's gi

According to another exemplary embodiment, R11 to R13 are the same as or different from each other, and each independently selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and an aryloxy group having 6 to 30 carbon atoms. It is a C6-C60 aryl group unsubstituted or substituted with one or more substituents.

According to another exemplary embodiment, R11 to R13 are the same as or different from each other, and each independently selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and an aryloxy group having 6 to 30 carbon atoms. a phenyl group unsubstituted or substituted with one or more substituents; or a biphenyl group unsubstituted or substituted with one or more substituents selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and an aryloxy group having 6 to 30 carbon atoms.

According to another exemplary embodiment, R11 to R13 are the same as or different from each other, and each independently a phenyl group unsubstituted or substituted with a methyl group, an ethyl group, a propyl group, a butyl group, or a phenoxy group; or a biphenyl group unsubstituted or substituted with a methyl group, an ethyl group, a propyl group, a butyl group, or a phenoxy group.

According to an exemplary embodiment of the present specification, Ar1 to Ar6 are the same as or different from each other, and each independently an aryl having 6 to 60 carbon atoms, substituted or unsubstituted with one or more substituents selected from the group consisting of an alkyl group, an alkoxy group, and an aryloxy group. energy; or an aryl group having 6 to 60 carbon atoms substituted with a curable group.

According to another exemplary embodiment, Ar1 to Ar6 are the same as or different from each other, and each independently selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and an aryloxy group having 6 to 30 carbon atoms. an aryl group having 6 to 60 carbon atoms that is unsubstituted or substituted with one or more substituents; or an aryl group having 6 to 60 carbon atoms substituted with a curable group.

In another exemplary embodiment, Ar1 to Ar6 are the same as or different from each other, and each independently a phenyl group unsubstituted or substituted with a methyl group or a butyl group; a phenyl group substituted with a curable group; or a biphenyl group substituted with a curable group.

According to an exemplary embodiment of the present specification, Ar11 to Ar13 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; an alkyl group having 1 to 20 carbon atoms; an aryl group having 6 to 60 carbon atoms which is unsubstituted or substituted with one or more substituents selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms and an aryloxy group having 6 to 30 carbon atoms; an alkoxy group having 1 to 20 carbon atoms; an aryloxy group having 6 to 60 carbon atoms; or an aryl group having 6 to 60 carbon atoms substituted with a curable group.

In an exemplary embodiment of the present specification, Ar11 to Ar13 are the same as or different from each other, and each independently hydrogen; or a phenyl group substituted with a curable group.

According to an exemplary embodiment of the present specification, at least one of Ar1, Ar2, and Ar11 is an aryl group substituted with a curable group.

In another exemplary embodiment, one of Ar1, Ar2, and Ar11 is an aryl group substituted with a curable group.

In another exemplary embodiment, one of Ar1, Ar2, and Ar11 is a phenyl group substituted with a curable group; or a biphenyl group substituted with a curable group.

According to an exemplary embodiment of the present specification, at least one of Ar3, Ar4, and Ar12 is an aryl group substituted with a curable group.

In another exemplary embodiment, one of Ar3, Ar4, and Ar12 is an aryl group substituted with a curable group.

In another exemplary embodiment, one of Ar3, Ar4, and Ar12 is a phenyl group substituted with a curable group; or a biphenyl group substituted with a curable group.

According to an exemplary embodiment of the present specification, at least one of Ar5, Ar6, and Ar13 is an aryl group substituted with a curable group.

In another exemplary embodiment, one of Ar5, Ar6, and Ar13 is an aryl group substituted with a curable group.

In another exemplary embodiment, one of Ar5, Ar6 and Ar13 is a phenyl group substituted with a curable group; or a biphenyl group substituted with a curable group.

According to an exemplary embodiment of the present specification, the curable group is any one of the following structures.

또는

이다.In one embodiment of the present specification, the curable group

or

am.

According to an exemplary embodiment of the present specification, Chemical Formula 1 is represented by Chemical Formula 4 or 5 below.

