KR102457841B1 - Copolymer, coating composition comprising the copolymer, organic light emitting device using the same, method of manufacturing the same and method of manufacturing the copolymer - Google Patents

Abstract

The present specification includes a unit represented by Formula 11 and an arylamine unit, a polydispersity index (PDI) of 1.3 or less, and a palladium content of 1 ppm or less, a coating composition comprising the copolymer, the coating composition An organic light emitting device including an organic material layer formed of

Description

Copolymer, coating composition comprising same, organic light emitting device using same, and manufacturing method thereof

The present specification relates to a copolymer, a coating composition including the same, an organic light emitting device including an organic material layer formed of the coating composition, a method for manufacturing the organic light emitting device, and a method for preparing the copolymer.

Conventionally, a deposition process has been mainly used to manufacture an organic light emitting device. However, there is a problem that a lot of material loss occurs when manufacturing an organic light emitting device through the deposition process. Materials used in organic light emitting devices for solution processes are being developed.

As a material for the solution process, not only monomolecular materials but also polymer materials with excellent coating properties are being developed. However, in the case of polymers prepared by the polymer synthesis method using the conventionally used palladium catalyst, the PDI is large and the palladium derivatives are There is a problem in that the performance and lifespan of the device are adversely affected by remaining and including a hydroxyl group and a halogen group at the end of the polymer.

Therefore, there is a need for development of a method for manufacturing a polymer material having a low PDI and exhibiting excellent performance and long life characteristics when applied to a device.

Korean Patent Publication No. 2012-0112277

The present specification provides a copolymer, a coating composition comprising the same, an organic light emitting device including an organic material layer formed of the coating composition, a method of manufacturing the organic light emitting device, and a method of manufacturing the copolymer.

The present specification provides a copolymer including a unit represented by the following Chemical Formula 11 and an arylamine unit, a polydispersity index (PDI) of 1.3 or less, and a palladium content of 1 ppm or less.

[Formula 11]

In the formula (11),

X1 is Si(R1)(R2) or C(R3)(R4),

R1 to R4 and Ar1 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; cyano group; a substituted or unsubstituted fluoroalkyl group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,

n1 is an integer of 0 to 6, and when n1 is 2 or more, a plurality of Ar1s are the same as or different from each other.

The present specification provides a coating composition comprising the above-described copolymer.

In addition to this, the present specification includes a first electrode; a second electrode; and at least one organic material layer provided between the first electrode and the second electrode, wherein at least one of the organic material layers provides an organic light emitting device including the above-described coating composition.

In addition, the present specification includes the steps of preparing a substrate; forming a first electrode on the substrate; forming one or more organic material layers on the first electrode; and forming a second electrode on the organic material layer, wherein the forming of the organic material layer provides a method of manufacturing an organic light emitting device comprising forming one or more organic material layers using the above-described coating composition. .

Finally, in the present specification, a step of reacting a compound represented by the following Chemical Formula 1 and an arylamine compound with a Grignard reagent containing magnesium, a polydispersity index (PDI) of 1.3 or less, and a palladium content of 1 ppm or less A method for preparing a copolymer and a copolymer prepared by the method are provided.

[Formula 1]

In Formula 1,

X1 is Si(R1)(R2) or C(R3)(R4),

R1 to R4 and Ar1 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; cyano group; a substituted or unsubstituted fluoroalkyl group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,

n1 is an integer of 0 to 6, and when n1 is 2 or more, a plurality of Ar1s are the same as or different from each other,

A1 and A2 are the same as or different from each other, and each independently represents a halogen group.

Since the copolymer according to an exemplary embodiment of the present invention includes the unit represented by Formula 11 and the arylamine unit, the palladium content is 1 ppm or less, and the polydispersity index (PDI) is 1.3 or less, charge mobility It is possible to increase the polymerization reproducibility of the copolymer by high

In addition, the copolymer according to an exemplary embodiment of the present invention is prepared by reacting a compound represented by Formula 1 and an arylamine compound with a Grignard reagent containing magnesium, and a block copolymer can be synthesized through the above preparation method. It may exhibit properties different from those of the random copolymer.

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

Hereinafter, the present specification will be described in detail.

According to an exemplary embodiment of the present specification, it comprises a step of reacting a compound represented by the following Chemical Formula 1 and an arylamine compound with a Grignard reagent containing magnesium, a polydispersity index (PDI) of 1.3 or less, and palladium Provided is a method for preparing a copolymer having a content of 1 ppm or less.

[Formula 1]

In Formula 1,

X1 is Si(R1)(R2) or C(R3)(R4),

R1 to R4 and Ar1 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; cyano group; a substituted or unsubstituted fluoroalkyl group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,

n1 is an integer of 0 to 6, and when n1 is 2 or more, a plurality of Ar1s are the same as or different from each other,

A1 and A2 are the same as or different from each other, and each independently represents a halogen group.

In the method for preparing the copolymer, the step of preparing the copolymer by reacting the compound represented by Chemical Formula 1 and the arylamine compound with a Grignard reagent containing magnesium is 1) the compound represented by Chemical Formula 1 containing magnesium a step of reacting with a Grignard reagent and a step of reacting the arylamine compound with a Grignard reagent containing magnesium, respectively, or 2) a Grignard containing the compound of Formula 1 and the arylamine compound simultaneously with magnesium It can be reacted with reagents.

The polydispersity index (PDI) of the copolymer prepared by the method for preparing the copolymer of the present invention is 1.3 or less, and preferably 1 or more and 1.2 or less. When the polydispersity index (PDI) of the copolymer satisfies the above range, polymerization reproducibility of the copolymer can be increased, and when manufacturing a device including the copolymer, a device having excellent performance and improved lifespan is manufactured can do.

