JP4830272B2 - Organic electroluminescence device - Google Patents

Description

The present invention relates to an organic electroluminescence element (hereinafter sometimes referred to as an organic EL element) having a hole injection layer and a light emitting layer.

  An organic EL element is an element using a low molecular or high molecular organic compound as a light emitting material.

  An organic EL element has a light emitting layer between electrodes, but a hole injection layer is generally used adjacent to the anode in order to improve the characteristics and life of the element.

As a hole injection layer, a conductive polymer having an acid group (polyaniline having a sulfonic acid group) and a non-conductive polymer that does not contain an aromatic ring in the main chain, such as polyvinyl alcohol, polyacrylic acid, polystyrene sulfonic acid, and the like An element having a layer containing benzene is known (Patent Document 1).
WO01 / 18888A1

However, the lifetime of the above elements is not yet sufficient, and an organic EL element having a longer lifetime has been desired.
An object of the present invention is to provide a long-life organic EL device.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have made a conductive polymer having an acid group as a hole injection layer and a non-conductive polymer having an acid group and an aromatic ring in the main chain. It was found that the use of a layer containing a long-life organic EL element led to the present invention.

That is, the present invention has a hole injection layer and a light emitting layer between electrodes composed of an anode and a cathode, and the hole injection layer has an acid group-containing conductive polymer (A) and the following general formula (1). And (2) and (3), an organic electroluminescence device comprising an acid group-containing polymer (B).

-(-Ar ₁ -X _1- ) m- (1)
[Wherein, m represents an integer of 10 or more, Ar ₁ represents a divalent aromatic group, and the divalent aromatic group includes an alkyl group having 1 to 10 carbon atoms and an alkoxy group having 1 to 10 carbon atoms. group, may be substituted with an aryl group or an aryloxy group having 6 to 10 carbon atoms of 6 to 10 carbon atoms, more Ar ₁ may be the same or different and at least one of Ar ₁ An acid group is bonded directly or via a linking group. X ₁ represents —O—, —S—, —SO—, —SO ₂ —, —CO—, —CR ′ ″ R ″ ″ — or a direct bond, and R ′ ″ and R ″. '' are each independently an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryloxy group an aryl group or a C 6-10 having 6 to 10 carbon atoms, more X ₁ is , May be the same or different. ]

_{- (- Ar 2 -X 2 -Ar} 3 -X 3 -) m- (2)
[Wherein, m represents an integer of 10 or more, Ar ₂ and Ar ₃ each independently represent a divalent aromatic group, and the divalent aromatic group includes an alkyl group having 1 to 10 carbon atoms, carbon It may be substituted with an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms or an aryloxy group having 6 to 10 carbon atoms, and a plurality of Ar ₂ and Ar ₃ may be the same or different. An acid group is bonded to at least one of Ar ₂ and Ar ₃ directly or via a linking group. X ₂ and X ₃ each independently represent —O—, —S—, —SO—, —SO ₂ —, —CO—, —CR ′ ″ R ″ ″ — or a direct bond; '''AndR''''each independently represent an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aryloxy group having 6 to 10 carbon atoms. And a plurality of X ₂ and X ₃ may be the same or different. ]


_{- (- Ar 4 -X 4 -Ar} 5 -X 5 -Ar 6 -X 6 -) m- (3)
[Wherein, m represents an integer of 10 or more, Ar ₄ , Ar ₅ and Ar ₆ each independently represents a divalent aromatic group, and the divalent aromatic group represents an alkyl group having 1 to 10 carbon atoms. Group, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms or an aryloxy group having 6 to 10 carbon atoms, and a plurality of Ar ₄ , Ar ₅ and Ar ₆ are each The acid groups may be the same or different, and an acid group is bonded to at least one of Ar ₄ , Ar ₅ and Ar ₆ directly or via a linking group. X _4, X ₅ and X ₆ are each independently —O—, —S—, —SO—, —SO ₂ —, —CO—, —CR ′ ″ R ″ ″ — or a direct bond. R ′ ″ and R ″ ″ each independently represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aryl having 6 to 10 carbon atoms Represents an oxy group, and a plurality of X _4, X ₅ and X ₆ may be the same or different from each other; ]

According to the present invention, a long-life organic EL element can be provided.

  In the present invention, the hole injection layer is a layer provided in contact with the anode, and is a layer having a function of improving hole injection efficiency from the anode.