[Formula 4]

[Formula 5]

In Formulas 4 and 5,

R1 to R4, R11 to R13, Ar1 to Ar6, Ar11 to Ar13, n1 to n4, and m1 to m3 have the same definitions as in Formula 1.

In an exemplary embodiment of the present specification, Chemical Formula 1 is represented by the following Chemical Formula 6 or 7.

[Formula 6]

[Formula 7]

In Formulas 6 and 7,

R1 to R4, R11 to R13, Ar1 to Ar6, Ar11 to Ar13, n1 to n4, and m1 to m3 have the same definitions as in Formula 1.

In an exemplary embodiment of the present specification, Chemical Formula 1 may be represented by any one of the following compounds.

The compound according to an exemplary embodiment of the present specification may have a core structure as in Preparation Examples to be described later. In addition, the substituents may be combined by a method known in the art, and the type, position or number of the substituents may be changed according to a method known in the art.

In one embodiment of the present specification, there is provided a coating composition comprising the compound of Formula 1 described above.

In an exemplary 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 state. The "liquid phase" means a liquid state at room temperature and pressure.

In one embodiment of the present specification, the solvent is, for example, a chlorine-based solvent such as chloroform, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, chlorobenzene, o-dichlorobenzene; ether solvents such as tetrahydrofuran and dioxane; aromatic hydrocarbon solvents such as toluene, xylene, trimethylbenzene, and mesitylene; aliphatic hydrocarbon solvents such as cyclohexane, methylcyclohexane, n-pentane, n-hexane, n-heptane, n-octane, n-nonane, and n-decane; ketone solvents such as acetone, methyl ethyl ketone, cyclohexanone, Isophorone, Tetralone, Decalone, and Acetylacetone; ester solvents such as ethyl acetate, butyl acetate, and ethyl cellosolve acetate; Polyvalents 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, and 1,2-hexanediol alcohols and derivatives thereof; alcohol solvents such as methanol, ethanol, propanol, isopropanol and cyclohexanol; sulfoxide solvents such as dimethyl sulfoxide; and amide solvents such as N-methyl-2-pyrrolidone and N,N-dimethylformamide; A solvent such as tetralin is exemplified, but any solvent capable of dissolving or dispersing the compound of Formula 1 according to an exemplary embodiment of the present invention is sufficient, and the present invention is not limited thereto.

In another exemplary embodiment, the solvent may be used alone or as a mixture of two or more solvents.

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 comprises a p-doping material.

In the present specification, the p-doping material refers to a material that allows the host material to have p-semiconductor properties. The p-semiconductor property refers to the property of receiving or transporting holes at the highest occupied molecular orbital (HOMO) energy level, that is, the property of a material having high hole conductivity.

The p-doping material may have any one of the following structures, but is not limited thereto.

In an exemplary embodiment of the present specification, the content of the p-doping material is 0% to 50% by weight based on the compound of Formula 1 above.

In another exemplary embodiment, the content of the p doping material includes 0 to 30% by weight based on the total solid content of the coating composition. In one embodiment of the present specification, the content of the p doping material is preferably 0.01 to 30% by weight based on the total solid content of the coating composition.

In another embodiment, the coating composition is a single molecule comprising a photocurable group and / or thermosetting group; Alternatively, it may further include a single molecule including a terminal group capable of forming a polymer by heat. Monomolecules containing a photocurable group and/or a thermosetting group as described above; Alternatively, the molecular weight of a single molecule including a terminal group capable of forming a polymer by heat may be a compound of 3,000 g/mol or less.

a single molecule comprising the photocurable group and/or the thermosetting group; Alternatively, a single molecule including a terminal group capable of forming a polymer by heat may be aryl such as phenyl, biphenyl, fluorene, or naphthalene; arylamine; Alternatively, it may refer to a single molecule in which a photocurable group and/or a thermosetting group or a terminal group capable of forming a polymer by heat is substituted with fluorene.

In another exemplary embodiment, the viscosity at room temperature of the coating composition is 2 cP to 10 cP.

When the above viscosity is satisfied, it is easy to manufacture a device. Specifically, a uniform film may be formed when the organic material layer in the device is formed.

