KR20180059043A - Amine-based compound, organic light emitting diode using the same and method of manufacturing the same - Google Patents

Abstract

The present specification provides an amine-based compound, a coating composition containing the same, an organic light emitting element formed by using the coating composition, and a manufacturing method thereof. By using the amine-based compound, the solubility increases to increase the solvent selectivity in an ink manufacturing process of a solution process, and the melting point and the curing temperature can be lowered.

Description

TECHNICAL FIELD [0001] The present invention relates to an amine-based compound, an organic light-emitting device using the same, and a method of manufacturing the same.

The present invention relates to an amine-based compound, a coating composition comprising the amine-based compound, an organic light-emitting device formed using the coating composition, and a method of manufacturing the same.

The organic light emission phenomenon is one example in which current is 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 positioned between the anode and the cathode, electrons and holes are injected into the organic layer from the cathode and the anode, respectively, when an electric current is applied between the two electrodes. Electrons and holes injected into the organic layer are recombined to form an exciton, and the exciton falls back to the ground state to emit light. An organic light emitting device using such a principle may be generally composed of an organic material layer including a cathode, an anode and an organic material layer disposed therebetween, for example, a hole injecting layer, a hole transporting layer, a light emitting layer, and an electron transporting layer.

As a material used in an organic light emitting device, a pure organic material or a complex in which an organic material and a metal form a complex is mostly used. Depending on the application, a hole injecting material, a hole transporting material, a light emitting material, an electron transporting material, . As the hole injecting material and the hole transporting material, an organic material having a p-type property, that is, an organic material that is easily oxidized and electrochemically stable at the time of oxidation is mainly used. On the other hand, as an electron injecting material or an electron transporting material, an organic material having an n-type property, that is, an organic material that is easily reduced and electrochemically stable when being reduced is mainly used. As the light emitting layer material, a material having both a p-type property and an n-type property, that is, a material having both a stable form in oxidation and in a reduced state is preferable, and a material having a high luminous efficiency for converting an exciton into light desirable.

In addition to the above, it is preferable that the material used in the organic light emitting device further has the following properties.

First, the material used in the organic light emitting device is preferably excellent in thermal stability. This is because joule heating occurs due to the movement of charges in the organic light emitting device. NPB, which is mainly used as a hole transport layer material, has a glass transition temperature of 100 ° C or less, which is a problem that is difficult to use in an organic light emitting device requiring a high current.

Secondly, in order to obtain a highly efficient organic light emitting device capable of driving at a low voltage, holes or electrons injected into the organic light emitting element should be smoothly transferred to the light emitting layer, and injected holes and electrons should not escape from the light emitting layer. For this purpose, the material used in the organic light emitting device should have an appropriate band gap and a HOMO or LUMO energy level. In the case of PEDOT: PSS used as a hole transport material in the organic light emitting device manufactured by the solution coating method, since the LUMO energy level is lower than the LUMO energy level of the organic material used as the light emitting layer material, There is a difficulty in.

In addition, materials used in organic light emitting devices should have excellent chemical stability, charge mobility, and interface characteristics with electrodes or adjacent layers. That is, the material used in the organic light emitting device should have little deformation of the material due to moisture or oxygen. In addition, by having appropriate hole or electron mobility, it is necessary to maximize the formation of excitons by balancing the density of holes and electrons in the light emitting layer of the organic light emitting device. And, for the stability of the device, the interface with the electrode including the metal or the metal oxide should be good.

In recent years, organic light emitting devices have been developed by using a solution process, particularly an inkjet process, in place of the existing deposition process. This can drastically reduce the cost of the organic light emitting device process. In the early days, it was attempted to develop organic light emitting devices by coating all the organic light emitting device layers by a solution process. However, since there are limitations in the current technology, only HIL, HTL, and EML are processed in a solution process, Is being studied. In order to increase the conventional coating properties, organic luminescent materials having a polymer shape have been widely used. However, due to batch-batch problems and purity problems inherent in polymers, many mono-molecular OLED materials are under development.

Korean Patent Publication No. 2012-0112277

It is an object of the present invention to provide an amine compound, a coating composition containing the amine compound, an organic light emitting device formed using the coating composition, and a method of manufacturing the same.

An embodiment of the present invention provides an amine compound represented by the following formula (1).

[Chemical Formula 1]

In Formula 1,

R1 and R2 are each independently selected from the group consisting of hydrogen, deuterium, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted amine group and a substituted or unsubstituted aryl group Group, < / RTI >

Y1 and Y2 each independently represent a photocurable group or a thermosetting group,

a to d are each independently an integer of 1 to 5,

When a to d are two or more, R1, R2, Y1 and Y2 are the same or different from each other,

When a and b are two or more, adjacent substituents may be bonded to each other to form a hydrocarbon ring.

In addition, one embodiment of the present disclosure includes a coating composition comprising the amine-based compound described above.

In addition, one embodiment of the present disclosure includes a cathode; Anode; And one or more organic layers disposed between the cathode and the anode, wherein at least one of the organic layers includes the coating composition described above, and the cured product of the coating composition is cured by heat treatment or light treatment The organic light emitting layer is in a state of being in a state of being exposed.

In addition, one embodiment of the present disclosure provides a method of manufacturing a semiconductor device, comprising: preparing a substrate; Forming a cathode or an anode on the substrate; Forming at least one organic material layer on the cathode or the anode; And forming an anode or a cathode on the organic material layer, wherein the forming the organic material layer includes forming one or more organic material layers using the above-mentioned coating composition,

Wherein the step of forming an organic layer formed using the coating composition comprises coating the coating composition on the cathode or the anode, and heat-treating or light-treating the coated composition. .

