KR101372850B1 - Dimethylenecyclohexane compound, method for preparing the same and organic light emitting device comprising the same - Google Patents

Abstract

The present invention relates to a dimethylene cyclohexane compound represented by Formula 1, a method for preparing the same, and an organic light emitting device having the same:

≪ Formula 1 >

In Formula 1, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , X ₁ , X ₂ , Ar ₁ , Ar ₂ , n ₁ , and n ₂ are of the invention See detailed description. By using the dimethylene cyclohexane compound, an organic light emitting device having improved driving voltage, efficiency, and color purity can be obtained.

Description

Dimethylenecyclohexane compound, method for preparing the same and organic light emitting device comprising the same}

1A to 1C are cross-sectional views each schematically showing the structure of one embodiment of an organic light emitting device according to the present invention;

The present invention relates to a dimethylene cyclohexane compound, a manufacturing method thereof, and an organic light emitting device having the same. More specifically, the present invention relates to an organic light emitting device having excellent electrical properties, thermal stability, and photochemical stability. When applied, the present invention relates to a dimethylene cyclohexane compound capable of exhibiting excellent driving voltage, efficiency and color purity characteristics, a method for preparing the same, and an organic light emitting device employing the organic film including the dimethylene cyclohexane compound.

A light emitting device is a self-emitting type device having a wide viewing angle, an excellent contrast, and a fast response time. The light emitting device includes an inorganic light emitting device using an inorganic compound and an organic light emitting device (OLED) using an organic compound, and the organic light emitting device has luminance, Many studies have been conducted in that driving voltage and response speed characteristics are excellent and multicolorization is possible.

The organic light emitting device generally has a stack structure of an anode / an organic light emitting layer / a cathode and includes an anode / a hole injecting layer / a hole transporting layer / a light emitting layer / an electron transporting layer / an electron injecting layer / a cathode or an anode / a hole injecting layer / a hole transporting layer / Blocking layer / electron transporting layer / electron injecting layer / cathode, and the like.

Japanese Patent Laid-Open No. 1999-003782 discloses anthracene substituted with two naphthyl groups as a compound that can be used in the light emitting layer or the hole injection layer. However, the driving voltage, efficiency and color purity characteristics of the organic light-emitting device employing the compound do not reach a satisfactory level, and an improvement thereof is urgent.

The technical problem to be achieved by the present invention is to provide a dimethylene cyclohexane compound that can improve the driving voltage, efficiency and color purity characteristics of the organic light emitting device.

Another technical problem to be achieved by the present invention is to provide a method for preparing the dimethylene cyclohexane compound.

Another object of the present invention is to provide an organic light emitting device comprising the dimethylene cyclohexane compound.

According to an aspect of the present invention,

It provides a dimethylene cyclohexane compound of formula (I):

≪ Formula 1 >

In Formula 1,

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are each independently hydrogen, a halogen atom, a cyano group, a hydroxyl group, an amino group, a substituted or unsubstituted C _1- C ₂₀ alkyl group, substituted or unsubstituted C ₁ -C ₂₀ alkoxy group, substituted or unsubstituted C ₆ -C ₃₀ aryl group, substituted or unsubstituted C ₂ -C ₃₀ heteroaryl group or formula -N (Z ' Is a substituted amino group having (Z ″), wherein Z ′ and Z ″ are each independently a substituted or unsubstituted C ₁ -C ₂₀ alkyl group, a substituted or unsubstituted C ₆ -C ₃₀ aryl group, a substituted or An unsubstituted C ₂ -C ₃₀ heteroaryl group, a substituted or unsubstituted C ₅ -C ₂₀ cycloalkyl group, or a substituted or unsubstituted C ₅ -C ₃₀ heterocycloalkyl group;

X ₁ and X ₂ are each independently a single bond, a double bond, a substituted or unsubstituted C ₁ -C ₂₀ alkylene group, a substituted or unsubstituted C ₂ -C ₂₀ alkenylene group, a substituted or unsubstituted C ₂ -C ₂₀ alkynylene group, substituted or unsubstituted C ₁ -C ₂₀ heteroalkylene group, substituted or unsubstituted C ₇ -C ₃₀ alkylenearylene group, substituted or unsubstituted C ₆ -C ₃₀ arylene group, substituted Or an unsubstituted C ₂ -C ₃₀ heteroarylene group;

n ₁ and n ₂ are each independently an integer of 0 to 5, wherein when n ₁ or n ₂ is 2 or more, a plurality of X ₁ or X ₂ may be the same or different from each other;

Ar ₁ and Ar ₂ independently represent a substituted or unsubstituted C ₆ -C ₃₀ aryl group, C ₂ -C ₃₀ heteroaryl group, C ₄ -C ₃₀ cycloalkyl group or C ₂ -C ₃₀ cycloheteroalkyl group;

Provided that at least one of Ar _{1 and} Ar ₂ includes two or more substituents.

According to one embodiment of the present invention, the substituents included in Ar ₁ or Ar ₂ are each independently a substituted or unsubstituted C ₆ -C ₃₀ aryl group, a substituted or unsubstituted C ₂ -C ₃₀ heteroaryl group, A substituted or unsubstituted C ₅ -C ₂₀ cycloalkyl group, a substituted or unsubstituted C ₅ -C ₃₀ heterocycloalkyl group, or a substituted amino group having the formula —N (R ′) (R ″), wherein R ′ and R ″, independently from each other, is hydrogen, a substituted or unsubstituted C ₁ -C ₂₀ alkyl group, a substituted or unsubstituted C ₆ -C ₃₀ aryl group, a substituted or unsubstituted C ₂ -C ₃₀ heteroaryl group, C ₅ -C ₂₀ cycloalkyl group, C ₅ -C ₃₀ heterocycloalkyl group.

In order to achieve the another object of the present invention, the second aspect of the present invention,

Reacting a compound represented by the following Formula 1a with a compound represented by the following Formula 1b and / or a compound represented by the following Formula 1c to form a compound represented by the following Formula 1d, and a compound represented by the following Formula 1d Dimethylene represented by Formula 1 as described above, comprising the step of forming a compound represented by Formula 1 by reacting with a compound represented by Formula L ₁ -Q ₁ , a compound represented by L ₂ -Q ₂ , etc. Provided are methods for preparing the cyclohexane compound:

<Formula 1a>

&Lt; EMI ID =

&Lt; Formula 1c >

<Formula 1d>

Among the above formulas,

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , X ₁ , X ₂ , n ₁ and n ₂ are the same as defined above;

Ar ₁ ^′ and Ar ₂ ^′ represent a substituted or unsubstituted C ₆ -C ₃₀ aryl group, C ₂ -C ₃₀ heteroaryl group, C ₄ -C ₃₀ cycloalkyl group or C ₂ -C ₃₀ cycloheteroalkyl group;

Ha ₁ and Ha ₂ are halogen, m ₁ and m ₂ are integers from 0 to 5;

Provided that at least one of m ₁ and m ₂ is an integer of 2 or more.

Q ₁ , Q _2, and the like are B-containing groups, and L ₁ , L _2, and the like are substituents included in Ar ₁ or Ar ₂ as defined above, and they have a formula —N (R ′) (R ″). In the case of a substituted amino group, Q <_1> , Q <_2>, etc. are H.