The present specification also provides an organic light emitting device formed using the coating composition.

In one embodiment of the present specification, the first electrode; a second electrode; and one or more organic material layers provided between the first electrode and the second electrode, wherein one or more of the organic material layers includes the coating composition or a cured product thereof, and the cured product of the coating composition is the The coating composition is in a cured state by heat treatment or light treatment.

In an exemplary embodiment of the present specification, the organic material layer including the coating composition or a cured product thereof is a hole transport layer or a hole injection layer.

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

In another embodiment, the organic material layer including the coating composition or a cured product thereof is a light emitting layer.

In another exemplary embodiment, the organic material layer including the coating composition or a cured product thereof is a light emitting layer, and the light emitting layer includes the compound of Formula 1 as a host of the light emitting layer.

In another exemplary embodiment, the organic material layer including the coating composition or a cured product thereof is a light emitting layer, and the light emitting layer includes the compound of Formula 1 as a dopant of the light emitting layer.

In the present specification, the cured product means that the coating composition is cured by heat treatment and/or light treatment.

In an exemplary embodiment of the present specification, the organic light emitting device includes a hole injection layer and a hole transport layer. It further includes one or more layers selected from the group consisting of an electron transport layer, an electron injection layer, an electron blocking layer, a hole blocking layer, a hole injection and transport layer, and an electron transport and injection layer.

In the exemplary 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 exemplary 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 exemplary 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.

The organic material layer of the organic light emitting device of the present specification may have a single-layer structure, but may have a multi-layer structure in which two or more organic material layers are stacked. For example, the organic light emitting device of the present invention may have a structure including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, a hole injection and transport layer, an electron injection and transport layer, etc. as an organic material layer. However, the structure of the organic light emitting device is not limited thereto and may include a smaller number of organic layers.

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

In FIG. 1 , a first electrode 201 , a hole injection layer 301 , a hole transport layer 401 , a light emitting layer 501 , an electron transport layer 601 , and a second electrode 701 are sequentially stacked on a substrate 101 . The structure of an organic light emitting device is illustrated. Here, the electron injection and transport layer means a layer that simultaneously injects and transports electrons. The hole injection layer 301 and/or the hole transport layer 401 of FIG. 1 may be formed using a coating composition including the compound of Formula 1 described above.

1 illustrates an organic light emitting device, but 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 device of the present specification may be manufactured using materials and methods known in the art, except that at least one layer of the organic material layer is formed using a coating composition including the compound of Formula 1 above.

For example, the organic light emitting device of the present specification may be manufactured by sequentially stacking an anode, an organic material layer, and a cathode on a substrate. At this time, by using a PVD (physical vapor deposition) method such as sputtering or e-beam evaporation, a metal or conductive metal oxide or an alloy thereof is deposited on a substrate to form an anode. and an organic material layer including at least one layer of a hole injection layer, a hole transport layer, a light emitting layer, an electron injection layer, an electron transport layer, a hole injection and transport layer, and an electron injection and transport layer thereon. It can be prepared by depositing a material that can be used as a cathode on it. In addition to this method, an organic light emitting device may be manufactured by sequentially depositing a cathode material, an organic material layer, and an anode material on a substrate.

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

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

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

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

In 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.

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

In one embodiment of the present specification, the step of forming one or more organic material layers using the coating composition comprises: coating the coating composition; and heat-treating or light-treating the coated coating composition.

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

In an exemplary embodiment of the present specification, the heat treatment may be performed through heat treatment, and the heat treatment temperature in the heat treatment step may be 85° C. to 250° C., and according to an exemplary embodiment, 100° C. to 250° C., In another exemplary embodiment, it may be 150 °C to 250 °C.

In another exemplary embodiment, the heat treatment time in the heat treatment step is 1 minute to 2 hours, according to an exemplary embodiment may be 1 minute to 1 hour, in another exemplary embodiment, 30 minutes to It can be 1 hour.