In the element of the present invention, the hole injection layer has an acid group-containing polymer (A) selected from the following general formulas (1), (2) and (3): And B).

  First, the conductive polymer (A) having an acid group used for the organic EL element will be described.

The conductive polymer is a general term for polymer substances showing metallic or semiconducting conductivity (Iwanami Rikagaku Dictionary 5th edition: issued in 1998).
Specific examples of the conductive polymer are described in “Conductive polymer” (Shinichi Yoshimura, Kyoritsu Shuppan), “Latest applied technology of conductive polymer” (supervised by Masao Kobayashi, CM Publishing).
Typical conductive polymers include polyacetylene, polyphenylene bonded at the para-position or meta-position, and a polymer in which a phenyl group is connected via a divalent group (for example, a phenyl group is connected via —CH═CH—). Polyphenylene vinylene, polyphenylene sulfide having a phenyl group connected through -S-, and polyphenylene oxide having a phenyl group connected through -O-), and the elements constituting the five-membered ring are elements other than C and H. Polymers with one and two- and five-positions (for example, polypyrrole with NH-containing five-membered ring connected with 2,5-position, polythiophene with five-membered ring containing S connected with 2,5-position, and five containing O Examples include polyfurans in which the member rings are connected at the 2,5-position, polyselenophene in which the five-membered ring containing Se is connected in the 2,5-position, and polytellurophene in which the five-membered ring containing Te is connected in the 2,5-position. ), Obtained by polymerizing aromatic amines Polymer (such as polyaniline, poly amino pyrene and the like) and the like. Among these, polyaniline, polythiophene, and polypyrrole are preferable, and polyaniline and polythiophene are more preferable.

  Examples of the conductive polymer (A) having an acid group include those in which an acid group is introduced into the conductive polymer exemplified above. Specifically, polyacetylene having an acid group, an acid group Polyphenylene, polyphenylene vinylene, polyphenylene sulfide having an acid group, polyphenylene oxide having an acid group, polypyrrole having an acid group, polythiophene having an acid group (for example, poly (3,4-dioxythiophene having an acid group), acid And polyfuran having an acid group, polyselenophene having an acid group, polytellurophene having an acid group, polyaniline having an acid group, and polyaminopyrene having an acid group.

  Here, examples of the acid group include a weak acid group such as a carboxyl group and a phospho group, a strong acid group such as a sulfo group and a sulfonylimide, a super strong acid such as a perfluoroalkylene sulfo group, a perfluorophenylene sulfo group, and a perfluoroalkylenesulfonyl imide. Group and the like. Among them, a strong acid group and a super strong acid group are preferable, and examples thereof include a sulfo group, a perfluoroalkylene sulfo group, and a perfluorophenylene sulfo group.

  The acid group is directly bonded to the conductive polymer, or alkylene having 1 to 10 carbon atoms, alkylene having 1 to 10 carbon atoms and containing -O-, oxyalkylene having 1 to 10 carbon atoms, You may couple | bond with polymer | macromolecule through connecting groups, such as C6-C10 arylene or C6-C10 oxyarylene. Examples of the alkylene having 1 to 10 carbon atoms include methylene, ethylene, n-propylene, isopropylene, n-butylene, sec-butylene, tert-butylene, isobutylene, n-pentylene, 2,2-dimethylpropylene, and cyclopentylene. Alkylene of 1 to 10 carbon atoms such as len, n-hexylene, cyclohexylene, 2-methylpentylene, 2-ethylhexylene, etc., halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, Examples include alkylene substituted with hydroxyl group, nitrile group, amino group, methoxy group, ethoxy group, isopropyloxy, phenyl, naphthyl, phenoxy, naphthyloxy and the like.