According to an exemplary embodiment of the present specification, the content of palladium in the copolymer prepared by the method for preparing the copolymer is 1 ppm or less, preferably 0 ppm or more and 0.1 ppm or less. The copolymer prepared by the method for preparing the copolymer of the present invention is polymerized using a Grignard reagent containing magnesium, so that the palladium content in the prepared copolymer satisfies the above range, and the polydispersity index (PDI) is 1.3 The following copolymers can be obtained. For this reason, as mentioned above, the polymerization reproducibility of a copolymer can be improved.

The content of palladium can be confirmed through elemental analysis using ICP-OES or ICP-MS analysis.

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

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

In the present specification, the term "combination of these" included in the expression of the markush format means a mixed or combined state of two or more selected from the group consisting of the components described in the expression of the markush form, It means to include two or more selected from the group consisting of components.

As used herein, the term 'unit' is a repeating structure included in the monomer of the copolymer, and refers to a structure in which the monomer is bonded to the copolymer by polymerization.

In the present specification, the meaning of 'including a unit' means included in the main chain in the copolymer.

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

는 다른 치환기 또는 결합부에 결합되는 부위를 의미한다.In this specification,

refers to a site bonded to another substituent or a bonding group.

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

As used herein, the term "substituted or unsubstituted" refers to deuterium; halogen group; cyano group; an alkyl group; alkoxy group; alkenyl group; amine group; cycloalkyl group; aryl group; and substituted or unsubstituted by one or more substituents selected from the group consisting of a heterocyclic group, or substituted or unsubstituted in which two or more substituents among the above-exemplified substituents are linked. For example, "a substituent in which two or more substituents are connected" may be a biphenyl group. That is, the biphenyl group may be an aryl group, and may be interpreted as a substituent in which two phenyl groups are connected.

In the present specification, examples of the halogen group include fluorine (F), chlorine (Cl), bromine (Br) or iodine (I).

In the present specification, the alkyl group may be a straight chain, branched chain, or cyclic chain, and the number of carbon atoms is not particularly limited, but may be 1 to 30. According to an example, the number of carbon atoms may be 1 to 20. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a tert-butyl group, an isobutyl group, a pentyl group; hexyl group; heptyl group; There is an octyl group, and the like, but is not limited thereto.

In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms, and specifically, cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3,4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, etc., but are not limited thereto. does not

In the present specification, the aryl group may be monocyclic or polycyclic, and may have 6 to 60 carbon atoms. According to an example, the carbon number of the aryl group may be 6 to 30. Specific examples of the aryl group include, but are not limited to, a phenyl group, a biphenyl group, a terphenyl group, a quarterphenyl group, a naphthyl group, an anthracenyl group, a phenanthryl group, a fluorenyl group, and the like.

,

및

등이 될 수 있다. 다만, 이에 한정되는 것은 아니다.In the present specification, the fluorenyl group may be substituted, and adjacent substituents may combine with each other to form a ring. When the fluorenyl group is substituted,

,

and

etc. can be However, the present invention is not limited thereto.

In the present specification, the heterocyclic group includes at least one atom or a heteroatom other than carbon, and specifically, the heteroatom may include at least one atom selected from the group consisting of O, N, Si and S, and the like. The number of carbon atoms of the heterocyclic group is not particularly limited, but may have 2 to 60 carbon atoms, and in one example may have 2 to 30 carbon atoms. Examples of the heterocyclic group include a thiophene group, a furan group, a pyrrole group, an imidazole group, a thiazole group, an oxazole group, an oxadiazole group, a pyridyl group, a bipyridyl group, a pyrimidyl group, a triazine group, a triazole group, acri Diyl group, pyridazine group, pyrazinyl group, quinolinyl group, quinazoline group, quinoxalinyl group, isoquinoline group, indole group, carbazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group , a benzofuranyl group, a phenanthroline group, a thiazolyl group, an isoxazolyl group, an oxadiazolyl group, a thiadiazolyl group, a benzothiazolyl group, a phenothiazinyl group, and a dibenzofuranyl group. is not limited to

The heterocyclic group may be monocyclic or polycyclic, and may be aromatic, aliphatic, or a condensed ring of aromatic and aliphatic.

The heteroaryl group may be selected from the examples of the heterocyclic group described above, except that the heteroaryl group is aromatic.

In the present specification, the arylene group may be selected from the examples of the above-described aryl group, except that it is a divalent group.

According to an exemplary embodiment of the present specification, A1 and A2 are the same as or different from each other, and are each independently -F, -Cl, -Br or -I.

According to another exemplary embodiment, A1 and A2 are the same as or different from each other, and each independently represents -Br or -I.

In another exemplary embodiment, A1 is -I, and A2 is -Br. The copolymer prepared using the compound in which A1 is -I and A2 is -Br has a low polydispersity index PDI value. can be manufactured.

According to an exemplary embodiment of the present specification, Chemical Formula 1 is represented by the following Chemical Formula 1-1.

[Formula 1-1]

In Formula 1-1,

The definitions of X1, Ar1 and n1 are as defined in Formula 1 above.

According to an exemplary embodiment of the present specification, X1 is Si(R1)(R2) or C(R3)(R4).

In an exemplary embodiment of the present specification, R1 to R4 and Ar1 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; cyano group; a substituted or unsubstituted fluoroalkyl group having 1 to 20 carbon atoms; a substituted or unsubstituted C 1 to C 20 alkyl group; a substituted or unsubstituted C 3 to C 30 cycloalkyl group; a substituted or unsubstituted aryl group having 6 to 60 carbon atoms; Or a substituted or unsubstituted heterocyclic group having 2 to 60 carbon atoms.