When the step of forming one or more organic material layers formed by using the coating composition includes the heat treatment or light treatment step, a plurality of the compounds included in the coating composition form cross-linking to provide an organic material layer including a thinned structure. can In this case, when another layer is laminated on the surface of the organic material layer formed by using the coating composition, it can be prevented from being dissolved, morphologically affected, or decomposed by a solvent.

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

As the anode material, a material having a large work function is generally preferred so that holes can be smoothly injected into the organic material layer. Specific examples of the anode material that can be used in the present invention include metals such as vanadium, chromium, copper, zinc, gold, or alloys thereof; metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); ZnO:Al or SnO ₂ : a combination of a metal such as Sb and an oxide; conductive polymers such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene](PEDOT), polypyrrole, and polyaniline, but are not limited thereto.

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

The hole injection layer is a layer for injecting holes from the electrode, and as a hole injection material, it has the ability to transport holes, so it has a hole injection effect at the anode, an excellent hole injection effect on the light emitting layer or the light emitting material, and is produced in the light emitting layer A compound which prevents the movement of excitons to the electron injection layer or the electron injection material and is excellent in the ability to form a thin film is preferred. 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 the hole injection material include the compound of Formula 1, metal porphyrin, oligothiophene, arylamine-based organic material, hexanitrile hexaazatriphenylene-based organic material, and quinacridone-based organic material. , perylene-based organic materials, anthraquinone, polyaniline, and polythiophene-based conductive polymers, but are not limited thereto.

The hole transport layer is a layer that receives holes from the hole injection layer and transports them to the light emitting layer. The hole transport material is a material capable of transporting holes from the anode or hole injection layer to the light emitting layer and has high hole mobility. material is suitable. Specific examples include, but are not limited to, an arylamine-based organic material, a conductive polymer, and a block copolymer having a conjugated portion and a non-conjugated portion together.

The hole injection and transport layer may include the material of the hole transport layer and the hole injection layer described above.

The light emitting material is a material capable of emitting light in the visible ray region by receiving and combining holes and electrons from the hole transport layer and the electron transport layer, respectively, and a material having good quantum efficiency for fluorescence or phosphorescence is preferable. Specific examples include 8-hydroxy-quinoline aluminum complex (Alq ₃ ); carbazole-based compounds; dimerized styryl compounds; BAlq; 10-hydroxybenzo quinoline-metal compounds; compounds of the benzoxazole, benzthiazole and benzimidazole series; Poly(p-phenylenevinylene) (PPV)-based polymers; spiro compounds; polyfluorene, rubrene, and the like, but is not limited thereto.

The emission layer may include a host material and a dopant material. The host material includes a condensed aromatic ring derivative or a heterocyclic compound containing compound. Specifically, condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, fluoranthene compounds, etc., and heterocyclic-containing compounds include carbazole derivatives, dibenzofuran derivatives, ladder type Furan compounds, pyrimidine derivatives, and the like, but are not limited thereto.

Examples of the dopant material include an aromatic amine derivative, a strylamine compound, a boron complex, a fluoranthene compound, and a metal complex. Specifically, the aromatic amine derivative is a condensed aromatic ring derivative having a substituted or unsubstituted arylamino group, and includes pyrene, anthracene, chrysene, periflanthene, and the like, having an arylamino group. As the styrylamine compound, a substituted or unsubstituted It is a compound in which at least one arylvinyl group is substituted in the arylamine, and one or two or more substituents selected from the group consisting of an aryl group, a silyl group, an alkyl group, a cycloalkyl group and an arylamino group are substituted or unsubstituted. Specifically, there are styrylamine, styryldiamine, styryltriamine, styryltetraamine, and the like, but is not limited thereto. In addition, the metal complex includes an iridium complex, a platinum complex, and the like, but is not limited thereto.

The electron transport layer is a layer that receives electrons from the electron injection layer and transports electrons to the light emitting layer. Do. Specific examples include Al complex of 8-hydroxyquinoline; complexes containing Alq ₃ ; organic radical compounds; hydroxyflavone-metal complexes, and the like, but are not limited thereto. The electron transport layer may be used with any desired cathode material as used in accordance with the prior art. In particular, examples of suitable cathode materials are conventional materials having a low work function and followed by a layer of aluminum or silver. Specifically cesium, barium, calcium, ytterbium and samarium, followed in each case by an aluminum layer or a silver layer.