  Examples of the alkylene having 1 to 10 carbon atoms and including -O- include, for example, methyleneoxymethylene, methyleneoxyethylene, methyleneoxypropylene, methyleneoxybutylene, methyleneoxypentylene, methyleneoxyhexylene, and methyleneoxyheptylene. , Methyleneoxyoctylene, methyleneoxynonylene, ethyleneoxymethylene, ethyleneoxyethylene, ethyleneoxypropylene, ethyleneoxybutylene, ethyleneoxypentylene, ethyleneoxyhexylene, ethyleneoxyheptylene, ethyleneoxyoctylene, propyleneoxy Methylene, propyleneoxyethylene, propyleneoxypropylene, propyleneoxybutylene, propyleneoxypentylene, propyleneoxyhexylene, propyleneoxyhept Tylene, butyleneoxymethylene, butyleneoxyethylene, butyleneoxypropylene, butyleneoxybutylene, butyleneoxypentylene, butyleneoxyhexylene, pentyleneoxymethylene, pentyleneoxyethylene, pentyleneoxypropylene, pentyleneoxybutylene, pentylene Oxypentylene, hexyleneoxymethylene, hexyleneoxyethylene, hexyleneoxypropylene, hexyleneoxybutylene, heptyleneoxymethylene, heptyleneoxyethylene, heptyleneoxypropylene, octyleneoxymethylene, octyleneoxy -O--containing alkylene such as ethylene, nonacyloxymethylene, etc., halogen atoms such as fluorine, chlorine, bromine, iodine, etc. Hexyl group, a nitrile group, an amino group, a methoxy group, an ethoxy group, isopropyloxy, phenyl, naphthyl, phenoxy, alkylene and the like which naphthyloxy contains a -O- was replaced.

  Examples of the oxyalkylene having 1 to 10 carbon atoms include methyleneoxy, ethyleneoxy, n-propyleneoxy, isopropyleneoxy, n-butyleneoxy, sec-butyleneoxy, tert-butyleneoxy, isobutyleneoxy, and n-pentylene. Oxyalkylene having 1 to 10 carbon atoms such as oxy, 2,2-dimethylpropyleneoxy, cyclopentyleneoxy, n-hexyleneoxy, cyclohexyleneoxy, 2-methylpentyleneoxy, 2-ethylhexyleneoxy, and the like Oxyalkylene in the above is substituted with halogen atom such as fluorine atom, chlorine atom, bromine atom, iodine atom, hydroxyl group, nitrile group, amino group, methoxy group, ethoxy group, isopropyloxy, phenyl, naphthyl, phenoxy, naphthyloxy, etc. Examples include oxyalkylene

  Examples of the arylene having 6 to 10 carbon atoms include arylene having 6 to 10 carbon atoms such as phenylene and naphthylene, halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, hydroxyl group, nitrile group and the like. And arylene substituted with an amino group, methoxy group, ethoxy group, isopropyloxy, phenyl, naphthyl, phenoxy, naphthyloxy, and the like.

  Examples of the oxyarylene having 6 to 10 carbon atoms include oxyarylene having 6 to 10 carbon atoms such as phenyleneoxy and naphthyleneoxy, halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, and hydroxyl group. Oxyarylene substituted with a nitrile group, amino group, methoxy group, ethoxy group, isopropyloxy, phenyl, naphthyl, phenoxy, naphthyloxy, and the like.

  When the conductive polymer (A) contains an aromatic ring, the number of acid groups is preferably 10% to 100%, more preferably 30% to 100%, based on the number of aromatic rings.

  The conductive polymer (A) is an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, a halogen atom, or the like. May be substituted.

Examples of the alkyl group having 1 to 10 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, n-pentyl, 2,2-dimethylpropyl, C1-C10 alkyl groups such as cyclopentyl, n-hexyl, cyclohexyl, 2-methylpentyl, 2-ethylhexyl, etc., halogen atoms such as fluorine atom, chlorine atom, bromine atom, iodine atom, hydroxyl group, etc. Examples thereof include an alkyl group substituted with a nitrile group, amino group, methoxy group, ethoxy group, isopropyloxy, phenyl, naphthyl, phenoxy, naphthyloxy, and the like.

  Examples of the alkoxy group having 1 to 10 carbon atoms include methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, sec-butyloxy, tert-butyloxy, isobutyloxy, n-pentyloxy, 2,2-dimethyl. C1-C10 alkoxy groups such as propyloxy, cyclopentyloxy, n-hexyloxy, cyclohexyloxy, 2-methylpentyloxy, 2-ethylhexyloxy and the like, fluorine atom, chlorine atom, bromine atom, iodine atom And alkoxy groups substituted with a halogen atom such as hydroxyl group, nitrile group, amino group, methoxy group, ethoxy group, isopropyloxy, phenyl, naphthyl, phenoxy, naphthyloxy and the like.