In order to achieve the another object of the present invention, the third aspect of the present invention, the first electrode; A second electrode; And an organic light emitting device including at least one organic film between the first electrode and the second electrode, wherein the organic film includes an dimethylene cyclohexane compound of Formula 1 as described above. .

The dimethylene cyclohexane compound of Chemical Formula 1 according to the present invention has excellent thermal stability, photochemical stability, and optical properties, and an organic light emitting device having the same may have excellent driving voltage, efficiency, and color purity.

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

The dimethylene cyclohexane compound according to the present invention is represented by the following general formula (1):

&Lt; Formula 1 >

In Formula 1, two double bonds and a dimethylene cyclohexane group respectively connected to the double bonds serve to increase solubility of the compound represented by Formula 1, wherein Ar _1- (X ₁ ) _n1 -and Ar _2- (X ₂ ) _{n 2} -is a film proccesibility of the compound represented by Formula 1 due to the substituents L ₁ , L ₂ , L ₃ and L ₄ included in Ar ₁ and Ar ₂ , It serves to further improve quantum efficiency, thermal stability, photo chemical stability and PL properties. Therefore, the dimethylene cyclohexane compound represented by Chemical Formula 1 is suitable as a material forming an organic film interposed between the first electrode and the second electrode of the organic light emitting device. The dimethylene cyclohexane compound of Formula 1 is suitable for use in organic membranes, particularly hole injection layers, hole transport layers or light emitting layers of the organic light emitting device.

In Formula 1, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are each independently hydrogen, a halogen atom, a cyano group, a hydroxyl group, an amino group, a substituted or unsubstituted A substituted C ₁ -C ₂₀ alkyl group, a substituted or unsubstituted C ₁ -C ₂₀ alkoxy group, a substituted or unsubstituted C ₆ -C ₃₀ aryl group, a substituted or unsubstituted C ₂ -C ₃₀ heteroaryl group or formula It may be a substituted amino group having -N (Z ') (Z "), wherein Z' and Z" are independently of each other, a substituted or unsubstituted C ₁ -C ₂₀ alkyl group, a substituted or unsubstituted A C ₆ -C ₃₀ aryl group, a substituted or unsubstituted C ₂ -C ₃₀ heteroaryl group, a substituted or unsubstituted C ₅ -C ₂₀ cycloalkyl group, or a substituted or unsubstituted C ₅ -C ₃₀ heterocycloalkyl group have.

In the present invention, when one or more hydrogen atoms included in various substituents such as an alkyl group, an alkoxy group, an aryl group, a heteroaryl group, a cycloalkyl group or a heterocycloalkyl group are substituted, their substituents are independently of each other, -F,- Cl, —Br, —CN, —NO ₂ , —OH; C ₁ -C ₂₀ alkyl group unsubstituted or substituted with —F, —Cl, —Br, —CN, —NO ₂ or —OH; C ₁ -C ₂₀ alkoxy group unsubstituted or substituted with —F, —Cl, —Br, —CN, —NO ₂ or —OH; C ₆ -C ₃₀ aryl groups unsubstituted or substituted with C ₁ -C ₂₀ alkyl groups, C ₁ -C ₂₀ alkoxy groups, —F, —Cl, —Br, —CN, —NO ₂ or —OH; Unsubstituted or C ₁ -C ₂₀ alkyl group, C ₁ -C ₂₀ alkoxy group, C ₂ -C ₃₀ heteroaryl group substituted with —F, —Cl, —Br, —CN, —NO ₂ or —OH; Unsubstituted or C ₁ -C ₂₀ alkyl group, C ₁ -C ₂₀ alkoxy group, C ₅ -C ₂₀ cycloalkyl group substituted with -F, -Cl, -Br, -CN, -NO ₂ or -OH; And an unsubstituted or C ₁ -C ₂₀ alkyl group, a C ₁ -C ₂₀ alkoxy group, a C ₅ -C ₃₀ heterocycloalkyl group substituted with -F, -Cl, -Br, -CN, -NO ₂ or -OH. It may be one or more selected from the group.

In Formula 1, X ₁ and X ₂ are each independently a single bond, a double bond, a substituted or unsubstituted C ₁ -C ₂₀ alkylene group, a substituted or unsubstituted C ₂ -C ₂₀ alkenylene group, substituted or Unsubstituted C ₂ -C ₂₀ alkynylene group, substituted or unsubstituted C ₁ -C ₂₀ heteroalkylene group, substituted or unsubstituted C ₇ -C ₃₀ alkylenearylene group, substituted or unsubstituted C ₆ -C _{A 30} arylene group, a substituted or unsubstituted C ₂ -C ₃₀ heteroarylene group.

The alkylene group represents a divalent alkyl group which is branched or straight chain, and the heteroalkylene group means that one or more carbon atoms present in the alkylene group are substituted with N, O, S, or P.

The arylene group is a divalent group having an aromatic ring system, and also includes a form in which two or more ring systems are bonded or fused to each other. The heteroarylene group refers to a divalent group having an aromatic ring ring system in which at least one carbon of the arylene group is substituted with at least one selected from the group consisting of N, O, S, and P.

When one or more hydrogen atoms present in various substituents such as the alkylene group, heteroalkylene group, arylene group or heteroarylene group are substituted, these substituents are independently of each other, -F, -Cl, -Br, -CN,- NO ₂ , -OH; C ₁ -C ₂₀ alkyl group unsubstituted or substituted with —F, —Cl, —Br, —CN, —NO ₂ or —OH; C ₁ -C ₂₀ alkoxy group unsubstituted or substituted with —F, —Cl, —Br, —CN, —NO ₂ or —OH; C ₆ -C ₃₀ aryl groups unsubstituted or substituted with C ₁ -C ₂₀ alkyl groups, C ₁ -C ₂₀ alkoxy groups, —F, —Cl, —Br, —CN, —NO ₂ or —OH; Unsubstituted or C ₁ -C ₂₀ alkyl group, C ₁ -C ₂₀ alkoxy group, C ₂ -C ₃₀ heteroaryl group substituted with —F, —Cl, —Br, —CN, —NO ₂ or —OH; Unsubstituted or C ₁ -C ₂₀ alkyl group, C ₁ -C ₂₀ alkoxy group, C ₅ -C ₂₀ cycloalkyl group substituted with -F, -Cl, -Br, -CN, -NO ₂ or -OH; And an unsubstituted or C ₁ -C ₂₀ alkyl group, a C ₁ -C ₂₀ alkoxy group, a C ₅ -C ₃₀ heterocycloalkyl group substituted with -F, -Cl, -Br, -CN, -NO ₂ or -OH. It may be one or more selected from the group.