The electron injection layer is a layer that injects electrons from the electrode, has the ability to transport electrons as an electron injection material, has an electron injection effect from the cathode, has an excellent electron injection effect on the light emitting layer or the light emitting material, and is generated in the light emitting layer A compound which prevents the exciton from moving to the hole injection layer and is excellent in the ability to form a thin film is preferable. Specifically, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, anthrone, etc., derivatives thereof, metals complex compounds and nitrogen-containing 5-membered ring derivatives, but are not limited thereto.

The electron injection and transport layer may include the material of the electron transport layer and the electron injection layer described above.

Examples of the metal complex compound include 8-hydroxyquinolinato lithium, bis(8-hydroxyquinolinato)zinc, bis(8-hydroxyquinolinato)copper, 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-crezolato)gallium, bis(2-methyl-8-quinolinato)(1-naphtolato)aluminum, bis(2-methyl-8-quinolinato)(2-naphtolato)gallium, etc. However, the present invention is not limited thereto.

The hole blocking layer is a layer that blocks the holes from reaching the cathode, and may be generally formed under the same conditions as the hole injection layer. Specifically, there are oxadiazole derivatives, triazole derivatives, phenanthroline derivatives, BCP, aluminum complex, and the like, but is not limited thereto.

The electron blocking layer is a layer that blocks electrons from reaching the anode, and a material known in the art may be used.

The organic light emitting device according to the present specification may be a top emission type, a back emission type, or a double side emission type depending on the material used.

Hereinafter, examples will be given to describe the present specification in detail. However, the embodiments according to the present specification may be modified in various other forms, and the scope of the present specification is not to be construed as being limited to the embodiments described below. The embodiments of the present specification are provided to more completely explain the present specification to those of ordinary skill in the art.

<Production Example>

Preparation Example 1: Preparation of Compound 1

10.0g (3.1 eq) of Intermediate 1, 4,4''-dibromo-5'-(4-bromophenyl)-1,1':3',1''-terphenyl 3.4g ( 1.0 eq), NaOtBu 3.0g (5 eq), and Pd(PtBu ₃ ) ₂ 128 mg (0.04 eq) were dissolved in 100 ml of Toluene and stirred under N ₂ atmosphere to react for 5 hours. After completion of the reaction, work-up was performed with H ₂ O and EA (ethyl acetate), and the organic layer was separated, dried, and filtered. Thereafter, the solvent was removed using a rotary vacuum evaporator. The obtained material was purified by column chromatography to obtain a white solid compound 1 after removal of the solvent.

Preparation Example 2: Preparation of compound 2

10.5 g (3.1 eq) of Intermediate 2, 4,4''-dibromo-5'-(4-bromophenyl)-1,1':3',1''-terphenyl 3.4 g (1.0 eq), NaOtBu in 250 ml RBF 3.0g (5 eq), Pd(PtBu ₃ ) ₂ 128 mg (0.04 eq) was dissolved in 100 ml of Toluene, stirred and stirred under N ₂ atmosphere to react for 5 hours. After completion of the reaction, work-up with H ₂ O and EA was performed, the organic layer was separated, dried, and filtered. Thereafter, the solvent was removed using a rotary vacuum evaporator. The obtained material was purified by column chromatography to obtain a white solid compound 2 after the solvent was removed.

Preparation Example 3: Preparation of compound 3

9.5 g (3.1 eq) of Intermediate 3, 4,4''-dibromo-5'-(4-bromophenyl)-1,1':3',1''-terphenyl 3.4 g (1.0 eq), NaOtBu in 250 ml RBF 3.0g (5 eq), Pd(PtBu ₃ ) ₂ 128 mg (0.04 eq) was dissolved in 100 ml of Toluene, stirred and stirred under N ₂ atmosphere to react for 5 hours. After completion of the reaction, work-up with H ₂ O and EA was performed, the organic layer was separated, dried, and filtered. Thereafter, the solvent was removed using a rotary vacuum evaporator. The obtained material was purified by column chromatography to obtain a white solid compound 3 after removal of the solvent.