According to another exemplary embodiment, R1 to R4 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; a substituted or unsubstituted C 1 to C 20 alkyl group; or a substituted or unsubstituted C6-C60 aryl group.

In another exemplary embodiment, R1 to R4 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; a substituted or unsubstituted C 1 to C 20 alkyl group; or an aryl group having 6 to 60 carbon atoms which is unsubstituted or substituted with an alkyl group having 1 to 20 carbon atoms.

In another exemplary embodiment, R1 to R4 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; a substituted or unsubstituted octyl group; or a phenyl group unsubstituted or substituted with a hexyl group.

According to an exemplary embodiment of the present specification, Ar1 is hydrogen or deuterium.

According to an exemplary embodiment of the present specification, n1 is 0 or 1.

In an exemplary embodiment of the present specification, the method for preparing the copolymer further comprises a compound represented by the following formula (3). In this case, 1) reacting the compound represented by Formula 1 with a Grignard reagent containing magnesium; reacting the arylamine compound with a Grignard reagent containing magnesium; and reacting the compound represented by Formula 3 with a Grignard reagent containing magnesium, respectively, or 2) simultaneously reacting the compound represented by Formula 1, the arylamine compound, and the compound represented by Formula 3 with magnesium It can be reacted with Grignard reagent containing When the method for preparing the copolymer further includes a compound represented by the following Chemical Formula 3, when the copolymer prepared in the method for preparing the copolymer is applied to a device, a device having excellent efficiency and long life can be manufactured.

[Formula 3]

In Formula 3,

Ar2 to Ar4 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; cyano group; a substituted or unsubstituted fluoroalkyl group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,

n2 and n3 are each an integer of 0 to 3, and when n2 and n3 are each 2 or more, the substituents in a plurality of parentheses are the same as or different from each other,

A3 and A4 are the same as or different from each other, and each independently represents a halogen group.

According to an exemplary embodiment of the present specification, A3 and A4 are the same as or different from each other, and each independently represents -F, -Cl, -Br or -I.

According to another exemplary embodiment, A3 and A4 are each -Br.

According to an exemplary embodiment of the present specification, Ar2 to Ar4 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; cyano group; a substituted or unsubstituted fluoroalkyl group having 1 to 20 carbon atoms; a substituted or unsubstituted C 1 to C 20 alkyl group; a substituted or unsubstituted C 3 to C 30 cycloalkyl group; a substituted or unsubstituted aryl group having 6 to 60 carbon atoms; Or a substituted or unsubstituted heterocyclic group having 2 to 60 carbon atoms.

In an exemplary embodiment of the present specification, Ar2 and Ar3 are the same as or different from each other, and each independently hydrogen; or deuterium.

According to another exemplary embodiment, Ar4 is an aryl group having 6 to 60 carbon atoms substituted with an aryl group having 6 to 60 carbon atoms substituted with an alkyl group having 1 to 20 carbon atoms.

In another exemplary embodiment, Ar4 is a phenyl group substituted with a tert-butylterphenyl group.

According to an exemplary embodiment of the present specification, n2 and n3 are 0 or 1, respectively.

According to an exemplary embodiment of the present specification, the Grignard reagent including magnesium is represented by the following formula (2).

[Formula 2]

In Formula 2,

R is substituted or unsubstituted alkyl, or substituted or unsubstituted allyl,

X is a halogen group.

According to an exemplary embodiment of the present specification, R is a substituted or unsubstituted C 1 to C 20 alkyl.

According to another exemplary embodiment, R is methyl, ethyl, propyl, or butyl.

In another exemplary embodiment, R is isopropyl.

According to an exemplary embodiment of the present specification, X is -F, -Cl, -Br or -I.

According to an exemplary embodiment of the present specification, the arylamine compound may be represented by the following Chemical Formula 4 or 5.

[Formula 4]

[Formula 5]

In Formulas 4 and 5,

L1 to L5 are the same as or different from each other, and each independently a direct bond; Or a substituted or unsubstituted arylene group,

R11 to R13 are the same as or different from each other, and are each independently a substituted or unsubstituted aryl group,

A5 to A8 are the same as or different from each other, and each independently represents a halogen group.

According to an exemplary embodiment of the present specification, L1 to L5 are the same as or different from each other, and each independently a direct bond; or a substituted or unsubstituted arylene group having 6 to 60 carbon atoms.

According to another exemplary embodiment, L1 to L5 are the same as or different from each other, and each independently a direct bond; or a substituted or unsubstituted arylene group having 6 to 30 carbon atoms.

In another exemplary embodiment, L1 to L5 are the same as or different from each other, and each independently a direct bond; or a substituted or unsubstituted phenylene group.

According to another exemplary embodiment, L1 to L5 are the same as or different from each other, and each independently a direct bond; or a phenylene group.

According to an exemplary embodiment of the present specification, R11 to R13 are the same as or different from each other, and each independently represents a substituted or unsubstituted C6-C60 aryl group.

According to another exemplary embodiment, R11 to R13 are the same as or different from each other, and each independently represents an aryl group having 6 to 60 carbon atoms that is unsubstituted or substituted with an alkyl group having 1 to 20 carbon atoms.

In another exemplary embodiment, R11 to R13 are the same as or different from each other, and each independently represents a phenyl group substituted with an alkyl group having 1 to 20 carbon atoms.

In an exemplary embodiment of the present specification, the copolymer prepared by the method for preparing the copolymer may be a block copolymer or a random copolymer, but is more preferably a block copolymer. When the block copolymer is applied to the device, it is possible to obtain a device having a lower driving voltage, excellent efficiency, and a long lifespan than when the random copolymer is applied to the device.