More specifically, X ₁ and X ₂ are each independently a single bond, methylene group, ethylene group, -O- methylene group, phenylene group, C ₁ -C ₁₀ alkylphenylene group, C ₁ -C ₁₀ alkoxyphenylene group , Halophenylene group, cyanophenylene group, dicyanophenylene group, trifluoromethoxyphenylene group, o-, m-, or p-tolylene group, o-, m- or p-cumenylene group, mesitylene group, phenoxyphenyl groups, (α, α- dimethyl-benzene) phenyl groups, (N, N'- dimethyl) aminophenyl groups, (N, N'- diphenyl) aminophenyl group, (C ₁ -C ₁₀ alkyl, cyclohexyl ) phenylene, (anthracenyl) phenyl group, a penta-alkylenyl group, an indenyl group, a naphthyl group, a C ₁ -C ₁₀ alkyl naphthyl group, a C ₁ -C ₁₀ alkoxy-naphthyl group, a halo-naphthyl group, a cyano Naphthylene group, biphenylenylene group, C ₁ -C ₁₀ alkyl biphenylenylene group, C ₁ -C ₁₀ alkoxy biphenylenylene group, anthracenylene group, azurenylene group, heptarelenylene group, acenaphthylenylene group, Fenarenil Group, fluorenylene group, methyl anthylene group, phenanthrenylene group, triphenylenylene group, pyrenylene group, chryseneylene group, ethyl- xensenylene group, pisenylene group, peryleneylene group, chloroperyleneylene group , Pentaphenylene group, pentaxenylene group, tetraphenylenylene group, hexaphenylene group, hexasenylene group, rubisenylene group, coronylene group, trinaphthyleneylene group, heptaphenylene group, heptasenylene group, pyrantrenylene group, Ovarenylene group, carbazolylene group, C _1-10 alkyl carbazolylene group, thiophenylene group, indolylene group, furinylene group, benzimidazolylene group, quinolinyl group, benzothiophenylene group, parathia Genylene group, pyrrolyylene group, pyrazolylene group, imidazolylene group, imidazolinylene group, oxazolylene group, thiazolylene group, triazolylene group, tetrazolylene group, oxadiazolylene group, pyridinylene group, pyridazinyl Len group, pyrimidinylene group, pyrazinylene group and tea Tre carbonyl group may be selected from (thianthrenylene) the group consisting of, but not limited to this.

Among these, a single bond, a phenylene group or an anthracenylene group is preferable.

X ₁ and X ₂ may be different from or identical to each other. Preferably, X ₁ and X ₂ are the same as each other.

N ₁ and n ₂ each represent a number of repetitions of -X ₁ -and -X _2- . N ₁ and n ₂ may be each independently an integer of 0 to 5, preferably an integer of 0 to 3.

In this case, when n ₁ is 2 or more, the plurality of X ₁ may be the same as or different from each other, and when n ₂ is 2 or more, the plurality of X ₂ may be the same as or different from each other.

Ar ₁ connected to the terminal in Formula 1 is unsubstituted or C ₆ -C ₃₀ aryl group, C ₂ -C ₃₀ heteroaryl group, C ₄ -C ₃₀ cycloalkyl group or C having a substituent such as L ₁ , L ₂ Represents a ₂ -C ₃₀ cycloheteroalkyl group, Ar ₂ is an unsubstituted or substituted group such as L ₃ , L ₄ , a C ₆ -C ₃₀ aryl group, a C ₂ -C ₃₀ heteroaryl group, a C ₄ -C ₃₀ cycloalkyl group Or a C ₂ -C ₃₀ cycloheteroalkyl group.

Provided that at least either one of Ar ₁ or Ar ₂ contains two or more substituents.

L ₁ , L ₂ , L ₃ , L ₄ and the like are each independently a substituted or unsubstituted C ₆ -C ₃₀ aryl group, a substituted or unsubstituted C ₂ -C ₃₀ heteroaryl group, a substituted or unsubstituted A C ₅ -C ₂₀ cycloalkyl group, a substituted or unsubstituted C ₅ -C ₃₀ heterocycloalkyl group, or a substituted amino group having the formula —N (R ′) (R ″), wherein R ′ and R ″ are independently of one another , Hydrogen, a substituted or unsubstituted C ₁ -C ₂₀ alkyl group, a substituted or unsubstituted C ₆ -C ₃₀ aryl group, a substituted or unsubstituted C ₂ -C ₃₀ heteroaryl group, a C ₅ -C ₂₀ cycloalkyl group, It may be a C ₅ -C ₃₀ heterocycloalkyl group.

The aryl group is a monovalent group having an aromatic ring system, and includes a form in which two or more ring systems are bonded or fused to each other. The heteroaryl group refers to a group in which at least one carbon in the aryl group is substituted with at least one selected from the group consisting of N, O, S, and P. Meanwhile, a cycloalkyl group refers to an alkyl group having a ring system, and the heterocycloalkyl group refers to a group in which at least one carbon of the cycloalkyl group is substituted with at least one selected from the group consisting of N, O, S and P.

When at least one hydrogen atom present in the aryl group, heteroaryl group, cycloalkyl group and heterocycloalkyl group is substituted, their substituents are independently of each other, -F, -Cl, -Br, -CN, -NO ₂ , -OH; C ₁ -C ₂₀ alkyl group unsubstituted or substituted with —F, —Cl, —Br, —CN, —NO ₂ or —OH; C ₁ -C ₂₀ alkoxy group unsubstituted or substituted with —F, —Cl, —Br, —CN, —NO ₂ or —OH; C ₆ -C ₃₀ aryl groups unsubstituted or substituted with C ₁ -C ₂₀ alkyl groups, C ₁ -C ₂₀ alkoxy groups, —F, —Cl, —Br, —CN, —NO ₂ or —OH; Unsubstituted or C ₁ -C ₂₀ alkyl group, C ₁ -C ₂₀ alkoxy group, C ₂ -C ₃₀ heteroaryl group substituted with —F, —Cl, —Br, —CN, —NO ₂ or —OH; Unsubstituted or C ₁ -C ₂₀ alkyl group, C ₁ -C ₂₀ alkoxy group, C ₅ -C ₂₀ cycloalkyl group substituted with -F, -Cl, -Br, -CN, -NO ₂ or -OH; And a C ₅ -C ₃₀ heterocycloalkyl group substituted with an unsubstituted or C ₁ -C ₂₀ alkyl group, a C ₁ -C ₂₀ alkoxy group, -F, -Cl, -Br, -CN, -NO ₂ or -OH It may be one or more selected from the group consisting of.