Preparation Example 4: Preparation of compound 4

9.8 g (3.1 eq) of intermediate 4, 4,4''-dibromo-5'-(4-bromophenyl)-1,1':3',1''-terphenyl 3.4 g (1.0 eq), NaOtBu in 250 ml RBF 3.0g (5 eq), Pd(PtBu ₃ ) ₂ 128 mg (0.04 eq) was dissolved in 100 ml of Toluene, stirred and stirred under N ₂ atmosphere to react for 5 hours. After completion of the reaction, work-up with H ₂ O and EA was performed, the organic layer was separated, dried, and filtered. Thereafter, the solvent was removed using a rotary vacuum evaporator. The obtained material was purified by column chromatography to obtain a white solid compound 4 after removal of the solvent.

Preparation Example 5: Preparation of Comparative Compound 1

In 250ml RBF, intermediate 1' 9.4g (3.1 eq), 4,4''-dibromo-5'-(4-bromophenyl)-1,1':3',1''-terphenyl 3.4g (1.0 eq), NaOtBu 3.0g (5 eq), Pd(PtBu ₃ ) ₂ 128 mg (0.04 eq) was dissolved in 100 ml of Toluene, stirred and stirred under N ₂ atmosphere to react for 5 hours. After completion of the reaction, work-up with H ₂ O and EA was performed, the organic layer was separated, dried, and filtered. Thereafter, the solvent was removed using a rotary vacuum evaporator. The obtained material was purified by column chromatography to obtain a white solid Comparative Compound 1 after solvent removal.

Preparation Example 6: Preparation of Comparative Compound 2

9.0g (3.1 eq) of intermediate 2', 4,4''-dibromo-5'-(4-bromophenyl)-1,1':3',1''-terphenyl 3.4g (1.0 eq) in 250ml RBF, NaOtBu 3.0g (5 eq), Pd(PtBu ₃ ) ₂ 128 mg (0.04 eq) was dissolved in 100ml of Toluene, stirred and stirred under N ₂ atmosphere to react for 5 hours. After completion of the reaction, work-up with H ₂ O and EA was performed, the organic layer was separated, dried, and filtered. Thereafter, the solvent was removed using a rotary vacuum evaporator. The obtained material was purified by column chromatography to obtain a white solid Comparative Compound 2 after solvent removal.

Preparation Example 7: Preparation of Comparative Compound 3

6.5g (3.1 eq) of intermediate 3', 4,4''-dibromo-5'-(4-bromophenyl)-1,1':3',1''-terphenyl 3.4g (1.0 eq) in 250ml RBF, NaOtBu 3.0g (5 eq), Pd(PtBu ₃ ) ₂ 128 mg (0.04 eq) was dissolved in 100ml of Toluene, stirred and stirred under N ₂ atmosphere to react for 5 hours. After completion of the reaction, work-up with H ₂ O and EA was performed, the organic layer was separated, dried, and filtered. Thereafter, the solvent was removed using a rotary vacuum evaporator. The obtained material was purified by column chromatography to obtain a white solid comparative compound 3 after removal of the solvent.

Preparation 8: Preparation of Comparative Compound 4

In 250ml RBF, intermediate 4' 5.5g (3.1 eq), 4,4''-dibromo-5'-(4-bromophenyl)-1,1':3',1''-terphenyl 3.4g (1.0 eq), NaOtBu 3.0g (5 eq), Pd(PtBu ₃ ) ₂ 128 mg (0.04 eq) was dissolved in 100ml of Toluene, stirred and stirred under N ₂ atmosphere to react for 5 hours. After completion of the reaction, work-up with H ₂ O and EA was performed, the organic layer was separated, dried, and filtered. Thereafter, the solvent was removed using a rotary vacuum evaporator. The obtained material was purified by column chromatography to obtain a white solid Comparative Compound 4 after solvent removal.

<Experimental example>

<Measurement of HOMO energy level>

The HOMO energy levels of Compounds 1 to 4 and Comparative Compounds 1 to 4 prepared in Preparation Examples 1 to 8 were measured, and are shown in Table 1 below.