According to an exemplary embodiment of the present specification, A5 to A8 are the same as or different from each other, and each independently represents -F, -Cl, -Br or -I.

According to an exemplary embodiment of the present specification, the copolymer prepared by the method for preparing the copolymer may include any one of units represented by Formula 1-A or 1-B below.

[Formula 1-A]

[Formula 1-B]

In Formulas 1-A and 1-B,

The definitions of X1, Ar1 and n1 are the same as those in Formula 1 above,

The definitions of L1 to L3, R11 and R12 are the same as those in Formula 4 above,

Ar2 to Ar4, n2 and n3 have the same definitions as in Formula 3 above,

p1 and q1 are 0<p1<1 in mole fraction, 0<q1<1, p1+q1 = 1,

p2, q2 and s2 are 0<p2<1, 0<q2<1, 0<s2<1, and p2+q2+s2 = 1 in mole fraction.

According to an exemplary embodiment of the present specification, there is provided a copolymer prepared by the above-described method for preparing the copolymer.

In an exemplary embodiment of the present specification, the copolymer prepared by the method for preparing the copolymer is a block copolymer.

According to an exemplary embodiment of the present specification, there is provided a coating composition comprising a copolymer prepared by the method for preparing the copolymer.

In an exemplary embodiment of the present specification, a copolymer comprising a unit represented by the following Chemical Formula 11 and an arylamine unit, a polydispersity index (PDI) of 1.3 or less, and a palladium content of 1 ppm or less is provided.

[Formula 11]

In the formula (11),

X1 is Si(R1)(R2) or C(R3)(R4),

R1 to R4 and Ar1 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; cyano group; a substituted or unsubstituted fluoroalkyl group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,

n1 is an integer of 0 to 6, and when n1 is 2 or more, a plurality of Ar1s are the same as or different from each other.

According to an exemplary embodiment of the present specification, the copolymer further includes a unit represented by the following Chemical Formula 12.

[Formula 12]

In the formula (12),

Ar2 to Ar4 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; cyano group; a substituted or unsubstituted fluoroalkyl group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,

n2 and n3 are each an integer of 0 to 3, and when n2 and n3 are each 2 or more, the substituents in the plurality of parentheses are the same as or different from each other.

According to another exemplary embodiment, the copolymer is a block copolymer.

According to an exemplary embodiment of the present specification, the arylamine unit may be represented by the following Chemical Formula 6 or 7.

[Formula 6]

[Formula 7]

In Formulas 6 and 7,

L1 to L5 are the same as or different from each other, and each independently a direct bond; Or a substituted or unsubstituted arylene group,

R11 to R13 are the same as or different from each other, and each independently represent a substituted or unsubstituted aryl group.

The contents of the substituent of the unit represented by Formula 11 are the same as the contents of the substituent of Formula 1 described above, and the contents of the substituent of the unit represented by Formula 12 are the same as the contents of the substituent of Formula 3 described above, , The contents of the substituents of Formulas 6 and 7 are the same as those of the substituents of Formulas 4 and 5 described above.

In an exemplary embodiment of the present specification, the terminal group of the copolymer may be hydrogen, but is not limited thereto, and the terminal group of all types of copolymers used in the art may be used. In particular, the copolymer prepared by the conventional polymer synthesis method using a palladium catalyst contains a hydroxyl group and a halogen group at the end of the polymer. .

In an exemplary embodiment of the present specification, the copolymer has a number average molecular weight of 5 KDa to 100 KDa. According to another exemplary embodiment, the number average molecular weight of the copolymer may be 30 KDa to 60 KDa, and in another example, 50 KDa to 65 KDa. When the copolymer satisfies the number average molecular weight range, it not only has high solubility in a solvent capable of solution processing, but also has an advantage in that the performance of the device is improved when applied to the device because the charge mobility is increased.

According to an exemplary embodiment of the present specification, the copolymer has a weight average molecular weight of 10 KDa to 1000 KDa. According to another exemplary embodiment, the weight average molecular weight of the copolymer is 60 KDa to 80 KDa. When the copolymer satisfies the weight average molecular weight range, it not only has high solubility in a solvent capable of solution processing, but also has an advantage in that the performance of the device is improved when applied to the device due to increased charge mobility.

In the present specification, molecular weight analysis may be performed using GPC equipment.

According to an exemplary embodiment of the present specification, there is provided a coating composition comprising the copolymer.

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

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

According to an exemplary embodiment of the present specification, the coating composition may further include a compound in a monomolecular form.

In another embodiment, the viscosity of the coating composition is 2 cP to 18 cP.

When the above viscosity is satisfied, it is easy to manufacture a cleaning agent. Preferably it is 3 cP - 18 cP, More preferably, it is 3 cP - 8 cP.

According to an exemplary embodiment of the present specification, in an exemplary embodiment of the present specification, the first electrode; a second electrode; and at least one organic material layer provided between the first electrode and the second electrode, wherein at least one of the organic material layers includes the coating composition.

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

According to an exemplary embodiment of the present specification, the organic material layer including the coating composition is a hole injection layer.

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

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

In an exemplary embodiment of the present specification, the organic light emitting device is a hole injection layer, a hole transport layer, a layer for performing hole injection and hole transport at the same time, an electron transport layer, an electron injection layer, a layer for simultaneously injecting and transporting electrons, an electron blocking layer It further includes one or more layers selected from the group consisting of a layer and a hole blocking layer.