More specifically, the L ₁ , L ₂ , L ₃ , L ₄ and the like are independently of each other, a phenyl group, a C ₁ -C ₁₀ alkylphenyl group, a C ₁ -C ₁₀ alkoxyphenyl group, halophenyl group, cyanophenyl group, dicyanophenyl group , Trifluoromethoxyphenyl group, o-, m- or p-tolyl group, o-, m- or p-cumenyl group, mesityl group, phenoxyphenyl group, (α, α-dimethylbenzene) phenyl group, (N, N'-dimethyl) aminophenyl group, (N, N'-diphenyl) aminophenyl group, (C ₁ -C ₁₀ alkylcyclohexyl) phenyl group, biphenyl group, C ₁ -C ₁₀ alkylbiphenyl group, C ₁ -C ₁₀ alkoxy Biphenyl group, pentarenyl group, indenyl group, naphthyl group, C ₁ -C ₁₀ alkylnaphthyl group, C ₁ -C ₁₀ alkoxynaphthyl group, halonaphthyl group, cyanonaphthyl group, biphenylenyl group, C ₁ -C ₁₀ Alkyl biphenylenyl group, C ₁ -C ₁₀ alkoxy biphenylenyl group, anthracenyl group, C ₁ -C ₁₀ alkyl anthracenyl group, C ₁ -C ₁₀ alkoxy anthracenyl group, azurenyl group, heptarenyl group, ace Naphthyleneyl, phenenyl, flu Renyl group, methyl anthryl group, phenanthrenyl group, triphenylenyl group, pyrenyl group, chrysenyl group, ethyl-crisenyl group, pisenyl group, perylenyl group, chloroperylenyl group, pentaphenyl group, pentacenyl group, Tetraphenylenyl group, hexaphenyl group, hexasenyl group, rubisenyl group, coronyl group, trinaphthylenyl group, heptaphenyl group, heptasenyl group, pyrantrenyl group, obarenyl group, carbazolyl group, C ₁ -C ₁₀ Alkyl carbazolyl group, thiophenyl group, indolyl group, furinyl group, benzimidazolyl group, quinolinyl group, benzothiophenyl group, parathiazinyl group, pyrrolyl group, pyrazolyl group, imidazolyl group, imidazolinyl group, Oxazolyl, thiazolyl, triazolyl, tetrazolyl, oxadiazolyl, pyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl, thianthrenyl, cyclopentyl, cyclo hexyl group, C ₁ -C ₁₀ alkyl, cyclohexyl, C ₁ -C ₁₀ alkoxy cycloalkyl Real group, oxiranyl group, pyrrolidinyl group, pyrazolidinyl group, imidazolidinyl group, piperidinyl group, piperazinyl group, morpholinyl group, 9,9-diphenyl-9H-fluoren-2-yl group It may be selected from the group consisting of a spirofluorenyl group and an amino group having -N (R ') (R "), but is not limited thereto. In this case, R 'and R "are each independently hydrogen, phenyl group, C ₁ -C ₁₀ alkylphenyl group, C ₁ -C ₁₀ alkoxyphenyl group, halophenyl group, cyanophenyl group, dicyanophenyl group, trifluoromethoxyphenyl group , o-, m-, or p-tolyl group, o-, m- or p-cumenyl group, mesityl group, phenoxyphenyl group, (α, α-dimethylbenzene) phenyl group, (N, N'-dimethyl) amino phenyl groups, (N, N'- diphenyl) aminophenyl group, (C ₁ -C ₁₀ alkyl, cyclohexyl) group, a (anthracenyl) phenyl group, a biphenyl group, C ₁ -C ₁₀ alkyl biphenyl group, C ₁ -C ₁₀ alkoxy Biphenyl group, pentarenyl group, indenyl group, naphthyl group, C ₁ -C ₁₀ alkylnaphthyl group, C ₁ -C ₁₀ alkoxynaphthyl group, halonaphthyl group, cyanonaphthyl group, biphenylenyl group and C ₁ -C ₁₀ It may be selected from the group consisting of alkyl biphenylenyl groups, but is not limited thereto.

Among these, a carbazole group, a phenyl group, a naphthyl group, an anthracenyl group, or a -N (R ') (R ") group in which R' and R" are independently of each other a naphthyl group and a phenyl group is preferable, and a carbazole group is furthermore preferred. desirable.

Preferred examples of the dimethylene cyclohexane of the formula (1) according to the present invention include compounds of the formula (2):

(2)

In Formula 2, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , X ₁ , X ₂ , n ₁ , n ₂ , L ₁ , L ₂ , L ₃ and L ₄ is as defined above.

As a more preferable example of the dimethylene cyclohexane of Chemical Formula 2, a compound of the following Chemical Formula 3 or 4 may be exemplified.

(3)

In Formula 3, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , L ₁ , L ₂ , L ₃ and L ₄ are as defined above.

&Lt; Formula 4 >

In Formula 4, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , L ₁ , L ₂ , L ₃ and L ₄ are as defined above, R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ are each independently hydrogen, halogen atom, cyano group, hydroxyl group, amino group, substituted or unsubstituted C ₁ -C ₂₀ alkyl group, substituted Or an unsubstituted C ₁ -C ₂₀ alkoxy group, a substituted or unsubstituted C ₆ -C ₃₀ aryl group, a substituted or unsubstituted C ₂ -C ₃₀ heteroaryl group, or formula -N (Z ′) (Z ″) Is a substituted amino group having Z 'and Z ", each independently, a substituted or unsubstituted C ₁ -C ₂₀ alkyl group, a substituted or unsubstituted C ₆ -C ₃₀ aryl group, a substituted or unsubstituted C ₂ -C ₃₀ heteroaryl group, a substituted or unsubstituted C ₅ -C ₂₀ cycloalkyl group, or a substituted or unsubstituted C ₅ -C ₃₀ heterocycloalkyl group.

According to one embodiment of the present invention, the cyclohexylene compound of Formula 1 according to the present invention may be represented by the following Chemical Formulas 5 to 8, but is not limited thereto:

&Lt; Formula 5 >

(6)

&Lt; Formula 7 >

(8)

Synthesis method of the dimethylene cyclohexane compound represented by Formula 1 is using a conventional organic synthesis method. One embodiment of a method for producing a dimethylene cyclohexane compound according to the present invention is a compound represented by the following formula 1a and a compound represented by the formula L ₁ -Q ₁ , a compound represented by L ₂ -Q ₂ , L _3- Reacting at least two selected from the group consisting of a compound represented by Q ₃ and a compound represented by L ₄ -Q ₄ to form a compound represented by the following Chemical Formula 1d, wherein the compound represented by Chemical Formula 1d is represented by Chemical Formula L Reacting with a compound represented by _1- Q ₁ and / or a compound represented by L ₂ -Q ₂ , and the like to form a compound represented by Formula 1 above:

<Formula 1a>

&Lt; EMI ID =

&Lt; Formula 1c >

<Formula 1d>

Among the above formulas,

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , X ₁ , X ₂ , n ₁ , and n ₂ refer to the part described with respect to Formula 1 above.

Wherein Ar ₁ ^'and Ar ^_2' is a substituted or unsubstituted C ₆ -C ₃₀ aryl group, C ₂ -C ₃₀ heteroaryl groups, C ₄ - C ₃₀ cycloalkyl group or C ₂ -C ₃₀ cycloalkyl represents a heterocyclic group;

Meanwhile, in Formulas 1b and 1c, Ha ₁ and Ha ₂ are each independently halogen such as F, Cl, Br, or I. Preferably, Ha ₁ and Ha ₂ are Br. m ₁ and m ₂ are integers of 0 to 5.

Provided that at least one of m ₁ and m ₂ is an integer of 2 or more.

Of the L ₁ -Q ₁ , L ₂ -Q ₂ , L ₃ -Q ₃ , L ₄ -Q ₄ of the above scheme, the definition of L ₁ group, L ₂ group, L ₃ group and L ₄ group, see the above bar And Q ₁ , Q ₂ , Q ₃ , Q ₄ are B-containing groups, or L ₁ , L ₂ , L ₃ , L ₄ are substituted amino groups having the formula -N (R ′) (R ″). In this case H.

,

,

또는

등을 포함하나, 이에 한정되지 않는다.Specific examples of the B-containing group, for example

,

,

or

But are not limited thereto.