<Measuring method of HOMO energy level>

Each of the materials prepared in Preparation Examples 1 to 8 was dissolved in toluene solution to 2wt/v%, coated on an ITO substrate (1500 rpm), and hard baking in an N ₂ atmosphere (~190℃, 1h) and cooled for 3 minutes. After each sample was immersed in a solvent for 10 minutes, AC3 (5nW 0.05eV step) was measured.

HOMO level compound 1 5.25 eV compound 2 5.27 eV compound 3 5.3 eV compound 4 5.31 eV Comparative compound 1 5.23 eV Comparative compound 2 5.29 eV Comparative compound 3 5.45 eV

<Production of organic light emitting device>

Example 1.

A glass substrate on which indium tin oxide (ITO) was deposited to a thickness of 1500 Å was placed in distilled water in which detergent was dissolved and washed with ultrasonic waves. After washing ITO for 30 minutes, ultrasonic washing was performed for 10 minutes by repeating twice with distilled water. After washing with distilled water, ultrasonic washing with a solvent of isopropyl alcohol and acetone was performed for 30 minutes each and dried, and then the substrate was transported to a glove box.

A coating composition mixed with Compound 1 (20mg), D1 (1mg) and toluene (1mg) was spin-coated on the prepared ITO transparent electrode to form a 300Å-thick hole injection layer, and the coating composition was heated on a hot plate in air for 1 hour. hardened. After transferring to a vacuum evaporator, the following a-NPD was vacuum deposited on the hole injection layer to form a hole transport layer.

After depositing a-NPD to a thickness of 40 nm, the following HOST 1 and DOPANT 1 were vacuum-deposited in a weight ratio of 9:1 on the hole transport layer to form a light emitting layer with a thickness of 30 nm. Then, the following Alq ₃ was vacuum-deposited to 50 nm to form an electron transport layer. A cathode was formed by depositing LiF with a thickness of 0.5 nm and aluminum with a thickness of 100 nm on the electron transport layer.

In the above process, the deposition rate of the organic material was maintained at 0.4 to 0.7 Å/sec, the deposition rate of LiF of the cathode was maintained at 0.3 Å/sec, and the deposition rate of aluminum was maintained at 2 Å/sec, and the vacuum degree during deposition was 2x10 ^-7 to 3x10 ^-5 torr was maintained.

[a-NPD] [Alq ₃ ]

[D1]

Examples 2 to 4 and Comparative Examples 1 to 4

An organic light emitting diode was manufactured in the same manner as in Example 1, except that the material shown in Table 2 below was used instead of Compound 1 as the host of the hole injection layer in Example 1.

Table 2 shows the results of measuring the characteristics of the organic light emitting device manufactured by the above method at a current density of 10 mA/cm ² . At a current density of 10 mA/cm ² , the time to be 90% of the initial luminance was measured and shown as the lifespan in Table 2 below.

device hole injection layer
host hole injection layer dopant Volt efficiency
(Cd/A) QE (%) Luminance (Cd/m ² ) Life T90
(10 mA/cm ² ) Example 1 compound 1 D1 4.00 5.18 5.42 515.4 77 Example 2 compound 2 D1 4.05 5.14 5.43 508.1 60 Example 3 compound 3 D1 3.89 5.22 5.56 516.5 81 Example 4 compound 4 D1 3.75 5.08 5.32 507.7 62 Comparative Example 1 Comparative compound 1 D1 - - - - - Comparative Example 2 Comparative compound 2 D1 4.70 3.16 3.33 500.1 5 Comparative Example 3 Comparative compound 3 D1 - - - - - Comparative Example 4 Comparative compound 4 D1 4.33 1.10 1.56 447.9 11

Examples 1 to 4 use the compound of the present invention as a host of the hole injection layer.

Comparative Compound 1 and Comparative Compound 3 used in Comparative Examples 1 and 3 have a large molecular weight and a rigid structure, and have low solubility in organic solvents because they do not contain a curable group in the compound, thereby obtaining a uniform thin film Therefore, the characteristics of the device could not be measured.