The amine compound according to one embodiment of the present invention can be subjected to a solution process, and the device can be made larger. The amine compound according to one embodiment of the present invention can be used as an organic material layer material of an organic light emitting device and can provide a low driving voltage, a high luminous efficiency and a high lifetime characteristic. The organic material layer formed using the amine compound according to one embodiment of the present specification is excellent in chemical resistance and film retention.

Further, since the solubility increases with the use of the amine compound, there is an advantage that the selection of the solvent during the production of the ink in the solution process can be broadened and the melting point and the curing temperature can be lowered.

1 shows an example of an organic light emitting device according to an embodiment of the present invention.
FIG. 2 shows the synthesis of 2,2 '- (5'-chloro- [1,1': 3 ', 1 "-terphenyl] -4,4'-diyl) bis (1,3-dioxolane) The results are shown by H-NMR.
Figures 3 and 4 are MS data for confirming the synthesis of a compound according to one embodiment of the present disclosure.
Figures 5 and 6 are GSC results to confirm the curing results of the compounds according to one embodiment of the present disclosure.

Hereinafter, the present invention will be described in more detail.

When a member is referred to herein as being " on " another member, it includes not only a member in contact with another member but also another member between the two members.

Whenever a component is referred to as " comprising ", it is to be understood that the component may include other components as well, without departing from the scope of the present invention.

One embodiment of the present invention provides a coating composition for an organic light emitting device comprising the amine compound represented by Formula 1. In the case of the coating composition for an organic light emitting diode comprising the amine compound represented by the above formula (1), it is easy to manufacture due to its excellent solubility, and a uniform coating layer can be formed using the coating composition. In addition, when mixed with a p-doping material used as a hole injecting layer, the hole transporting ability is improved due to the amine compound, so that the driving voltage is low and the light emitting efficiency is high.

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

는 다른 치환기에 연결되는 부위를 의미한다.In the present specification,

Quot; refers to a moiety that is connected to another substituent.

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

As used herein, the term " substituted or unsubstituted " heavy hydrogen; A halogen group; A nitrile group; A nitro group; A hydroxy group; An alkyl group; An alkoxy group; An alkenyl group; Silyl group; An ester group; A cycloalkyl group; An aryl group; An amine group; An arylamine group, and a heterocyclic group, or a substituted or unsubstituted aryl group to which at least two of the substituents exemplified above are connected. For example, " a substituent to which at least two 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 the present specification, examples of the halogen group include fluorine, chlorine, bromine or iodine.

In the present specification, the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 50. Specific examples include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec- N-pentyl, 3-dimethylbutyl, 2-ethylbutyl, heptyl, n-hexyl, Cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethyl Heptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 4-methylhexyl, 5-methylhexyl and the like.

In the present specification, the alkoxy group may be linear, branched or cyclic. The number of carbon atoms of the alkoxy group is not particularly limited, but is preferably 1 to 40 carbon atoms. Specific examples include methoxy, ethoxy, n-propoxy, isopropoxy, i-propyloxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentyloxy, neopentyloxy, N-hexyloxy, n-hexyloxy, 3,3-dimethylbutyloxy, 2-ethylbutyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, benzyloxy, But is not limited thereto.

Substituents comprising the alkyl groups, alkoxy groups and other alkyl moieties described herein include both straight chain and branched forms.

In the present specification, the alkenyl group may be straight-chain or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. Specific examples include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, Butenyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, (Diphenyl-1-yl) vinyl-1-yl, stilbenyl, stilenyl, and the like.

In the present specification, the silyl group specifically includes a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, a vinyldimethylsilyl group, a propyldimethylsilyl group, a triphenylsilyl group, a diphenylsilyl group, However, the present invention is not limited thereto.

In the present specification, the ester group may be substituted with an ester group oxygen in a straight chain, branched chain or cyclic alkyl group having 1 to 25 carbon atoms or an aryl group having 6 to 30 carbon atoms. Specifically, it may be a compound of the following structural formula, but is not limited thereto.

In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms. According to one embodiment, the cycloalkyl group has 3 to 40 carbon atoms. According to another embodiment, the cycloalkyl group has 3 to 20 carbon atoms. According to another embodiment, the cycloalkyl group has 3 to 6 carbon atoms. Specific examples include cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, and the like, but are not limited thereto.

In the present specification, the aryl group is not particularly limited, but preferably has 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 phenyl group, a biphenyl group, a terphenyl group or the like as the monocyclic aryl group, but is not limited thereto. Examples of the polycyclic aryl group include, but are not limited to, a naphthyl group, an anthracenyl group, a phenanthryl group, a pyrenyl group, a perylenyl group, a klycenyl group and a fluorenyl group.

In the present specification, a 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,

,

, A spirofluorenyl group

(9,9-dimethylfluorenyl group), and

(9,9-diphenylfluorenyl group), and the like. However, the present invention is not limited thereto.

The aryl group may be substituted with an alkyl group to act as an arylalkyl group. The alkyl group may be selected from the examples described above.

In the present specification, the number of carbon atoms of the amine group is not particularly limited, but is preferably 1 to 30. The amine group may be substituted with the above-mentioned alkyl group, aryl group, heterocyclic group, alkenyl group, cycloalkyl group, and combinations thereof. Specific examples of the amine group include methylamine group, dimethylamine group, ethylamine group, diethylamine A phenanthrene group, a phenylmethyl group, a phenylmethyl group, a phenylmethyl group, a naphthylamine group, a biphenylamine group, an anthracenylamine group, a 9-methyl-anthracenylamine group, a diphenylamine group, a phenylnaphthylamine group, , Triphenylamine group and the like, but are not limited thereto.