Scheme 1 below illustrates the synthetic route of the dimethylene cyclohexane compound of the present invention in more detail:

First, the compound represented by Chemical Formula 1a is reacted with the compounds represented by Chemical Formulas 1b and 1c to obtain a compound represented by Chemical Formula 1d. The compound represented by Chemical Formula 1a may generally be used by purchasing a commercialized reagent, and the compounds represented by 1b and 1c may be an aryl compound substituted with methyl halide and triethyl phosphite (P (OEt)). ₃ ) can be obtained by reaction (for example, can be obtained by reacting bromobenzyl bromide with triethyl phosphite), but is not limited thereto. Thereafter, the compound represented by Formula 1d is reacted with the compounds represented by Formula L ₁ -Q ₁ , L ₂ -Q ₂ , L ₃ -Q ₃ , L ₄ -Q _4, etc. Can be obtained. The reaction can be carried out, for example, in the presence of K ₂ CO ₃ and Pd (PPh ₃ ) ₄ . The compounds represented by L ₁ -Q ₁ , L ₂ -Q ₂ , L ₃ -Q ₃ , L ₄ -Q _4, etc. may be, for example, L ₁ group, L ₂ group, L ₃ group, L ₄ group, or the like. It may be boronic acid or dioxaborolane having a respective _one , or an amine having an L ₁ group, an L ₂ group, an L ₃ group, an L ₄ group, or the like, but is not limited thereto. All compounds synthesized therefrom were confirmed by their 1H NMR and mass spectrometers.

In the method for producing the dimethylene cyclohexane compound, Ar ₁ and Ar ₂ are the same as each other, n ₁ and n ₂ are the same as each other, Ha ₁ and Ha ₂ are the same as each other, and L ₁ and L ₂ May be identical to each other.

The dimethylene cyclohexane compound according to the present invention as described above can be applied to the organic light emitting device. An organic light emitting device according to the present invention comprises a first electrode; A second electrode; And at least one layer of an organic film between the first electrode and the second electrode, wherein the organic film may include a dimethylene cyclohexane compound represented by Formula 1 as described above. More specifically, the organic layer may be a hole injection layer, a hole transport layer or a light emitting layer.

The structure of the organic light emitting device according to the present invention is very diverse. The organic EL device may further include at least one layer selected from the group consisting of a hole injecting layer, a hole transporting layer, a hole blocking layer, an electron blocking layer, an electron transporting layer, and an electron injecting layer between the first electrode and the second electrode.

More specifically, embodiments of the organic light emitting device according to the present invention refer to FIGS. 1A, 1B and 1C. The organic light emitting device of FIG. 1A has a structure consisting of a first electrode / hole injection layer / light emitting layer / electron transport layer / electron injection layer / second electrode, and the organic light emitting device of FIG. 1B includes a first electrode / hole injection layer / hole transport layer. / Light emitting layer / electron transport layer / electron injection layer / second electrode. In addition, the organic light emitting device of FIG. 1C has a structure of a first electrode / hole injection layer / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / electron injection layer / second electrode. In this case, at least one of the hole injection layer, the hole transport layer and the light emitting layer may include a dimethylene cyclohexane compound according to the present invention.

The light emitting layer of the organic light emitting device according to the present invention may include a phosphorescent or fluorescent dopant including red, green, blue or white. The phosphorescent dopant may be an organometallic compound containing at least one element selected from the group consisting of Ir, Pt, Os, Ti, Zr, Hf, Eu, Tb and Tm.

Hereinafter, a method of manufacturing an organic light emitting diode according to the present invention will be described with reference to the organic light emitting diode illustrated in FIG. 1C.

First, a first electrode material having a high work function on the substrate is formed by a deposition method, a sputtering method, or the like to form a first electrode. The first electrode may be an anode. Herein, a substrate used in a conventional organic light emitting device is used, and a glass substrate or a transparent plastic substrate having excellent mechanical strength, thermal stability, transparency, surface smoothness, ease of handling, and waterproofness is preferable. As the material for the first electrode, indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO ₂ ), zinc oxide (ZnO) or the like which is transparent and excellent in conductivity is used.

Next, a hole injection layer (HIL) may be formed on the first electrode by various methods such as a vacuum deposition method, a spin coating method, a casting method, and an LB method.

In the case of forming the hole injection layer by vacuum deposition, the deposition conditions vary depending on the compound used as the material of the hole injection layer, the structure and thermal properties of the hole injection layer, and the like. It is preferable that a vacuum degree of 10 ^-8 to 10 ^-3 torr, a deposition rate of 0.01 to 100 mW / sec, and a film thickness are usually appropriately selected in the range of 10 mV to 5 m.

In the case of forming the hole injection layer by spin coating, the coating conditions vary depending on the compound used as the material of the hole injection layer and the structure and thermal characteristics of the desired hole injection layer, but the coating speed is about 2000 rpm to 5000 rpm. After the coating, the heat treatment temperature for removing the solvent is preferably selected from a temperature range of about 80 ° C to 200 ° C.

The hole injection layer material may be a dimethylene cyclohexane compound having Formula 1 as described above. Or phthalocyanine compounds such as copper phthalocyanine disclosed in US Pat. No. 4,356,429 or the starburst type amine derivatives described in Advanced Material, 6, p.677 (1994), for example, TCTA, m-MTDATA, m-. MTDAPB, Pani / DBSA (Polyaniline / Dodecylbenzenesulfonic acid: polyaniline / dodecylbenzenesulfonic acid) or PEDOT / PSS (Poly (3,4-ethylenedioxythiophene) / Poly (4-styrenesulfonate): Poly (3,4) -Ethylenedioxythiophene) / poly (4-styrenesulfonate)), Pani / CSA (Polyaniline / Camphor sulfonic acid: polyaniline / camphorsulfonic acid) or PANI / PSS (Polyaniline) / Poly (4-styrenesulfonate): polyaniline) / Known hole injection materials such as poly (4-styrenesulfonate)) and the like can be used.

 Pani / DBSA

 PEDOT / PSS

The thickness of the hole injection layer may be about 100 Å to 10000 Å, preferably 100 Å to 1000 Å. If the thickness of the hole injection layer is less than 100 angstroms, the hole injection characteristics may be degraded. If the thickness of the hole injection layer exceeds 10000 angstroms, the driving voltage may increase.

Next, a hole transport layer (HTL) may be formed on the hole injection layer by various methods such as a vacuum deposition method, a spin coating method, a casting method, and an LB method. In the case of forming the hole transporting layer by the vacuum deposition method and the sputtering method, the deposition conditions and the coating conditions vary depending on the compound used, but are generally selected from substantially the same range of conditions as the formation of the hole injection layer.

The hole transport layer material may be a dimethylene cyclohexane compound having Formula 1 as described above. Or carbazole derivatives such as N-phenylcarbazole, polyvinylcarbazole and the like, N, N'-bis (3-methylphenyl) -N, N'- diphenyl- [ Amine having an aromatic condensed ring such as N, N'-tetramethyldisiloxane, -4,4'-diamine (TPD) and N, N'-di (naphthalen- The same known hole transport materials can be used.

The thickness of the hole transporting layer may be about 50 Å to 1000 Å, preferably 100 Å to 600 Å. When the thickness of the hole transporting layer is less than 50 Å, the hole transporting property may be degraded. When the thickness of the hole transporting layer is more than 1000 Å, the driving voltage may increase.