  Examples of the aryl group having 6 to 10 carbon atoms include aryl groups having 6 to 10 carbon atoms such as phenyl and naphthyl, halogen atoms such as fluorine, chlorine, bromine and iodine atoms, hydroxyl groups, and nitriles. And aryl groups substituted with a group, amino group, methoxy group, ethoxy group, isopropyloxy, phenyl, naphthyl, phenoxy, naphthyloxy, and the like.

  Examples of the aryloxy group having 6 to 10 carbon atoms include aryloxy groups having 6 to 10 carbon atoms such as phenoxy and naphthyloxy, halogen atoms such as fluorine, chlorine, bromine and iodine atoms, hydroxyl And an aryloxy group substituted by a group, a nitrile group, an amino group, a methoxy group, an ethoxy group, isopropyloxy, phenyl, naphthyl, phenoxy, naphthyloxy, and the like.

  Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Specific examples of the conductive polymer (A) having an acid group include the following.
(Here, the introduction rate of acid groups varies depending on the synthesis method, etc., but here, a conductive polymer in which the introduction rate of acid groups is 100% with respect to the number of aromatic rings is exemplified)

  The average molecular weight of the conductive polymer (A) having an acid group is preferably 3,000 to 100,000, more preferably 10,000 to 300,000, expressed as a number average molecular weight in terms of polystyrene.

In addition, the electrical conductivity of the conductive polymer (A) having an acid group is usually 1 × 10 ⁻⁵ S / cm or more.

The hole injection layer of the element of the present invention is a polymer having an acid group selected from the following general formulas (1), (2) and (3) in addition to the conductive polymer (A) having an acid group. (B) is contained.

-(-Ar ₁ -X _1- ) m- (1)
[Wherein, m represents an integer of 10 or more, Ar ₁ represents a divalent aromatic group, and the divalent aromatic group includes an alkyl group having 1 to 10 carbon atoms and an alkoxy group having 1 to 10 carbon atoms. group, may be substituted with an aryl group or an aryloxy group having 6 to 10 carbon atoms of 6 to 10 carbon atoms, more Ar ₁ may be the same or different and at least one of Ar ₁ An acid group is bonded directly or via a linking group. X ₁ represents —O—, —S—, —SO—, —SO ₂ —, —CO—, —CR ′ ″ R ″ ″ — or a direct bond, and R ′ ″ and R ″. '' are each independently an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryloxy group an aryl group or a C 6-10 having 6 to 10 carbon atoms, more X ₁ is , May be the same or different. ]

_{- (- Ar 2 -X 2 -Ar} 3 -X 3 -) m- (2)
[Wherein, m represents an integer of 10 or more, Ar ₂ and Ar ₃ each independently represent a divalent aromatic group, and the divalent aromatic group includes an alkyl group having 1 to 10 carbon atoms, carbon It may be substituted with an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms or an aryloxy group having 6 to 10 carbon atoms, and a plurality of Ar ₂ and Ar ₃ may be the same or different. An acid group is bonded to at least one of Ar ₂ and Ar ₃ directly or via a linking group. X ₂ and X ₃ each independently represent —O—, —S—, —SO—, —SO ₂ —, —CO—, —CR ′ ″ R ″ ″ — or a direct bond; '''AndR''''each independently represent an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aryloxy group having 6 to 10 carbon atoms. And a plurality of X ₂ and X ₃ may be the same or different. ]


_{- (- Ar 4 -X 4 -Ar} 5 -X 5 -Ar 6 -X 6 -) m- (3)
[Wherein, m represents an integer of 10 or more, Ar ₄ , Ar ₅ and Ar ₆ each independently represents a divalent aromatic group, and the divalent aromatic group represents an alkyl group having 1 to 10 carbon atoms. Group, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms or an aryloxy group having 6 to 10 carbon atoms, and a plurality of Ar ₄ , Ar ₅ and Ar ₆ are each The acid groups may be the same or different, and an acid group is bonded to at least one of Ar ₄ , Ar ₅ and Ar ₆ directly or via a linking group. X _4, X ₅ and X ₆ are each independently —O—, —S—, —SO—, —SO ₂ —, —CO—, —CR ′ ″ R ″ ″ — or a direct bond. R ′ ″ and R ″ ″ each independently represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aryl having 6 to 10 carbon atoms Represents an oxy group, and a plurality of X _4, X ₅ and X ₆ may be the same or different from each other; ]

Ar ₁ , Ar ₂ , Ar ₃ , Ar ₄ , Ar _{5, and} Ar ₆ in formula (1), formula (2), and formula (3) each independently represent a divalent aromatic group, Examples of the group include hydrocarbon aromatic groups such as phenylene, naphthylene, biphenylylene, and fluorenediyl, and heteroaromatic groups such as pyridinediyl, quinoxalinediyl, and thiophenediyl. A divalent hydrocarbon-based aromatic group is preferable. Here, the divalent aromatic is substituted with an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aryloxy group having 6 to 10 carbon atoms. May be.