In the present specification, an arylamine group means an amine group substituted with an aryl group, and the above-mentioned examples can be applied to an aryl group.

As used herein, the term " adjacent " means that the substituent is a substituent substituted on an atom directly connected to the substituted atom, a substituent stereostructically closest to the substituent, or another substituent substituted on the substituted atom . For example, two substituents substituted in the benzene ring to the ortho position and two substituents substituted on the same carbon in the aliphatic ring may be interpreted as " adjacent " groups to each other.

In the present specification, the ring formed by bonding adjacent groups to each other may be monocyclic or polycyclic, and may form a hydrocarbon ring.

The hydrocarbon ring may be selected from the examples of the cycloalkyl group or the aryl group except that the hydrocarbon ring is not the monovalent group.

According to one embodiment of the present invention, R 1 and R 2 are each independently hydrogen, deuterium, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted amine group And a substituted or unsubstituted aryl group.

According to another embodiment, R 1 and R 2 are each independently selected from the group consisting of hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 40 carbon atoms, a substituted or unsubstituted carbon number An alkoxy group having 1 to 40 carbon atoms, a substituted or unsubstituted amine group having 1 to 30 carbon atoms, and a substituted or unsubstituted aryl group having 6 to 60 carbon atoms.

According to another embodiment, R 1 and R 2 are each independently selected from the group consisting of hydrogen, deuterium, substituted or unsubstituted C 1 -C 30 amine groups and substituted or unsubstituted C 6 -C 60 aryl groups. It is one.

According to another embodiment, R 1 and R 2 are each independently selected from the group consisting of hydrogen, deuterium, substituted or unsubstituted C 1 -C 20 amine groups and substituted or unsubstituted C 6 -C 40 aryl groups. It is one.

According to another embodiment, R 1 and R 2 are each independently a substituted or unsubstituted aryl group having 6 to 40 carbon atoms.

According to another embodiment, R 1 and R 2 are each independently a phenyl group; A biphenyl group; A naphthylenyl group; Or a phenanthryl group.

According to another embodiment, R 1 and R 2 are each independently a phenyl group or a biphenyl group.

As used herein, the term " thermosetting group or photocurable group " may mean a reactive substituent that causes crosslinking between the compounds by exposure to heat and / or light. The crosslinking can be produced by heat treatment or light irradiation, and connecting the radicals generated by decomposition of the carbon-carbon multiple bond, cyclic structure.

이고, 상기 열경화성기 또는 광경화성기가 열처리 또는 광처리에 의하여 가교되는

의 구조로 다른 아민계 화합물과 연결될 수 있다.For example, when the thermosetting group or the photocurable group is

, And the thermosetting group or the photocurable group is crosslinked by heat treatment or light treatment

Can be linked to other amine-based compounds.

According to one embodiment of the present disclosure, Y1 and Y2 each independently comprise a thermosetting group or a photocurable group, and the thermosetting group or photocurable group is selected from the following structures.

In the above structure, R7 is hydrogen; heavy hydrogen; A halogen group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted amine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted silyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.

According to another embodiment, R7 is hydrogen or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms.

According to another embodiment, R7 is hydrogen or an alkyl group having 1 to 20 carbon atoms.

According to another embodiment, R7 is hydrogen or an alkyl group having 1 to 6 carbon atoms.

In one embodiment of the present invention, an amine compound containing a thermosetting group or a photocurable group can be manufactured by a solution coating method, which is economical in terms of time and cost.

Further, in the case of forming a coating layer using a coating composition comprising an amine compound containing a thermosetting group or a photocurable group, since a thermosetting group or a photocurable group is crosslinked by heat or light, It is possible to prevent the amine compound contained in the coating composition from being washed out by the solvent when the layers are laminated so that the additional layer can be laminated on the upper part while maintaining the coating layer.

In addition, when a coating layer is formed by forming a crosslinking by a thermosetting group or a photocurable group, the coating layer has an increased chemical resistance to a solvent and a high film retention ratio.

In addition, in the case of the amine compound according to one embodiment of the present invention, the organic light emitting device can be manufactured by the solution coating method, and the device can be made larger.

According to one embodiment of the present invention, in the case of an amine compound in which crosslinking is performed by heat treatment or light irradiation, since a plurality of amine compounds are crosslinked to be provided in a thin film form in the organic light emitting device, the compound has an excellent thermal stability. Accordingly, the organic light emitting device using the amine compound according to one embodiment of the present invention has an excellent lifetime characteristic.

In addition, since the amine compound according to one embodiment of the present invention includes an amine structure in the core structure, it can have an appropriate energy level and band gap as a hole injecting, hole transporting material, or light emitting material in an organic light emitting device. In addition, by controlling the substituent of the compound of Chemical Formula 1 according to one embodiment of the present invention, it is possible to control the appropriate energy level and bandgap finely, improve the interfacial characteristics between the organic materials, Can be provided.

According to one embodiment of the present invention, the compound of Formula 1 is any one selected from the following compounds.

The compound according to one embodiment of the present specification can be produced by a production method described below.

For example, the compound of Formula 1 can be prepared as a core structure as shown in Reaction Scheme 1 below. Substituent groups may be attached by methods known in the art, and the type, position or number of substituent groups may be varied according to techniques known in the art.