Next, a light emitting layer (EML) may be formed on the hole transporting layer by a method such as a vacuum evaporation method, a spin coating method, a casting method, or an LB method. When a light emitting layer is formed by a vacuum deposition method and a spin coating method, the deposition conditions vary depending on the compound used, but generally, the conditions are substantially the same as those for forming the hole injection layer.

The light emitting layer may include a dimethylene cyclohexane compound of Formula 1 according to the present invention as described above. At this time, it may be used with a known host material suitable for the dimethylene cyclohexane compound of Formula 1, or may be used with a known dopant material. It is also possible to use the dimethylene cyclohexane compound of Formula 1 alone. In the case of the host material, for example, Alq ₃ or CBP (4,4'-N, N'-dicarbazole-biphenyl), PVK (poly (n-vinylcarbazole)) or the like can be used. In the case of the dopant material, IDE102, IDE105 and C545T available from Hayashibara Co., Ltd., which are available from Idemitsu Co., Ltd., can be used as the fluorescent dopant. Ir (PPy) ₃ (PPy = 2-phenylpyridine), F2Irpic which is a blue phosphorescent dopant, red phosphorescent dopant RD 61 by UDC, etc. can be used. The compound of formula 9 shows the structure of DPAVBi usable as dopant.

&Lt; Formula 9 >

The doping concentration of the dopant is not particularly limited, but the content of the dopant is generally 0.01 to 15 parts by weight based on 100 parts by weight of the host.

The thickness of the light emitting layer may be about 100 Å to 1000 Å, preferably 200 Å to 600 Å. When the thickness of the light emitting layer is less than 100 Å, the light emitting characteristics may be degraded. If the thickness of the light emitting layer is more than 1000 Å, the driving voltage may increase.

When used with a phosphorescent dopant in the light emitting layer, in order to prevent the triplet excitons or holes from diffusing into the electron transport layer, holes such as vacuum deposition, spin coating, cast, LB, etc. are formed on the hole transport layer. The blocking layer HBL may be formed. In the case of forming the hole blocking layer by the vacuum deposition method and the spin coating method, the conditions vary depending on the compound used, but are generally selected from substantially the same range of conditions as the formation of the hole injection layer. Known hole blocking materials that can be used include, for example, oxadiazole derivatives, triazole derivatives, phenanthroline derivatives, hole blocking materials described in JP 11-329734 (A1), BCP and the like.

The thickness of the hole blocking layer may be about 50 Å to 1000 Å, preferably 100 Å to 300 Å. This is because when the thickness of the hole blocking layer is less than 50 kV, the hole blocking property may be deteriorated. When the thickness of the hole blocking layer is more than 1000 kV, the driving voltage may increase.

Next, the electron transport layer (ETL) is formed using various methods such as vacuum deposition, spin coating, and casting. In the case of forming the electron transporting layer by the vacuum deposition method and the spin coating method, the conditions vary depending on the compound used, but generally, the conditions are substantially the same as those for forming the hole injection layer. The electron transport layer material functions to stably transport electrons injected from an electron injection electrode (Cathode), and known materials such as quinoline derivatives, particularly tris (8-quinolinorate) aluminum (Alq ₃ ), TAZ, Balq, and the like. You can also use

The thickness of the electron transporting layer may be about 100 ANGSTROM to 1000 ANGSTROM, preferably 200 ANGSTROM to 500 ANGSTROM. When the thickness of the electron transporting layer is less than 100 angstroms, the electron transporting characteristics may be deteriorated. When the thickness of the electron transporting layer exceeds 1000 angstroms, the driving voltage may increase.

Further, an electron injection layer (EIL), which is a material having a function of facilitating the injection of electrons from the cathode, may be laminated on the electron transporting layer, which is not particularly limited.

As the electron injection layer, any material known as an electron injection layer forming material such as LiF, NaCl, CsF, Li ₂ O, BaO, or the like can be used. The deposition conditions of the electron injection layer vary depending on the compound used, but are generally selected from substantially the same range of conditions as the formation of the hole injection layer.

The thickness of the electron injection layer may be about 1 A to 100 A, preferably 5 A to 50 A. If the thickness of the electron injection layer is less than 1 angstrom, the electron injection characteristics may be deteriorated. If the thickness of the electron injection layer exceeds 100 angstroms, the driving voltage may increase.

Finally, the second electrode can be formed on the electron injection layer by a vacuum evaporation method, a sputtering method, or the like. The second electrode may be used as a cathode. As the metal for forming the second electrode, a metal, an alloy, an electrically conductive compound having a low work function, or a mixture thereof may be used. Specific examples thereof include lithium (Li), magnesium (Mg), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), magnesium- . In addition, a transmissive cathode using ITO and IZO may be used to obtain the front light emitting device.

The organic light emitting device of the present invention comprises a first electrode, a hole injection layer (HIL), a hole transport layer (HTL), a light emitting layer (EML), a hole blocking layer (HBL), an electron transport layer (ETL), an electron injection layer shown in FIG. (EIL), as well as an organic light emitting device having a second electrode structure, as well as an organic light emitting device having various structures (for example, the organic light emitting device shown in Figure 1A to be described in more detail in the following embodiments), of course. .

Hereinafter, the synthesis examples and examples of the compounds of the formulas (5), (7) and (8) according to the present invention are specifically illustrated, but the present invention is not limited to the following synthesis examples and examples.

(Example)

Synthesis Example 1

A compound of formula 5 was synthesized according to the reaction route of Scheme 2:

<Reaction Scheme 2>

Synthesis of intermediate A

1,3-dibromotoluene (4 mmol, 1.0 g) and NBS (N-bromosuccinimide, 6 mmol, 1.07 g) benzoyl peroxide (0.4 mmol, 96 mg) were added to 100 ml of benzene and refluxed for 5 hours. Purified by column chromatography and recrystallization, and dried in vacuo to give 1,3-dibromo-5-bromomethyl-benzene (881 mg, yield = 67%). Again (triethylphosphite [P (OCH ₂ CH ₃ ) ₃ ] (20 mmol, 3.5 g) was mixed and stirred for 12 hours at reflux. The solvent was removed under reduced pressure, and then cooled to room temperature, 5 (2.15 g, 87%) was obtained.

¹ H-NMR (CDCl ₃ , 300 MHz, ppm): 7.41 (s, 1H), 7.16 (s, 2H), 5.22 (s, 2H), 3.11-3.32 (m, 4H), 1.21 (t, 6H)

Synthesis of intermediate B

The intermediate A (10 mmol, 3.86 g) and cyclohexane-1,4-dione (4.5 mmol, 0.5 g) were dissolved in a solvent of tetrahydrofuran (THF, 300 ml), followed by t-BuOK (11 mmol, 1.25 g). After the reaction was carried out at 60 ° C. for one day, the solution was left alone to remove the solvent, and then methanol (100 ml) was added, filtered and washed with methanol again. Subsequently, purification was performed by silica gel column chromatography (CHCl ₃ ) to obtain 2.2 g (83% yield) of intermediate B.