Examples of the alkyl group having 1 to 10 carbon atoms include methyl, ethyl, n-propyl, isopropyl, allyl, n-butyl, sec-butyl, tert-butyl, isobutyl, n-pentyl, 2,2- C1-C10 alkyl groups such as dimethylpropyl, cyclopentyl, n-hexyl, cyclohexyl, 2-methylpentyl, 2-ethylhexyl, etc., halogen atoms such as fluorine atom, chlorine atom, bromine atom, iodine atom, etc. Examples include an alkyl group substituted by a hydroxyl group, a nitrile group, an amino group, a methoxy group, an ethoxy group, isopropyloxy, phenyl, naphthyl, phenoxy, naphthyloxy, and the like.

  Examples of the optionally substituted alkoxy group having 1 to 10 carbon atoms include methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, sec-butyloxy, tert-butyloxy, isobutyloxy and n-pentyl. C1-C10 alkoxy groups such as oxy, 2,2-dimethylpropyloxy, cyclopentyloxy, n-hexyloxy, cyclohexyloxy, 2-methylpentyloxy, 2-ethylhexyloxy, etc., fluorine atoms, chlorine Examples thereof include halogen atoms such as atoms, bromine atoms and iodine atoms, alkoxy groups substituted by hydroxyl groups, nitrile groups, amino groups, methoxy groups, ethoxy groups, isopropyloxy, phenyl, naphthyl, phenoxy, naphthyloxy and the like.

Examples of the optionally substituted aryl group having 6 to 10 carbon atoms include aryl groups having 6 to 10 carbon atoms such as phenyl and naphthyl, and these groups include fluorine atom, chlorine atom, bromine atom and iodine atom. Examples include an aryl group substituted with a halogen atom, a hydroxyl group, a nitrile group, an amino group, a methoxy group, an ethoxy group, isopropyloxy, phenyl, naphthyl, phenoxy, naphthyloxy, or the like.

Examples of the optionally substituted aryloxy group having 6 to 10 carbon atoms include aryloxy groups having 6 to 10 carbon atoms such as phenoxy and naphthyloxy, and these groups include fluorine atom, chlorine atom, bromine atom and iodine. Examples thereof include halogen atoms such as atoms, hydroxyl groups, nitrile groups, amino groups, methoxy groups, ethoxy groups, isopropyloxy, phenyl, naphthyl, phenoxy, naphthyloxy substituted aryloxy groups, and the like.

Ar ₁ , Ar ₂ , Ar ₃ , Ar ₄ , Ar _5, Ar ₆ in the general formula (1), the general formula (2), and the general formula (3) may be substituted with the above substituents. Among them, Ar ₁ , Ar ₂ , Ar ₃ , Ar ₄ , Ar _5, Ar ₆ are more preferably phenylene and biphenylylene, and more preferably phenylene.

  Examples of the acid group in the general formula (1), the general formula (2), and the general formula (3) include a weak acid group such as a carboxyl group and a phospho group, a strong acid group such as a sulfo group and a sulfonylimide, and a perfluoroalkylene. Examples include a super strong acid group such as a sulfo group, a perfluorophenylene sulfo group, and a perfluoroalkylenesulfonylimide. Among them, a strong acid group and a super strong acid group are preferable, and examples thereof include a sulfo group, a perfluoroalkylene sulfo group, and a perfluorophenylene sulfo group. The number of acid groups is preferably 10% to 100%, more preferably 30% to 100%, based on the number of aromatic rings.