Comparative Example 2 uses Comparative Compound 2 having a different bonding position between Chemical Formula 1 and the curable group of the present application, and it can be seen that the properties of the device are very poor than in Examples 1 to 4.

In addition, in Comparative Example 4, the bonding position of the curable group is different from that of Chemical Formula 1 of the present application, and Comparative Compound 4 in which dibenzofuran is bonded to the fluorene position is used. can

101: substrate
201: first electrode
301: hole injection layer
401: hole transport layer
501: light emitting layer
601: electron transport layer
701: second electrode

Claims (11)

A compound represented by the following formula (1):
[Formula 1]

In Formula 1,
R1 to R4 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; or an alkyl group,
R11 to R13 are the same as or different from each other, and each independently represents an aryl group unsubstituted or substituted with one or more substituents selected from the group consisting of an alkyl group, an alkoxy group, and an aryloxy group,
Ar1 to Ar6 are the same as or different from each other, and each independently an aryl group unsubstituted or substituted with one or more substituents selected from the group consisting of an alkyl group, an alkoxy group, and an aryloxy group; Or an aryl group substituted with a curable group,
Ar11 to Ar13 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; an alkyl group; an aryl group unsubstituted or substituted with one or more substituents selected from the group consisting of an alkyl group, an alkoxy group, and an aryloxy group; alkoxy group; aryloxy group; Or an aryl group substituted with a curable group,
At least one of Ar1, Ar2, and Ar11 is an aryl group substituted with a curable group, at least one of Ar3, Ar4, and Ar12 is an aryl group substituted with a curable group, and at least one of Ar5, Ar6 and Ar13 is an aryl group substituted with a curable group ,
n1, n3 and n4 are each an integer of 1 to 4, n2 is an integer of 1 to 3, and when n1 to n4 are each 2 or more, two or more substituents in parentheses are the same as or different from each other,
Each of m1 to m3 is an integer of 1 to 7, and when m1 to m3 are each 2 or more, two or more substituents in parentheses are the same as or different from each other. The method according to claim 1,
Formula 1 is a compound represented by Formula 2 or 3 below:
[Formula 2]

[Formula 3]

In Formulas 2 and 3,
R1 to R4, R11 to R13, Ar1 to Ar6, Ar11 to Ar13, n1 to n4, and m1 to m3 have the same definitions as in Formula 1. The method according to claim 1,
A compound wherein the curable group is any one of the following structures:

. The method according to claim 1,
Formula 1 is a compound represented by Formula 4 or 5 below:
[Formula 4]

[Formula 5]

In Formulas 4 and 5,
R1 to R4, R11 to R13, Ar1 to Ar6, Ar11 to Ar13, n1 to n4, and m1 to m3 have the same definitions as in Formula 1. The method according to claim 1,
Formula 1 is a compound represented by the following Formula 6 or 7:
[Formula 6]

[Formula 7]

In Formulas 6 and 7,
R1 to R4, R11 to R13, Ar1 to Ar6, Ar11 to Ar13, n1 to n4, and m1 to m3 have the same definitions as in Formula 1. The method according to claim 1,
The compound of Formula 1 is represented by any one of the following compounds:

. A coating composition comprising a compound according to any one of claims 1 to 6. a first electrode;
a second electrode; and
At least one organic material layer provided between the first electrode and the second electrode,
At least one of the at least one organic material layer is an organic light emitting device comprising the coating composition of claim 7 or a cured product thereof. 9. The method of claim 8,
The organic material layer comprising the coating composition or a cured product thereof is an organic light emitting device that is a hole transport layer or a hole injection layer. preparing a first electrode;
forming one or more organic material layers on the first electrode; and
Comprising the step of forming a second electrode on the one or more organic material layer,
The method of manufacturing an organic light emitting device, wherein the forming of the one or more organic material layers includes forming an organic material layer using the coating composition of claim 7 . 11. The method of claim 10,
The step of forming an organic material layer using the coating composition is
coating the coating composition; and heat-treating or light-treating the coated coating composition.

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