The present disclosure also provides coating compositions comprising the amine-based compounds described above.

In one embodiment of the present disclosure, the coating composition may be in a liquid phase. The " liquid phase " means that the liquid phase is at normal temperature and pressure.

In one embodiment of the present disclosure, the coating composition comprises the amine compound and a solvent.

In one embodiment of the present invention, the solvent includes, for example, chlorinated solvents such as chloroform, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, chlorobenzene and 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; Examples of polyhydric alcohols 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, Alcohols and their derivatives; Alcohol solvents such as methanol, ethanol, propanol, isopropanol, and cyclohexanol; Sulfoxide-based solvents such as dimethylsulfoxide; And amide solvents such as N-methyl-2-pyrrolidone and N, N-dimethylformamide; A solvent such as tetralin is exemplified, but a solvent capable of dissolving or dispersing the carbazole derivative according to one embodiment of the present invention is sufficient, and the solvent is not limited thereto.

In another embodiment, the solvents may be used alone or in combination of two or more solvents.

In one embodiment of the present invention, the coating composition may further include one or two compounds selected from the group consisting of a compound having a thermosetting group or a photocurable group introduced into the molecule and a polymer compound.

In one embodiment of the present invention, the coating composition may further comprise a compound having a thermosetting group or a photocurable group introduced into the molecule. When the coating composition further contains a compound having a thermosetting group or a photocurable group introduced into the molecule, the degree of curing of the coating composition can be further increased.

In one embodiment of the present invention, the molecular weight of the compound having a thermosetting group or a photo-curable group introduced into the molecule is from 100 g / mol to 1,500 g / mol.

In one embodiment of the present invention, the coating composition may further comprise a polymer compound. When the coating composition further comprises a polymer compound, the ink property of the coating composition can be enhanced. That is, the coating composition further comprising the polymer compound may provide a suitable viscosity for coating or ink jetting.

In one embodiment of the present disclosure, the viscosity of the coating composition is between 2 cP and 15 cP. When having a viscosity in the above range, it is easy to manufacture the device.

In one embodiment of the present invention, the molecular weight of the polymer compound is 10,000 g / mol to 200,000 g / mol.

In one embodiment of the present invention, the coating composition may further include one or more additives selected from the group consisting of a thermal polymerization initiator and a photopolymerization initiator.

Examples of the thermal polymerization initiator include methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, acetylacetone peroxide, methyl cyclohexanone peroxide, cyclohexanone peroxide, isobutyryl peroxide, 2,4-dichlorobenzoyl peroxide , Bis-3,5,5-trimethylhexanoyl peroxide, lauryl peroxide, benzoyl peroxide, p-chlorobenzoyl peroxide, dicumyl peroxide, 2,5-dimethyl- Oxy-hexane, 1,3-bis (t-butylperoxy-isopropyl) benzene, t-butyl cumyl peroxide, di- T-butylperoxy) hexane-3, tris- (t-butylperoxy) triazine, 1,1-ditertiary butyl peroxy-3,3,5-trimethylcyclohexane, 1,1- Butylperoxycyclohexane, 2,2-di (t-butylperoxy) butane, 4,4-di-t-butoxypivalicylic acid n-butyl ester, 2,2- 4-t-butylperoxys Butyl peroxy isobutyrate, t-butyl peroxyhexahydroterephthalate, t-butyl peroxy-3,5,5-trimethyl hexaate, t-butyl peroxybenzoate, di and peroxides such as t-butyl peroxytrimethyl adipate, and azo compounds such as azobisisobutylnitrile, azobisdimethylvaleronitrile, and azobiscyclohexyl nitrile, but are not limited thereto.

Examples of the photopolymerization initiator include diethoxyacetophenone, 2,2-dimethoxy-1,2-diphenylethan-1-one, 1 -hydroxy-cyclohexylphenyl-ketone, 4- (2-hydroxyethoxy) Phenyl-2-propyl) ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) 1-one, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime , Etc., benzoin ethers such as benzoin, benzoin methylurate, benzoin etchurateur, benzoin isobutyrate, benzoin isopropyrate, etc., Based photopolymerization initiator such as benzophenone, 4-hydroxybenzophenone, 2-benzoylnaphthalene, 4-benzoylbiphenyl, 4-benzoylphenyl ether, acrylated benzophenone and 1,4-benzoylbenzene, 2-isopropylthioxanthone, 2- Examples of the photopolymerization initiator include thioxanthone photopolymerization initiators such as thioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone and 2,4-dichlorothioxanthone, and other photopolymerization initiators include ethyl anthraquinone, 2 , 2,4,6-trimethylbenzoylphenyl ethoxyphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, bis (2,4- Dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, methylphenyl glyoxycellester, 9,10-phenanthrene, acridine compound, triazine compound, imidazole compound have. The photopolymerization initiator having the photopolymerization promoting effect may be used alone or in combination with the photopolymerization initiator. Examples thereof include triethanolamine, methyldiethanolamine, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, benzoic acid (2-dimethylamino) ethyl and 4,4'-dimethylaminobenzophenone, It is not limited thereto.

In one embodiment of the present disclosure, the coating composition further comprises no p-doping material.

In yet another embodiment, the coating composition further comprises a p-doping material.

In this specification, the p-doped material means a material that has a p-type semiconductor property as a host material. p semiconductor property means a property of injecting or transporting holes at a highest occupied molecular orbital (HOMO) energy level, that is, a material having a high conductivity of holes.