The acid group is directly bonded to Ar ₁ , Ar ₂ , Ar ₃ , Ar ₄ , Ar _5, Ar ₆ in the general formula (1), general formula (2), and general formula (3), or carbon Linkage such as alkylene having 1 to 10 carbons, alkylene having 1 to 10 carbon atoms and containing -O-, oxyalkylene having 1 to 10 carbon atoms, arylene having 6 to 10 carbon atoms, or oxyarylene having 6 to 10 carbon atoms It may be bonded to the polymer via a group. Examples of the alkylene having 1 to 10 carbon atoms include methylene, ethylene, n-propylene, isopropylene, n-butylene, sec-butylene, tert-butylene, isobutylene, n-pentylene, 2,2-dimethylpropylene, and cyclopentylene. Alkylene of 1 to 10 carbon atoms such as len, n-hexylene, cyclohexylene, 2-methylpentylene, 2-ethylhexylene, etc., halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, Examples include alkylene substituted with hydroxyl group, nitrile group, amino group, methoxy group, ethoxy group, isopropyloxy, phenyl, naphthyl, phenoxy, naphthyloxy and the like.

Examples of the alkylene having 1 to 10 carbon atoms and including -O- include, for example, methyleneoxymethylene, methyleneoxyethylene, methyleneoxypropylene, methyleneoxybutylene, methyleneoxypentylene, methyleneoxyhexylene, and methyleneoxyheptylene. , Methyleneoxyoctylene, methyleneoxynonylene, ethyleneoxymethylene, ethyleneoxyethylene, ethyleneoxypropylene, ethyleneoxybutylene, ethyleneoxypentylene, ethyleneoxyhexylene, ethyleneoxyheptylene, ethyleneoxyoctylene, propyleneoxy Methylene, propyleneoxyethylene, propyleneoxypropylene, propyleneoxybutylene, propyleneoxypentylene, propyleneoxyhexylene, propyleneoxyhept Tylene, butyleneoxymethylene, butyleneoxyethylene, butyleneoxypropylene, butyleneoxybutylene, butyleneoxypentylene, butyleneoxyhexylene, pentyleneoxymethylene, pentyleneoxyethylene, pentyleneoxypropylene, pentyleneoxybutylene, pentylene Oxypentylene, hexyleneoxymethylene, hexyleneoxyethylene, hexyleneoxypropylene, hexyleneoxybutylene, heptyleneoxymethylene, heptyleneoxyethylene, heptyleneoxypropylene, octyleneoxymethylene, octyleneoxy -O--containing alkylene such as ethylene, nonacyloxymethylene, etc., halogen atoms such as fluorine, chlorine, bromine, iodine, etc. Hexyl group, a nitrile group, an amino group, a methoxy group, an ethoxy group, isopropyloxy, phenyl, naphthyl, phenoxy, alkylene and the like which naphthyloxy contains a -O- was replaced.

  Examples of the oxyalkylene having 1 to 10 carbon atoms include methyleneoxy, ethyleneoxy, n-propyleneoxy, isopropyleneoxy, n-butyleneoxy, sec-butyleneoxy, tert-butyleneoxy, isobutyleneoxy, and n-pentylene. Oxyalkylene having 1 to 10 carbon atoms such as oxy, 2,2-dimethylpropyleneoxy, cyclopentyleneoxy, n-hexyleneoxy, cyclohexyleneoxy, 2-methylpentyleneoxy, 2-ethylhexyleneoxy, and the like Oxyalkylene in the above is substituted with halogen atom such as fluorine atom, chlorine atom, bromine atom, iodine atom, hydroxyl group, nitrile group, amino group, methoxy group, ethoxy group, isopropyloxy, phenyl, naphthyl, phenoxy, naphthyloxy, etc. Examples include oxyalkylene

Examples of the arylene having 6 to 10 carbon atoms include arylene having 6 to 10 carbon atoms such as phenylene and naphthylene, halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, hydroxyl group, nitrile group and the like. And arylene substituted with an amino group, methoxy group, ethoxy group, isopropyloxy, phenyl, naphthyl, phenoxy, naphthyloxy, and the like.

Examples of the oxyarylene having 6 to 10 carbon atoms include oxyarylene having 6 to 10 carbon atoms such as phenyleneoxy and naphthyleneoxy, halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, and hydroxyl group. Oxyarylene substituted with a nitrile group, amino group, methoxy group, ethoxy group, isopropyloxy, phenyl, naphthyl, phenoxy, naphthyloxy, and the like.

The average molecular weight of the polymer (B) having an acid group represented by the formulas (1), (2), and (3) is preferably 3000 to 100,000, more preferably 10,000 in terms of polystyrene-equivalent number average molecular weight. ~ 300,000.