¹ H-NMR (CDCl ₃ , 300 MHz, ppm): 7.85 (s, 2H), 7.10 (d, 4H), 6.25 (s, 2H), 2.53-2.31 (m, 8H)

Synthesis of Compound of Formula 5

The intermediate B (10 mmol, 5.76 g) was dissolved in o-xylene (200 ml) solvent, then carbazole (60 mmol, 10 g), Pd ₂ dba ₃ (4.0 mmol, 3.7 g), P (t-Bu ) ₃ (3.0 mmol, 0.6 g) and sodium t-butoxide (60 mmol, 5.8 g) were added followed by stirring at reflux for 24 h. After cooling to room temperature, the solvent was removed, separated and purified by silica gel column chromatography, and then recrystallized. 4.1 g (yield 45%) of compound 5 was obtained from white solid powder of formula (5).

¹ H-NMR (CDCl ₃ , 300 MHz, ppm): 8.15 (m, 8H), 7.6-7.2 (m, 30H), 6.15 (s, 2H), 2.53-2.30 (m, 8H)

Synthesis Example 2

A compound of formula 7 was synthesized according to the reaction route of Scheme 3:

<Reaction Scheme 3>

Synthesis of intermediate C

4-bromobenzyl bromide (40 mmol, 10 g) was mixed with triethylphosphite [P (OCH ₂ CH ₃ ) ₃ ] (80 mmol, 13.3 g) and stirred at 185 ° C. for 6 hours. After the solvent was removed under reduced pressure, the mixture was cooled to room temperature to obtain white solid powder (11.8 g, 96%).

¹ H-NMR (CDCl ₃ , 300 MHz, ppm): 7.42 (d, 2H), 7.18 (d, 2H), 4.02 (m, 4H), 3.12 (s, 1H), 3.05 (s, 1H), 1.25 ( t, 6H)

Synthesis of intermediate D

The intermediate C (100 mmol, 31.6 g) was dissolved in a solvent of tetrahydrofuran (THF, 300 ml), and then t-BuOK (110 mmol, 12.5 g) was added and reacted at 50 ° C. for 1 hour, followed by 1,4-cyclo Hexanedione (40 mmol, 5 g) was added dropwise and reacted at 70 ° C. for one day, ethanol (20 ml) was added and dried in vacuo, followed by 200 ml of methylene chloride. The organic layer collected therefrom was washed twice with 200 ml of water, dried over anhydrous magnesium sulfate, and then filtered to dry only the solvent portion. Subsequently, purification was performed by silica gel column chromatography to obtain 9.7 g (yield 58%) of intermediate D.

¹ H-NMR (CDCl ₃ , 300 MHz, ppm): 7.42 (d, 4H), 7.10 (d, 4H), 6.25 (s, 2H), 2.53-2.31 (m, 8H)

The obtained intermediate D (10.6 mmol, 4.45 g) was dissolved in o-xylene (80 ml) solvent, and then the compound of formula 11 was dissolved (14.9 mmol, 6.62 g), Pd ₂ (dba) ₃ (tri (dibenzylideneacetone). Dipalladium (0)) (0.54 mmol, 0.5 g), t-butylphosphine (0.41 mmol, 0.083 g) and NaO-t-Bu (30 mmol, 2.88 g) were added and then stirred at room temperature for 4 hours. It was. After the reaction was completed, 100 ml of dichloromethane was added, washed twice with 100 mL of water, the organic layer was collected, dried over anhydrous magnesium sulfate, the solvent was evaporated to obtain a product, and then separated and purified by silica gel column chromatography. , By recrystallization. 3.7 g (yield 55%) of the compound of formula (7) were obtained.

¹ H-NMR (CDCl ₃ , 300 MHz, ppm): 7.81 (m, 4H), 7.64 (m, 4H), 7.54-7.52 (m, 6H), 7.41 (m, 6H), 7.3-7.2 (m, 22H ), 6.34 (s, 2H), 2.61-2.37 (m, 8H)

Synthesis Example 3

A compound of formula 8 was synthesized according to the reaction route of Scheme 4:

<Reaction Scheme 4>

Preparation of the intermediate C and intermediate D is the same as in Synthesis Example 2, the obtained intermediate D (10.6 mmol, 4.45 g) was dissolved in o-xylene (80 ml) solvent, and then the compound of formula 12 (14.9 mmol, 6.59 g), Pd ₂ (dba) ₃ (tri (dibenzylideneacetone) dipalladium (0)) (0.54 mmol, 0.5 g), t-butylphosphine (0.41 mmol, 0.083 g), NaO-t-Bu (30 mmol, 2.88 g) was added, followed by stirring at room temperature for 4 hours. After the reaction was completed, 100 ml of dichloromethane was added, washed twice with 100 mL of water, the organic layer was collected, dried over anhydrous magnesium sulfate, the solvent was evaporated to obtain a product, and then separated and purified by silica gel column chromatography. , By recrystallization. 2.9 g (44% yield) of compound of formula 8 were obtained.

¹ H-NMR (CDCl ₃ , 300 MHz, ppm): 8.13 (m, 4H), 7.84 (m, 4H), 7.60-7.50 (m, 4H), 7.39 (m, 6H), 7.3-7.2 (m, 22H ), 6.32 (s, 2H), 2.59-2.39 (m, 8H)

Example 1

Using the compound of Formula 7 alone as a host of the light emitting layer, an organic light emitting device having the following structure was manufactured.

ITO / α-NPD (750 Hz) / 5 wt% Ir (piq) 3 (Compound 7) (350 Hz) / Balq (50 Hz) / Alq ₃ (180 Hz) / LiF (10 Hz) / Al (2000 Hz)

The anode was cut into a size of 15 Ω / cm ² (1000 Å) ITO glass substrate 50mm x 500mm x 0.7mm and ultrasonically cleaned for 15 minutes in acetone, isopropyl alcohol and pure water, followed by UV ozone cleaning for 15 minutes. This is called substrate 1. Α-NPD was vacuum-deposited on the substrate 1 to form a hole transport layer of 750 kPa. A host and guest compound (Ir (piq) 3) was vacuum deposited on the hole transport layer to form a light emitting layer having a thickness of 350 Å. Thereafter, the Alq ₃ compound was vacuum-deposited to a thickness of 180 에 on the emission layer to form an electron transport layer. LiF 10 Å (electron injection layer) and Al 2000 Å (cathode) were sequentially vacuum deposited on the electron transport layer to manufacture an organic light emitting device as shown in FIG. 1A.

Example 2

Using the compound of Formula 7 as a host of the light emitting layer, an organic light emitting device having the following structure was manufactured.

ITO / PEDOT (500 Hz) / 5 wt% Ir (piq) 3 (Compound 7) (550 Hz) / Balq (50 Hz) / Alq 3 (180 Hz) / LiF (10 Hz) / Al (2000 Hz)

The anode was cut into 50 mm x 500 mm x 0.7 mm sized 15 Ω / cm ² (1000 Å) ITO glass substrate, sonicated for 15 minutes in acetone, isopropyl alcohol and pure water, followed by UV ozone cleaning for 15 minutes. This is called substrate 1. The PEDOT was heat-treated at 110 ° C. for 5 minutes on a substrate 1 and then heat-treated at 10 ° C. for 10 minutes at 200 ° C. to form a hole transport layer of 500 kV. On the hole transport layer, a mixture of host and guest compounds (1. compound 7 (neat), 2. CH 24 + red dopant (5 wt%), 3. CH 25 + red dopant (5 wt%) = 1 wt%, dichloromethane is used) ) And spin-treated at 110 ° C. for 30 minutes to form a light emitting layer having a thickness of 550 μs. Thereafter, an electron transport layer was formed by vacuum depositing 50 μm of Balq and 180 μm of Alq ₃ compound on the emission layer. LiF 10 Å (electron injection layer) and Al 2000 Å (cathode) were sequentially vacuum deposited on the electron transport layer to manufacture an organic light emitting device as shown in FIG. 1A.