In one embodiment of the present disclosure, the p-doped material may be represented by any one of the following structures.

In one embodiment of the present invention, the content of the p-doping material is 0% by weight to 50% by weight based on the amine compound of the formula (1).

In one embodiment of the present disclosure, the content of the p-doped material comprises 0 to 30% by weight based on the total solids content of the coating composition.

In one embodiment of the present disclosure, the content of the p-doped material preferably comprises 1 to 30% by weight based on the total solid content of the coating composition, and in another embodiment, the p-doped material More preferably 10 to 30% by weight based on the total solids content of the coating composition.

In yet another embodiment, the coating composition comprises a single molecule comprising a thermosetting group or a photocurable group; Or a monomer capable of forming a polymer by heat. A single molecule containing a thermosetting group or a photocurable group as described above; Or a molecular weight of a monomolecule including an end group capable of forming a polymer by heat can be 2,000 g / mol or less.

As in one embodiment of the present disclosure, the coating composition comprises a monomolecule comprising a thermosetting group or a photocurable group; Or a monomolecule containing an end group capable of forming a polymer by thermal polymerization, it is more preferable that the curing temperature can be lowered, and it is composed of similar structures that do not affect the physical properties of the amine compound of the present specification .

Monomers including the thermosetting group or the photocurable group; Or monomers comprising an end group capable of forming a polymer by thermal polymerization include aryl, such as phenyl, biphenyl, fluorene, naphthalene; Arylamine; Or a monomolecule in which a terminal group capable of forming a thermosetting group, a photo-curable group or a polymer by heat is substituted for the fluorene.

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

One embodiment of the present disclosure includes a cathode; Anode; And one or more organic layers disposed between the cathode and the anode, wherein at least one of the organic layers includes a cured product of the coating composition, wherein the cured product of the coating composition is heat- And the organic light emitting device is in a state of being cured by the light emitting diode.

In one embodiment of the present invention, the organic material layer including the cured product of the coating composition is a hole transporting layer, a hole injecting layer, or a layer simultaneously transporting holes and injecting holes.

In another embodiment, the organic layer comprising the cured product of the coating composition is a light emitting layer.

In another embodiment, the organic layer including the cured product of the coating composition is a light emitting layer, and the light emitting layer includes the amine compound as a host of the light emitting layer.

In one embodiment of the present invention, the organic light emitting element is a hole injection layer, a hole transport layer, An electron transport layer, an electron injection layer, an electron blocking layer, and a hole blocking layer.

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 compound 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, at least one organic layer, and an anode are sequentially stacked on a substrate.

The organic material layer of the organic light emitting device of the present invention may have a single layer structure, but may have a multilayer structure in which two or more organic material layers are stacked. For example, the organic light emitting device in this specification may have a structure including a hole injecting layer, a hole transporting layer, a light emitting layer, an electron transporting layer, and an electron injecting layer 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 an organic light emitting device according to one embodiment of the present specification is illustrated in FIG.

1 shows an organic light emitting device in which an anode 201, a hole injecting layer 301, a hole transporting layer 401, a light emitting layer 501, an electron transporting layer 601 and a cathode 701 are sequentially stacked on a substrate 101 Are illustrated.

1, the hole injection layer 301 is formed using a coating composition containing an amine compound.

FIG. 1 illustrates an organic light emitting device and is not limited thereto.

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

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

For example, the organic light emitting device of the present specification can be manufactured by sequentially laminating an anode, an organic layer, and a cathode on a substrate. At this time, a metal or a metal oxide having conductivity or an alloy thereof is deposited on the substrate by a PVD (physical vapor deposition) method such as sputtering or e-beam evaporation to form an anode Forming an organic material layer including a hole injecting layer, a hole transporting layer, a light emitting layer and an electron transporting layer thereon, and then depositing a material usable as a cathode thereon. In addition to such a method, an organic light emitting device can be formed by sequentially depositing a cathode material, an organic material layer, and an anode material on a substrate.

An embodiment of the present invention provides a method of manufacturing an organic light emitting device formed using the coating composition.

Specifically, in one embodiment of the present disclosure, there is provided a method comprising: preparing a substrate; Forming a cathode or an anode on the substrate; Forming at least one organic material layer on the cathode or the anode; And the step of forming the organic material layer may include forming at least one organic material layer using the coating composition described above.

In one embodiment of the present invention, the organic layer formed using the coating composition is formed using spin coating.

In another embodiment, the organic layer formed using the coating composition is formed by inkjet printing.

In another embodiment, the organic layer formed using the coating composition is formed by a printing method.

In one embodiment of the present invention, the printing method includes, but is not limited to, a nozzle printing method, an offset printing method, a transfer printing method, and a screen printing method.

Since the coating composition according to one embodiment of the present invention has a structural characteristic and is suitable for a solution process, the coating composition can be formed by a printing method, so that there is an economical effect in time and cost in manufacturing a device.

In one embodiment of the present disclosure, the step of forming an organic layer formed using the coating composition comprises: coating the coating composition on the cathode or the anode; And heat treating or light treating the coated coating composition.

In one embodiment of the present invention, the heat treatment temperature in the heat treatment step is 85 캜 to 300 캜.

In another embodiment, the heat treatment time in the heat treatment step may be from 1 minute to 1 hour.

In one embodiment of the present invention, when the coating composition contains no additive, it is preferable that the coating is heat-treated at a temperature of 100 ° C to 300 ° C to perform crosslinking, and crosslinking proceeds at a temperature of 150 ° C to 250 ° C .