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

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

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

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

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

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

In FIG. 1 , an anode 201 , a hole injection layer 301 , a hole transport layer 401 , a light emitting layer 501 , an electron injection layer 601 , and a cathode 701 are sequentially stacked on a substrate 101 . The structure of the device is illustrated.

1 illustrates an organic light emitting device, but is not limited thereto.

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

The organic light emitting device of the present specification may be manufactured using materials and methods known in the art, except that at least one layer of the organic material layer is formed using the coating composition including the above-described copolymer.

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

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

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

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

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

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

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

In one embodiment of the present specification, the step of forming the organic material layer formed using the coating composition comprises: coating the coating composition on the first electrode; and drying the coated coating composition.

According to another exemplary embodiment, the drying step may be performed in an N ₂ atmosphere or air, but is not limited thereto.

In one embodiment of the present specification, the heat treatment temperature of the drying step is 85 ℃ to 250 ℃, according to an embodiment may be 100 ℃ to 250 ℃, in another embodiment, 150 ℃ to It may be 220 °C.

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

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

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

The hole injection layer is a layer for injecting holes from the electrode, and as a hole injection material, it has the ability to transport holes, so it has a hole injection effect at the anode, an excellent hole injection effect on the light emitting layer or the light emitting material, and is produced in the light emitting layer A compound which prevents the movement of excitons to the electron injection layer or the electron injection material and is excellent in the ability to form a thin film is preferred. It is preferable that the highest occupied molecular orbital (HOMO) of the hole injection material is between the work function of the anode material and the HOMO of the surrounding organic material layer. Specific examples of the hole injection material include metal porphyrin, oligothiophene, arylamine-based organic material, hexanitrile hexaazatriphenylene-based organic material, quinacridone-based organic material, and perylene-based organic material. of organic substances, anthraquinones, polyaniline and polythiophene-based conductive polymers, and the like, but are not limited thereto.

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

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

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

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

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

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

Examples of the metal complex compound include 8-hydroxyquinolinato lithium, bis(8-hydroxyquinolinato)zinc, bis(8-hydroxyquinolinato)copper, bis(8-hydroxyquinolinato)manganese, Tris(8-hydroxyquinolinato)aluminum, tris(2-methyl-8-hydroxyquinolinato)aluminum, tris(8-hydroxyquinolinato)gallium, bis(10-hydroxybenzo[h] Quinolinato) beryllium, bis (10-hydroxybenzo [h] quinolinato) zinc, bis (2-methyl-8-quinolinato) chlorogallium, bis (2-methyl-8-quinolinato) ( o-crezolato)gallium, bis(2-methyl-8-quinolinato)(1-naphtolato)aluminum, bis(2-methyl-8-quinolinato)(2-naphtolato)gallium, etc. However, the present invention is not limited thereto.

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

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

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

< production example >

production example 1. Preparation of copolymer 1

M1 (0.1g, 0.1353mmol), lithium chloride (0.0057g, 0.1353mmol) was put in a 100mL flask, N ₂ purged, anhydrous tetrahydrofuran (THF, 3mL) was added, stirred for 30 minutes, and then 2M isopropyl Magnesium chloride (2M isopropyl magnesium chloride in THF, 0.0677 mL, 0.1353 mmol) was added and stirred at room temperature for 1 hour. (Solution A)

Put M2 (0.7848g, 1.2177mmol) and lithium chloride (0.0516g, 1.2177mmol) in another flask, and after purging with N ₂ , add anhydrous THF (27mL) and stir for 30 minutes, then 2M isopropylmagnesium chloride (2M isopropyl magnesium chloride in THF, 0.6093 mL, 1.2177 mmol) was added and stirred at room temperature for 1 hour. (Solution B)

Ni(dppp)Cl ₂ (33mg, 0.06mmol) dispersed in THF (5mL) was added to solution A and stirred at room temperature for 1 hour, then the prepared solution B was transferred to solution A with a syringe and reacted at 50°C for 12 hours. did. After the reaction was completed with 5M HCl aqueous solution, it was washed once with water, twice with 10 wt% dilute hydrochloric acid, twice with 3 wt% aqueous ammonia solution, twice with water, and the resulting solution was added dropwise to ethanol, and precipitation occurred. The precipitate was dissolved in toluene and purified by passing through an alumina column and a silica gel column in this order. After dripping the obtained solution to ethanol and stirring, the obtained precipitate was filtered and dried, and the copolymer 1 was obtained.

production example 2. Preparation of copolymer 2

M3 (0.0297g, 0.02706mmol), lithium chloride (0.0011g, 0.1353mmol) was put in a 100mL flask, N ₂ purged, anhydrous THF (3mL) was added, stirred for 30 minutes, and then 2M isopropylmagnesium chloride (2M) isopropyl magnesium chloride in THF, 0.0135 mL, 0.0270 mmol) was added and stirred at room temperature for 1 hour. (Solution A)

In another flask, put M1 (0.1g, 0.1353mmol), lithium chloride (lithium chloride, 0.0057g, 0.1353mmol), after purging with N ₂ , add anhydrous THF (3mL) and stir for 30 minutes, then 2M isopropylmagnesium chloride (2M) isopropyl magnesium chloride in THF, 0.0677 mL, 0.1353 mmol) was added and stirred at room temperature for 1 hour. (Solution B) Put M2 (0.7673g, 1.1906mmol) and lithium chloride (0.00504g, 1.1906mmol) in another flask, and after purging with N ₂ , add anhydrous THF (27mL) and stir for 30 minutes, then 2M isopropyl Magnesium chloride (2M isopropyl magnesium chloride in THF, 0.5957 mL, 1.1906 mmol) was added and stirred at room temperature for 1 hour. (Solution C)