Example 3

An organic light-emitting device was manufactured in the same manner as in Example 1, except that the compound of Formula 8 was used instead of the compound of Formula 7 as the host compound of the emission layer in Example 1.

Example 4

An organic light-emitting device was manufactured in the same manner as in Example 2, except that the compound of Formula 8 was used instead of the compound of Formula 7 as the host compound of the emission layer in Example 2.

Experimental Example

For the compounds of Chemical Formulas 7 and 8 and the organic EL devices obtained in Examples 2 and 4, a driving voltage, color purity, luminous efficiency, highest luminance, current density, and EL were measured using a PR650 (Spectroscan) Source Measurement Unit. Peak wavelengths were evaluated, respectively, and are shown in Tables 1 and 2 below.

division turn on
Voltage [V] CIE color coordinates
[100cd standard] Drive voltage [V] and efficiency [cd / A] x y 100cd 600cd 1200cd Compound 7 6 0.2565 0.4369 11.2V 0.056 - - - - Compound 8 12.6 - - - - - - - - Example 1 4.2 0.6654 0.3198 6 V 5.64 7.6 V 6.73 8.4 V 8 Example 2 9.2 0.6713 0.3264 16 V 0.426 18.8V 0.65 20V 0.5 Example 3 3.8 0.6705 0.3216 5.2V 6.45 6.8 V 7.64 7.8V 9.44 Example 4 5.6 0.6739 0.3242 14.6 V 0.59 18V 0.71 19.6 V 0.51

Highest brightness Current density (@ 100cd) EL spectrum (@ 100cd) Compound 7 158 5.94 (mA / cm ² ) - Compound 8 92 164.5 (mA / cm ² ) - Example 1 > 7231 1.77 (mA / cm ² ) 630 nm Example 2 1929 23.4 (mA / cm ² ) 628 nm Example 3 > 7466 1.55 (mA / cm ² ) 630 nm

Tables 1 and 2 in the above formulas 7 and 8 and the organic light emitting device employing the same according to the present invention, because the red light emitting material for deposition showed excellent results during the deposition process compared to the spin process, spin process and It was confirmed that both of the deposition process functions as a host material of the red light emitting material.

The dimethylene cyclohexane compound represented by Formula 1 according to the present invention has excellent luminescence properties and thermal stability. Therefore, by using the dimethylene cyclohexane compound according to the present invention, it is possible to obtain an organic light emitting device having a low driving voltage, excellent color purity, high efficiency.

Claims (13)

A dimethylene cyclohexane compound represented by any one of the following Chemical Formulas 1 and 8: &Lt; Formula 1 >

In Formula 1, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are hydrogen; X ₁ and X ₂ represent a phenylene group; n ₁ and n ₂ are each independently an integer of 0 to 3, wherein when n ₁ or n ₂ is 2 or more, a plurality of X ₁ or X ₂ may be the same as or different from each other; Ar ₁ and Ar ₂ independently of each other represent a phenyl group or a fluorenyl group; Provided that at least one of Ar _{1 and} Ar ₂ includes two or more substituents, The substituents included in Ar ₁ or Ar ₂ independently represent a phenyl group or a carbazole group; (8)

. delete delete delete delete The dimethylene cyclohexane compound of claim 1, wherein the compound of Formula 1 is a compound of Formula 2: (2)

In Formula 2, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , X ₁ , X ₂ , n ₁ and n ₂ are the same as defined in claim 1, L ₁ , L ₂ , L ₃ and L ₄ each independently represent a phenyl group or a carbazole group. The dimethylene cyclohexane compound of claim 1, wherein the compound of Formula 1 is a compound of Formula 3 or 4 below: (3)

In Formula 2, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , X ₁ , X ₂ , n ₁ and n ₂ are the same as defined in claim 1, L ₁ , L ₂ , L ₃ and L ₄ are as defined in claim 6, &Lt; Formula 4 >

In Formula 2, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , X ₁ , X ₂ , n ₁ and n ₂ are the same as defined in claim 1, L ₁ , L ₂ , L ₃ and L ₄ are as defined in claim 6, R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , and R ₁₆ are hydrogen. The dimethylene cyclohexane compound of claim 1, wherein the compound of Formula 1 is represented by any one of the following Formulas 5 to 7. &Lt; Formula 5 >

(6)

&Lt; Formula 7 >

Reacting the compound represented by Formula 1a with the compound represented by Formula 1b and / or the compound represented by Formula 1c to form a compound represented by Formula 1d; The compound represented by Formula 1d comprises a compound represented by Formula L ₁ -Q ₁ , a compound represented by L ₂ -Q ₂ , a compound represented by L ₃ -Q ₃ , and a compound represented by L ₄ -Q ₄ A method for preparing the dimethylene cyclohexane compound of formula 1 according to claim 1, comprising the step of forming a compound represented by formula 1 according to claim 1 by reacting with at least two selected from the group: <Formula 1a>

&Lt; EMI ID =

&Lt; Formula 1c >

<Formula 1d>

Among the above formulas, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are hydrogen; X ₁ and X ₂ represent a phenylene group; n ₁ and n ₂ are each independently an integer of 0 to 3, wherein when n ₁ or n ₂ is 2 or more, a plurality of X ₁ or X ₂ may be the same as or different from each other; Ar ₁ ^′ and Ar ₂ ^′ independently of one another represent a phenyl group or a fluorenyl group; Ha ₁ and Ha ₂ represent a halogen element; m ₁ and m ₂ represent an integer of 0 to 5, provided that at least one of m ₁ and m ₂ represents an integer of 2 or more; L ₁ -Q ₁ , L ₂ -Q ₂ , L ₃ -Q ₃ , L ₄ -Q ₄ in the above scheme are independently of each other,

,

,

,

And carbazole groups. A first electrode; A second electrode; And at least one layer of organic film between the first electrode and the second electrode, wherein the organic film is formed according to any one of claims 1, 6, 7, and 8. An organic light-emitting device comprising a methylene cyclohexane compound. The organic light emitting device of claim 10, wherein the organic layer is a hole injection layer, a hole transport layer, or a light emitting layer. The method of claim 10, further comprising at least one layer selected from the group consisting of a hole injection layer, a hole transport layer, an electron blocking layer, a hole blocking layer, an electron transport layer and an electron injection layer between the first electrode and the second electrode. An organic light emitting device characterized in that. The method of claim 12, wherein the device is a first electrode / hole injection layer / light emitting layer / electron transport layer / electron injection layer / second electrode, the first electrode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / An organic light emitting device having a structure of a second electrode or a first electrode / hole injection layer / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / electron injection layer / second electrode.

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