In addition, the coating compositions herein may further comprise initiators, but are more preferably not used.

In the case where the organic compound layer formed using the coating composition includes the heat treatment or light treatment step, an organic compound layer including a structure in which a plurality of amine compounds included in the coating composition form a bridge to form a thin film may be provided . In this case, the organic layer formed using the coating composition can be prevented from being dissolved, morphologically affected or decomposed by the solvent applied on the surface.

Therefore, when the organic material layer formed using the coating composition is formed by including the heat treatment or the light treatment step, the resistance to the solvent is increased, so that the multilayer can be formed by repeating the solution deposition and crosslinking method, Life characteristics can be increased.

In one embodiment of the present invention, the coating composition containing the amine compound may be a coating composition prepared by mixing and dispersing the amine compound in a polymer binder.

In one embodiment of the present invention, the polymer binder is preferably one that does not extremely inhibit charge transport, and that does not strongly absorb visible light. Examples of the polymeric binder include poly (N-vinylcarbazole), polyaniline and derivatives thereof, polythiophene and derivatives thereof, poly (p-phenylenevinylene) and derivatives thereof, poly (2,5-thienylenevinylene) A derivative thereof, a polycarbonate, a polyacrylate, polymethyl acrylate, polymethyl methacrylate, polystyrene, polyvinyl chloride, polysiloxane and the like.

In addition, the amine compound according to one embodiment of the present invention includes a fluorene and an amine group, so that the organic compound layer may contain the amine compound alone, or the coating composition containing the amine compound may be thinned through heat treatment or light treatment Or may be incorporated as a copolymer using coating compositions mixed with other monomers. In addition, it can be incorporated as a copolymer or as a mixture using a coating composition mixed with another polymer.

As the anode material, a material having a large work function is preferably used so that injection of holes into the organic material layer is smooth. Specific examples of the anode material that can be used in the present invention 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); ZnO: Al or SnO _2: a combination of a metal and an oxide such as Sb; Conductive polymers such as poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDOT), polypyrrole and polyaniline.

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 magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead or alloys thereof; Layer structure materials such as LiF / Al or LiO ₂ / Al, but are not limited thereto.

The hole injecting layer is a layer for injecting holes from the electrode. The hole injecting layer has a hole injecting effect for hole injecting effect on the anode, a hole injecting effect for the light emitting layer or the light emitting material due to its ability to transport holes to the hole injecting material, A compound which prevents the migration of excitons to the electron injecting layer or the electron injecting material and is also excellent in the thin film forming ability is preferable. It is preferable that the highest occupied molecular orbital (HOMO) of the hole injecting material be between the work function of the anode material and the HOMO of the surrounding organic layer. Specific examples of the hole injecting material include metal porphyrin, oligothiophene, arylamine-based organic materials, hexanitrile hexaazatriphenylene-based organic materials, quinacridone-based organic materials, and perylene- , Anthraquinone, polyaniline and polythiophene-based conductive polymers, but the present invention is not limited thereto.

The hole transport layer is a layer that transports holes from the hole injection layer to the light emitting layer and transports holes from the anode or the hole injection layer to the light emitting layer as the hole transport material. The material is suitable. Specific examples include arylamine-based organic materials, conductive polymers, and block copolymers having a conjugated portion and a non-conjugated portion together, but are not limited thereto.

The light emitting material is preferably a material capable of emitting light in the visible light region by transporting and receiving holes and electrons from the hole transporting layer and the electron transporting layer, respectively, and having good quantum efficiency for fluorescence or phosphorescence. Specific examples include 8-hydroxy-quinoline aluminum complex (Alq ₃ ); Carbazole-based compounds; Dimerized styryl compounds; BAlq; 10-hydroxybenzoquinoline-metal compounds; Compounds of the benzoxazole, benzothiazole and benzimidazole series; Polymers of poly (p-phenylenevinylene) (PPV) series; Spiro compounds; Polyfluorene, rubrene, and the like, but are not limited thereto.

The light emitting layer may include a host material and a dopant material. The host material is a condensed aromatic ring derivative or a heterocyclic compound. Specific examples of the condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, and fluoranthene compounds. Examples of the heterocycle-containing compounds include carbazole derivatives, dibenzofuran derivatives, Furan compounds, pyrimidine derivatives, and the like, but are not limited thereto.

Examples of the dopant material include aromatic amine derivatives, styrylamine compounds, boron complexes, fluoranthene compounds, and metal complexes. Specific examples of the aromatic amine derivatives include condensed aromatic ring derivatives having substituted or unsubstituted arylamino groups, and examples thereof include pyrene, anthracene, chrysene, and peripherrhene having an arylamino group. Examples of the styrylamine compound include substituted or unsubstituted Wherein at least one aryl vinyl group is substituted with at least one aryl vinyl group, and at least one substituent selected from the group consisting of an aryl group, a silyl group, an alkyl group, a cycloalkyl group and an arylamino group is substituted or unsubstituted. Specific examples thereof include, but are not limited to, styrylamine, styryldiamine, styryltriamine, styryltetraamine, and the like. Examples of the metal complex include iridium complex, platinum complex, and the like, but are not limited thereto.

The electron transporting layer is a layer that receives electrons from the electron injection layer and transports electrons to the light emitting layer. The electron transporting material is a material capable of transferring electrons from the cathode well to the light emitting layer. Do. Specific examples include an 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 transporting layer can be used with any desired cathode material as used according to the prior art. In particular, an example of a suitable cathode material is a conventional material having a low work function followed by an aluminum layer or a silver layer. Specifically cesium, barium, calcium, ytterbium and samarium, in each case followed by an aluminum layer or a silver layer.