Ni(dppp)Cl ₂ (33mg, 0.06mmol) dispersed in THF (5mL) was added to solution A and stirred at room temperature for 1 hour, then the prepared solution B was transferred to solution A with a syringe and reacted at 50°C for 1 hour. did. Then, the solution C was transferred to the mixed solution of the solution A and the solution B with a syringe and reacted at 50° C. for 12 hours. After the reaction was completed with 5M HCl aqueous solution, it was washed once with water, twice with 10 wt% dilute hydrochloric acid, twice with 3 wt% aqueous ammonia solution, twice with water, and the resulting solution was added dropwise to ethanol, and precipitation occurred. The precipitate was dissolved in toluene and purified by passing through an alumina column and a silica gel column in this order. After dripping the obtained solution to ethanol and stirring, the obtained deposit was filtered out and dried, and the copolymer 2 was obtained.

production example 3. Preparation of copolymer 3

In a 100mL flask, put M1 (0.1g, 0.1353mmol), M2 (0.7848g, 1.2177mmol) and lithium chloride (lithium chloride, 0.057g, 1.353mmol) and N ₂ purging, then put anhydrous THF (30mL) and put it for 30 minutes After stirring, 2M isopropyl magnesium chloride (2M isopropyl magnesium chloride in THF, 0.677 mL, 1.353 mmol) was added and stirred at room temperature for 1 hour. Ni(dppp)Cl ₂ (33mg, 0.06mmol) dispersed in THF (5mL) was added, and the temperature was raised to 50°C, followed by reaction for 12 hours. After the reaction was completed with 5M HCl aqueous solution, it was washed once with water, twice with 10 wt% dilute hydrochloric acid, twice with 3 wt% aqueous ammonia solution, twice with water, and the resulting solution was added dropwise to ethanol, and precipitation occurred. The precipitate was dissolved in toluene and purified by passing through an alumina column and a silica gel column in this order. After dripping the obtained solution to ethanol and stirring, the obtained precipitate was filtered out and dried, and the copolymer 3 was obtained.

production example 4. Preparation of copolymer 4

Put M1 (0.1g, 0.1353mmol), M2 (0.7673g, 1.1906mmol), M3 (0.0297g, 0.02706mmol) and lithium chloride (0.057g, 1.353mmol) in a 100mL flask, N ₂ After purging, anhydrous THF (30 mL) was added, and after stirring for 30 minutes, 2M isopropyl magnesium chloride in THF, 0.677 mL, 1.353 mmol) was added and stirred at room temperature for 1 hour. Ni(dppp)Cl ₂ (33mg, 0.06mmol) dispersed in THF (5mL) was added, and the temperature was raised to 50°C, followed by reaction for 12 hours. After the reaction was completed with 5M HCl aqueous solution, it was washed once with water, twice with 10 wt% dilute hydrochloric acid, twice with 3 wt% aqueous ammonia solution, twice with water, and the resulting solution was added dropwise to ethanol, and precipitation occurred. The precipitate was dissolved in toluene and purified by passing through an alumina column and a silica gel column in this order. After the obtained solution was dripped and stirred in ethanol, the obtained precipitate was filtered out and made to dry, and the copolymer 4 was obtained.

production example 5. Preparation of copolymer 5

M1 (0.1g, 0.1353mmol), lithium chloride (0.0057g, 0.1353mmol) was put in a 100mL flask, N ₂ purged, anhydrous THF (3mL) was added, stirred for 30 minutes, and then 2M isopropylmagnesium chloride (2M) isopropyl magnesium chloride in THF, 0.0677 mL, 0.1353 mmol) was added and stirred at room temperature for 1 hour. (Solution A)

Put M4 (0.7250g, 1.2177mmol) and lithium chloride (0.0516g, 1.2177mmol) in another flask, and after purging with N ₂ , add anhydrous THF (27mL) and stir for 30 minutes, then 2M isopropylmagnesium chloride (2M isopropyl magnesium chloride in THF, 0.6093 mL, 1.2177 mmol) was added and stirred at room temperature for 1 hour. (Solution B)

Ni(dppp)Cl ₂ dispersed in THF (5 mL) (33mg, 0.06mmol) was added to solution A and stirred at room temperature for 1 hour, then the prepared solution B was transferred to solution A with a syringe and reacted at 50° C. for 12 hours. After the reaction was completed with 5M HCl aqueous solution, it was washed once with water, twice with 10 wt% dilute hydrochloric acid, twice with 3 wt% aqueous ammonia solution, twice with water, and the resulting solution was added dropwise to ethanol, and precipitation occurred. The precipitate was dissolved in toluene and purified by passing through an alumina column and a silica gel column in this order. After the obtained solution was added dropwise to ethanol and stirred, the obtained precipitate was filtered out and dried to obtain a copolymer 5.

compare production example 1. Preparation of copolymer 6

2,2'-(9,9-bis(4-hexylphenyl)-9H-fluorene-2,7-diyl)bis(4,4,5,5-tetramethyl-1,3,2-diox saborolane) (0.9754 g, 1.518 mmol), 2,7-dibromo-9,9-bis(4-hexylphenyl)-9H-fluorene (0.7492 g, 1.336 mmol), N1,N4-bis(4) -Bromophenyl)-N1,N4-bis(4-(tert-butyl)-2,6-dimethylphenyl)benzene-1,4-diamine (0.1121 g, 0.1518 mmol) was placed in a 100 mL round flask (RBF) After dissolving in 50mL toluene, 20wt% aq. Et 4 NOH (15 mL) was added, the temperature was raised to 90° C., and the mixture was stirred for 30 minutes. Tetrakistriphenylphosphine palladium (0) (Tetrakistriphenylphosphine palladium (0)) (10 mg) was dissolved in 5 mL toluene, put at a time, and stirred for 48 hours. The temperature was lowered, precipitated in methanol, filtered, washed with methanol, water, ethanol, and hexane, dissolved in methylene chloride, charcoal, CPS-T, and MgSO ₄ were added, followed by stirring at room temperature for 30 minutes. The stirred mixture was passed through triethylamine-treated silica, methylene chloride was removed, dissolved in a small amount of toluene, and adsorbed to triethylamine-treated silica, and then loaded onto a column and washed with hexane. After dissolving in the column again with toluene to remove the toluene, leaving only a portion, precipitated in methanol, filtered and dried to obtain Co-conjugate 6.