Specific examples of the polymer (B) having an acid group are shown below. (In the following formula, t represents 0 or 1.
A plurality of t may be the same or different, but at least one is 1. )

Among the polymers of the general formula (1), general formula (2), and general formula (3), most preferred is a polymer in which an acid group is introduced into a super engineering plastic having a Tg of 200 ° C. or higher. For example, the sulfonated polyether ketone polymer exemplified in JP-A-11-502249 and the sulfonated polyethersulfone type exemplified in JP-A-10-45913 and JP-A-10-21943 A polymer.

Among the polymer (B) having an acid group, those having an electric conductivity of 1 × 10 ⁻⁷ S / cm or less are preferable.

In addition to the conductive polymer (A) having an acid group and the polymer (B) having an acid group, the hole injection layer possessed by the element of the present invention further comprises a low molecular weight hole injection material and a polymer type. Other materials such as a hole injection material and a conductive polymer may be included.

  Here, examples of the low molecular weight hole injection material include a pyralizone derivative, an arylamine derivative, a stilbene derivative, and a triphenyldiamine derivative. JP-A-63-70257, 63-175860, JP-A-2-135359, 2-135361, 2-209988, 3-79992, 3-152184 The hole transport material described in the publication is preferably used.

Examples of the polymer hole injection material include a polymer having a carbazole group, a polymer having an aromatic amine group, and a conductive polymer.
Examples of the polymer having a carbazole group and the polymer having an aromatic amine group include polyvinylcarbazole and its derivatives, and a polymer compound having an aromatic amine group in the main chain or side chain. Those described in JP-A-95537, JP-A-11-35687, and JP-A-2000-80167 are preferably used.

Examples of conductive polymers include polyacetylene and derivatives thereof, polyphenylene and derivatives thereof bonded at the para-position or meta-position, and polymers in which a phenyl group is connected via a divalent group (for example, a phenyl group via —CH═CH—). Polyphenylene vinylene and derivatives thereof linked to each other, polyphenylene sulfide and derivatives thereof linked to phenyl groups via —S—, polyphenylene oxide and derivatives thereof linked to phenyl groups via —O—), and five-membered rings Is a polymer containing one element other than C and H and connected at the 2,5 position (for example, polypyrrole and its derivatives with NH containing 5 and 5 rings connected at the 2,5 position, five members including S Polythiophene and its derivatives linked at the 2,5-position, polyfuran and derivatives thereof linked at the 5- and 5-positions containing O, and polysethenium with a 5-membered ring containing Se and linked at the 2,5-position Nophene and its derivatives, including polyterrophene and its derivatives in which a 5-membered ring containing Te is linked at the 2,5-positions, and polymers obtained by polymerizing aromatic amines (for example, polyaniline and its derivatives, polyamino And pyrene and derivatives thereof). Among these, polyaniline and derivatives thereof, polythiophene and derivatives thereof, polypyrrole and derivatives thereof are preferable, and polyaniline and derivatives thereof, polythiophene and derivatives thereof are preferable.

The organic EL device of the present invention has a light emitting layer in addition to the hole injection layer.
As a light emitting material used for the light emitting layer, a low molecular light emitter and a polymer light emitter can be used, but a polymer light emitter is preferable because a manufacturing process is easy.

  Examples of the low molecular weight light emitter include naphthalene or a derivative thereof, anthracene or a derivative thereof, perylene or a derivative thereof, a dye such as a polymethine group, a xanthene group, a coumarin group, and a cyanine group, 8-hydroxyquinoline or a derivative thereof. A metal complex, an aromatic amine, tetraphenylcyclopentadiene or a derivative thereof, or tetraphenylbutadiene or a derivative thereof can be used. Specific examples are described in JP-A-57-51781 and JP-A-59-194393.

The polymer light emitter is not limited as long as it is a polymer exhibiting fluorescence or phosphorescence, but a polymer light emitter having a repeating unit represented by the following general formula (4) and / or the following general formula (5) is preferable. Used for.
These polymer light emitters have a polystyrene-equivalent number average molecular weight of 1 × 10 ³ to 1 × 10 ⁷ , preferably 5 × 10 ³ to 1 × 10 ⁷ , and more preferably 1 × 10 ⁴ to. 5 × 10 ⁶ .