The electron injection layer is a layer for injecting electrons from an electrode and has an ability to transport electrons and has an electron injection effect from the cathode, an excellent electron injection effect on the light emitting layer or the light emitting material, A compound which prevents migration to a layer and is excellent in a thin film forming ability is preferable. Specific examples thereof include fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, A complex compound and a nitrogen-containing five-membered ring derivative, but are not limited thereto.

Examples of the metal complex compound include 8-hydroxyquinolinato lithium, bis (8-hydroxyquinolinato) zinc, bis (8-hydroxyquinolinato) copper, bis (8- Tris (8-hydroxyquinolinato) aluminum, tris (2-methyl-8-hydroxyquinolinato) aluminum, tris (8- hydroxyquinolinato) gallium, bis (10- Quinolinato) beryllium, bis (10-hydroxybenzo [h] quinolinato) zinc, bis (2-methyl-8- quinolinato) chlorogallium, bis (2-methyl-8-quinolinato) (2-naphtholato) gallium, and the like, But is not limited thereto.

The hole blocking layer is a layer which prevents the cathode from reaching the hole, and can be generally formed under the same conditions as the hole injecting layer. Specific examples thereof include, but are not limited to, oxadiazole derivatives, triazole derivatives, phenanthroline derivatives, BCP, aluminum complexes and the like.

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

In one embodiment of the present invention, the coating composition may be included in an organic solar cell or an organic transistor in addition to the organic light emitting device.

Hereinafter, the present invention will be described in detail by way of examples with reference to the drawings. However, the embodiments according to the present disclosure can be modified in various other forms, and the scope of the present specification is not construed as being limited to the embodiments described below. Embodiments of the present disclosure are provided to more fully describe the present disclosure to those of ordinary skill in the art.

Production Example 1. Preparation of Formula 1-1

2,2 '- (5'- chloro - [1,1 ': 3', 1 " - 테 페렌 ] -4,4 ' - diyl ) bis (1,3- dioxolane ) (Compound 2)

[Reaction Scheme 1]

Add 1, 3-dibromo-5-chlorobenzene (10 g, 36.98 mmol), (4-formylphenyl) boronic acid (11.4 g, 75.8 mmol) and Potassium carbonate (15.33 g, 110.09 mmol) into a 1 L round bottom flask 200 ml of toluene, 100 ml of ethanol and 100 ml of water were added, and the mixture was heated to 80 ° C and dissolved with stirring. When the reaction material was dissolved in the solvent, Tetrakis (triphenylphosphine) palladium (2.14 g, 1.849 mmol) was added thereto and reacted for 24 hours. The temperature was lowered and extracted with EA and water. The residue was removed with MgSO ₄ , stirred with charcoal, and passed through silica gel. The solvent was removed, and white crystals were obtained using THF and methanol. (Yield: 62%).

The above obtained 5'-chloro- [1,1 ': 3', 1 "-terphenyl] -4,4" -dicarbaldehyde (Compound 1) (7.35 g, 22.91 mmol) was placed in 250 mL RBF, After the addition of TsOH (0.04 g, 0.23 mmol) and ethylene glycol (5.1 ml, 91.64 mmol), dean-stark was placed and reacted for 24 hours while removing water at high temperature. After quenching with NaHCO ₃ and working up with EA and brine, the residue was filtered off with MgSO ₄ and the solvent was removed. After column with EA: Hex = 1: 5, it was precipitated with EA and Hex and filtered to obtain a white solid. (Yield: 53%) < 1 > H NMR results of the synthesis of Compound 2 are shown in Fig.

[Reaction Scheme 2]

(6.5 g, 17.98 mmol), Compound 2 (7.0 g, 17.12 mmol), NaOtBu (17.12 mmol) 6.58 g, 68.48 mmol) in 250 mL RBF to N ₂ purging. After adding 60 ml of toluene bubbled with nitrogen and heating the mixture to 90 ° C, the starting materials were dissolved. Pd (PtBu ₃ ) ₂ (0.437 g, 0.86 mmol) was added and the mixture was heated to 120 ° C and stirred for 2 hours. And work-up with EA and water. The residue was removed with MgSO ₄ , stirred with charcoal, and passed through a pad of silica gel. The solvent was removed, and the product was columned with EA: Hex = 1: 5 to obtain a white solid (Compound 3). (Yield: 84%)

Compound (3) (7.5 g, 10.19 mmol) was dissolved in 100 ml of THF, 10 ml of water and 1N HCl (1.3 ml, 1.01 mmol) were added and stirred for 3 hours while refluxing at 70 ° C. As the reaction proceeded, a fluorescent yellow solid was observed to precipitate. The temperature was lowered and the fluorescent yellow solid was immediately filtered with THF and dried in a vacuum oven at 50 ° C for 24 hours to obtain Compound 4 having a purity of 99.9%. (Yield: 86%)

Weighed CH ₃ PPh ₃ Br (10.96 g, 30.68 mmol) vacuum-dried at 50 ° C was weighed in 500 mL RBF and N ₂ purged. 350 mL distilled THF was added and 2.5 M n-BuLi (11.2 mL, 27.9 mmol) was dropping and stirred for about 30 minutes to give the product. The temperature of the bath was adjusted to 0 ° C, and the compound 4 was added to proceed the olefination reaction. At this time, Compound 4 was put into a solid state because its solubility was not very good, and the reaction time was also lengthened to overnight. After confirming that the reaction had been completed, the reaction was terminated with water, and work up with EA and Brine. The residue was removed with Na ₂ SO ₄ , and the solvent was blown off. TEA was added to the deacidized silica gel to obtain EA: Hex = 1: 250 flash column. After removing the solvent, recrystallization was performed using MC and EA to obtain a white solid (Compound 1-1). (Yield: 27%)

Compound 1-2 was also obtained by the same method using the starting material.