compare production example 2. Preparation of copolymer 7

2,2'-(9,9-bis(4-hexylphenyl)-9H-fluorene-2,7-diyl)bis(4,4,5,5-tetramethyl-1,3,2-diox saborolane) (1.121 g, 1.518 mmol), 2,7-dibromo-9,9-bis(4-hexylphenyl)-9H-fluorene (0.8611 g, 1.336 mmol), N1,N4-bis(4) -Bromophenyl)-N1,N4-bis(4-(tert-butyl)-2,6-dimethylphenyl)benzene-1,4-diamine (0.1121 g, 0.1518 mmol), 3,7-dibromo- 10-(4,4''''-di-tert-butyl-5',5'''-bis(4-(tert-butyl)phenyl)-[1,1':3',1'': 3'',1''':3''',1''''-quinkerphenyl]-5''-yl)-10H-phenoxazine (0.0333 g, 0.0303 mmol) in a 100 mL round bottom flask (RBF) After dissolving in 50mL toluene, 20wt% aq. Et ₄ NOH (15 mL) was added, the temperature was raised to 90° C., and the mixture was stirred for 30 minutes. Tetrakistriphenylphosphine palladium (0) (Tetrakistriphenylphosphine palladium (0)) (10 mg) was dissolved in 5 mL toluene, put at a time, and stirred for 48 hours. The temperature was lowered, precipitated in methanol, filtered, washed with methanol, water, ethanol, and hexane, dissolved in methylene chloride, charcoal, CPS-T, and MgSO ₄ were added, followed by stirring at room temperature for 30 minutes. The stirred mixture was passed through triethylamine-treated silica, methylene chloride was removed, dissolved in a small amount of toluene, and adsorbed to triethylamine-treated silica, and then loaded onto a column and washed with hexane. Then, it was dissolved again in the column with toluene to remove the toluene, and only a portion was left behind to precipitate in methanol, filtered and dried to obtain Copolymer 7.

Experimental example 1. molecular weight, PDI Measurement example

The number average molecular weight (Mn) and weight average molecular weight (Mw) of the copolymers prepared in Preparation Examples 1 to 5 and Comparative Preparation Examples 1 and 2 were analyzed by gel permeation chromatography (GPC), and from the analysis results The number average molecular weight (Mn) and the weight average molecular weight (Mw) in terms of polystyrene were computed. The results are shown in Table 1 below.

<Analysis Conditions>

Measuring device: WATERS GPC

Column: Agilent mixed B X 2

Column temperature: 40°C

Moving layer: tetrahydrofuran

Flow rate: 1.0 mL/min

Number average molecular weight (KDa) Weight average molecular weight (KDa) PDI copolymer 1 57 73 1.28 copolymer 2 59 74 1.25 copolymer 3 65 77 1.19 copolymer 4 54 68 1.26 copolymer 5 62 68 1.10 copolymer 6 81 170 2.10 copolymer 7 70 126 1.80

Copolymers 1 to 5 synthesized by the Grignard metathesis method including magnesium showed a low PDI of 1.3 or less, but copolymers 6 to 7 showed a high PDI of 1.7 or more. From Table 1, it can be confirmed that the Grignard metathesis method including magnesium is suitable for polymerizing reproducible polymers because low PDI is indirect evidence showing that polymerization is being carried out as intended.

Experimental example 2.

Example One

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

On the thus prepared ITO transparent electrode, the following compound A and compound B were mixed at a weight ratio of 8:2, and a solution dissolved in cyclohexanone was spin-coated to form a film to a thickness of 400 Å. This was heated at 220° C. for 30 minutes in a nitrogen atmosphere to form a hole injection layer. Then, the following copolymer HTL1 was dissolved in toluene and spin-coated on the hole injection layer to form a film at 200 Å, and heated at 190° C. for 1 hour in a nitrogen atmosphere to form a hole transport layer. Thereafter, the copolymer 1 prepared in Preparation Example 1 was dissolved in toluene to form a film at 200 Å, and heated at 160° C. for 30 minutes under a nitrogen atmosphere to form a light emitting layer. An electron injection layer and a cathode were formed by vacuum thermal evaporation of NaF and Al on the light emitting layer.

[Compound A]

[Compound B]

[HTL1]

Then, sealing was performed by bonding sealing glass and a glass substrate to glass using a photocurable epoxy resin, and the organic electroluminescent element of a multilayer structure was produced. Subsequent operation was performed at room temperature (25 degreeC) in air|atmosphere.

Example 2

An organic light emitting diode was manufactured in the same manner as in Example 1, except that the light emitting layer was formed using copolymer 2 instead of copolymer 1 in Example 1.

Example 3

An organic light emitting diode was manufactured in the same manner as in Example 1, except that the light emitting layer was formed using copolymer 3 instead of copolymer 1 in Example 1.

Example 4

An organic light emitting diode was manufactured in the same manner as in Example 1, except that the light emitting layer was formed using Copolymer 4 instead of Copolymer 1 in Example 1.

Example 5

An organic light emitting diode was manufactured in the same manner as in Example 1, except that the light emitting layer was formed using Copolymer 5 instead of Copolymer 1 in Example 1.

comparative example One

An organic light emitting diode was manufactured in the same manner as in Example 1, except that the light emitting layer was formed using copolymer 6 instead of copolymer 1 in Example 1.

comparative example 2

An organic light emitting diode was manufactured in the same manner as in Example 1, except that the light emitting layer was formed using Copolymer 7 instead of Copolymer 1 in Example 1.

Table 2 shows the results of measuring the driving voltage, current efficiency, external quantum efficiency, and lifespan of the organic light-emitting device manufactured by the above method at a current density of 10 mA/cm ² . The external quantum efficiency can be obtained by (the number of emitted photons) / (the number of injected charge carriers), and the Life time is a measurement of the time at which the initial luminance becomes 95% at a current density of 10 mA/cm ² .

Example light emitting layer Driving voltage (V) current efficiency
(cd/A) EQE (%) life time
(95%,h) Example 1 copolymer 1 3.57 7.49 7.40 50 Example 2 copolymer 2 3.79 8.64 8.38 61 Example 3 copolymer 3 4.97 3.45 4.58 35 Example 4 copolymer 4 4.09 4.15 5.58 42 Example 5 copolymer 5 3.90 8.25 8.21 55 Comparative Example 1 copolymer 6 4.47 3.19 3.58 29 Comparative Example 2 copolymer 7 4.49 3.00 3.19 27

As shown in Table 2, copolymers 1 to 5 polymerized by the Grignard metathesis method showed higher performance than copolymers 6 and 7 polymerized by the Suzuki polymerization method.

In addition, the same monomers were used for copolymers 1 and 2 sequentially injected after each monomer was reacted with Grignard reagent separately, but the used monomers were simultaneously injected and reacted with Grignard reagent It showed higher performance than the polymerized copolymers 3 and 4. Copolymers 1 and 2 are expected to be polymerized as block copolymers in terms of polymerization method, and copolymers 3 and 4 are expected to be polymerized as random copolymers in polymerization mode. Copolymer 5 using a monomer substituted with -I and -Br at positions 2 and 7 of fluorene has a lower PDI than copolymer 1 using a monomer substituted with -Br at both positions 2 and 7 and also showed high performance.

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

Claims (12)

Having the structure of the following formula 1-A,
polydispersity index (PDI) of 1.3 or less,
Copolymers having a palladium content of 1 ppm or less:
[Formula 1-A]

In Formula 1-A,
X1 is Si(R1)(R2) or C(R3)(R4),
R1 to R4 and Ar1 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; cyano group; a substituted or unsubstituted fluoroalkyl group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,
n1 is an integer of 0 to 6, and when n1 is 2 or more, a plurality of Ar1s are the same as or different from each other,
L1 to L3 are the same as or different from each other, and each independently a direct bond; Or a substituted or unsubstituted arylene group,
R11 and R12 are the same as or different from each other, and are each independently a substituted or unsubstituted aryl group,
p1 and q1 are 0<p1<1 in mole fraction, 0<q1<1, and p1+q1 = 1. delete The method according to claim 1,
The copolymer is a block copolymer. A coating composition comprising the copolymer according to claim 1 . a first electrode;
a second electrode; and
At least one organic material layer provided between the first electrode and the second electrode,
At least one of the organic material layers is an organic light emitting device comprising the coating composition of claim 4. 6. The method of claim 5,
The organic material layer including the coating composition is an organic light emitting device that is a light emitting layer. preparing a substrate;
forming a first electrode on the substrate;
forming one or more organic material layers on the first electrode; and
Forming a second electrode on the organic material layer,
The step of forming the organic material layer is a method of manufacturing an organic light emitting device comprising the step of forming one or more organic material layer using the coating composition of claim 4. Comprising the step of reacting the compound represented by the formula (1) and the arylamine compound with a Grignard reagent containing magnesium,
polydispersity index (PDI) of 1.3 or less,
The content of palladium is 1 ppm or less,
A method for preparing a copolymer having a structure of the following formula 1-A:
[Formula 1]

In Formula 1,
X1 is Si(R1)(R2) or C(R3)(R4),
R1 to R4 and Ar1 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; cyano group; a substituted or unsubstituted fluoroalkyl group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,
n1 is an integer of 0 to 6, and when n1 is 2 or more, a plurality of Ar1s are the same as or different from each other,
A1 and A2 are the same as or different from each other, each independently a halogen group,
[Formula 1-A]

In Formula 1-A,
X1 is Si(R1)(R2) or C(R3)(R4),
R1 to R4 and Ar1 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; cyano group; a substituted or unsubstituted fluoroalkyl group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,
n1 is an integer of 0 to 6, and when n1 is 2 or more, a plurality of Ar1s are the same as or different from each other,
L1 to L3 are the same as or different from each other, and each independently a direct bond; Or a substituted or unsubstituted arylene group,
R11 and R12 are the same as or different from each other, and are each independently a substituted or unsubstituted aryl group,
p1 and q1 are 0<p1<1 in mole fraction, 0<q1<1, and p1+q1 = 1. 9. The method of claim 8,
Formula 1 is a method for preparing a copolymer represented by the following Formula 1-1:
[Formula 1-1]

In Formula 1-1,
The definitions of X1, Ar1 and n1 are as defined in Formula 1 above. delete A copolymer prepared by the method for preparing a copolymer according to claim 8 or 9. 12. The method of claim 11,
The copolymer is a block copolymer.

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