MS data for identifying the compounds 1-1 and 1-2 are shown in FIGS. 3 and 4, respectively.

Example  10

               IB VNPB

         Compound 5           Compound 6         Compound 7

The P doping material (IB); The compound VNPB; And an organic solvent (cyclohexanone) were mixed to prepare a coating composition. The ratio of VNPB: p-dopant was mixed at a weight ratio of 0.8: 0.2. The glass substrate on which ITO (indium tin oxide) was deposited to a thickness of 1500 Å was immersed in distilled water containing detergent and washed with ultrasonic waves. After the ITO was washed for 30 minutes, ultrasonic washing was repeated 10 times with distilled water twice. After the distilled water was washed, ultrasonic washing was performed with a solvent of isopropyl alcohol and acetone for 30 minutes each, and the substrate was transported to a glove box. The coating composition was spin-coated on the prepared ITO transparent electrode to form a 300 Å thick hole injection layer, and the coating composition was cured under a N ₂ atmosphere on a hot plate at 220 ^° C for 30 minutes. The compound 1-1 on the hole injection layer, an organic solvent spin coating a composition dissolved in a weight ratio of 1% (Toluene Toluene) to form a hole transport layer of 400Å thickness on a hot plate under a N ₂ atmosphere, 230 ^o C, 30 Min to cure the coating composition. Thereafter, the compound 5 and the compound 6 (8% concentration, 300 Å), the compound 7 (200 Å), LiF (12 Å) and Al (2000 Å) were sequentially deposited by vacuum evaporator. In the above process, the deposition rate of the organic material was maintained at 0.4 to 0.7 Å / sec, the cathode LiF was maintained at 0.3 Å / sec, and the deposition rate of aluminum was maintained at 2 Å / sec, and the degree of vacuum during deposition was 2 × 10 ^-7 to 5 × 10 ^-8 torr. ≪ / RTI >

Example 2

Was prepared under the same conditions except that the compound 1-2 was used instead of the compound 1-1.

Comparative Example

Compound A

Was prepared under the same conditions except that Compound A was used instead of Compound 1-1.

The driving voltage (V) Current efficiency (cd / A) Power Efficiency (lm / W) Example 1 8.40 4.93 2.46 Example 2 4.67 4.69 3.15 Comparative Example 6.5 2.80 1.15

Referring to Table 1, the comparative example shows lower current efficiency and power efficiency than the first and second embodiments.

In order to confirm the curing temperature of the compounds 1-1 and 1-2, the compounds 1-1 and 1-2 were applied in a single molecule form and subjected to a heat treatment. GSC results are shown in FIG. 5 and FIG. 6, respectively. It can be seen from FIG. 5 that curing occurs at about 210 ° C. in the case of the compound 1-1 and near 180 ° C. in the case of the compound 1-2. Therefore, the amine-based compound according to one embodiment of the present invention has a low curing temperature even after coating with a polymer, so that the cross-likned polymer can be sufficiently formed only by heat treatment.

101: substrate
201: anode
301: Hole injection layer
401: hole transport layer
501: light emitting layer
601: electron transport layer
701: Cathode

Claims (8)

An amine compound represented by the following formula (1):
[Chemical Formula 1]

In Formula 1,
R1 and R2 are each independently selected from the group consisting of hydrogen, deuterium, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted amine group and a substituted or unsubstituted aryl group Group, < / RTI >
Y1 and Y2 each independently represent a photocurable group or a thermosetting group,
a to d are each independently an integer of 1 to 5,
When a to d are two or more, R1, R2, Y1 and Y2 are the same or different from each other,
When a and b are two or more, adjacent substituents may be bonded to each other to form a hydrocarbon ring. The method according to claim 1,
Wherein the thermosetting group or photocurable group is selected from the following structures:

In the above structure,
R7 is hydrogen; heavy hydrogen; A halogen group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted amine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted silyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group. The method according to claim 1,
(1) is any one selected from the following compounds:

A coating composition comprising an amine-based compound according to any one of claims 1 to 3. 5. The coating composition of claim 4, wherein the coating composition further comprises a p-doping material represented by any one of the following structures:

. Cathode;
Anode; And
And at least one organic layer provided between the cathode and the anode,
Wherein at least one of the organic layers comprises a cured product of the coating composition of claim 4,
Wherein the cured product of the coating composition is in a cured state by heat treatment or light treatment. [Claim 7] The organic light emitting device according to claim 6, wherein the organic material layer including the cured product of the coating composition is a hole transporting layer, a hole injecting layer, or a layer simultaneously transporting holes and injecting holes. Preparing a substrate;
Forming a cathode or an anode on the substrate;
Forming at least one organic material layer on the cathode or the anode; And
Forming an anode or a cathode on the organic material layer,
Wherein the forming of the organic material layer includes forming at least one organic material layer using the coating composition of claim 4,
Wherein the step of forming an organic layer formed using the coating composition comprises coating the coating composition on the cathode or the anode, and heat-treating or light-treating the coated composition. .

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