_{-Ar 7 - (Y 1) k} - (4)
[Wherein Ar ₇ represents an arylene group, a divalent heterocyclic group or a divalent group having a metal complex structure, Y ₁ represents —CR ₁ ═CR ₂ — or —C≡C—, R ₁ and R ₂ each independently represent a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group or a cyano group. k is an integer of 0-2. When a plurality of Y ₁ are present, they may be the same or different. ]

K in the general formula (4) is preferably 0 or 1.

（５）


〔ここで、Ａｒ₈およびＡｒ₉はそれぞれ独立にアリーレン基または２価の複素環基を示す。またＲ₃は、アルキル基、アリール基、１価の複素環基、下記式（６）で示される基または下記式（７）で示される基を示す。ｚは１〜４の整数である。
Ｒ₃がアリール基または１価の複素環基の場合、該アリール基、該１価の複素環基はアルキル基、アルコキシ基、アルキルチオ基、置換シリル基、置換アミノ基、アリール基、アリールオキシ基、アリールアルキル基、アリールアルコキシ基、アリールアルケニル基、アリールアルキニル基、１価の複素環基等の置換基を有していてもよい。〕

(5)


[Ar ₈ and Ar ₉ each independently represents an arylene group or a divalent heterocyclic group. R ₃ represents an alkyl group, an aryl group, a monovalent heterocyclic group, a group represented by the following formula (6), or a group represented by the following formula (7). z is an integer of 1-4.
When R ₃ is an aryl group or a monovalent heterocyclic group, the aryl group and the monovalent heterocyclic group are an alkyl group, an alkoxy group, an alkylthio group, a substituted silyl group, a substituted amino group, an aryl group, and an aryloxy group. , An arylalkyl group, an arylalkoxy group, an arylalkenyl group, an arylalkynyl group, and a monovalent heterocyclic group. ]

—Ar ₁₀ — (— Y ₂ —) pR ₄ (6)
(Here, Ar ₁₀ is an arylene group or a divalent heterocyclic group. R ₄ represents a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group, or a group represented by the following formula (4). Y ₂ represents —CR ₅ ═CR ₆ — or —C≡C—, wherein R ₅ and R ₆ each independently represents a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group or a cyano group. P represents an integer of 0 to 2. When R ₄ , R ₅ and R ₆ are an aryl group or a monovalent heterocyclic group, the aryl group and the monovalent heterocyclic group are an alkyl group, an alkoxy group Group, alkylthio group, substituted silyl group, substituted amino group, aryl group, aryloxy group, arylalkyl group, arylalkoxy group, arylalkenyl group, arylalkynyl group, monovalent heterocyclic group, etc. May be.)

（７）

（ここで、Ａｒ₁₁およびＡｒ₁₂はそれぞれ独立にアリーレン基または２価の複素環基である。また、Ｒ₇はアルキル基、アリール基または１価の複素環基を示す。Ｒ₈は水素原子、アルキル基、アリール基または１価の複素環基を示す。ｑは１〜４の整数である。
Ｒ₇およびＲ₈がアリール基または１価の複素環基の場合、該アリール基、該１価の複素環基はアルキル基、アルコキシ基、アルキルチオ基、置換シリル基、置換アミノ基、アリール基、アリールオキシ基、アリールアルキル基、アリールアルコキシ基、アリールアルケニル基、アリールアルキニル基、１価の複素環基等の置換基を有していてもよい。）

(7)

(Wherein Ar ₁₁ and Ar ₁₂ are each independently an arylene group or a divalent heterocyclic group. R ₇ represents an alkyl group, an aryl group or a monovalent heterocyclic group. R ₈ represents a hydrogen atom. , An alkyl group, an aryl group or a monovalent heterocyclic group, q is an integer of 1 to 4;
When R ₇ and R ₈ are an aryl group or a monovalent heterocyclic group, the aryl group and the monovalent heterocyclic group are an alkyl group, an alkoxy group, an alkylthio group, a substituted silyl group, a substituted amino group, an aryl group, It may have a substituent such as an aryloxy group, an arylalkyl group, an arylalkoxy group, an arylalkenyl group, an arylalkynyl group, and a monovalent heterocyclic group. )

Further, R ₁ , R ₂ , R ₄ , R ₅ , R ₆ , R ₈ are alkoxy groups, alkylthio groups, substituted silyl groups, substituted amino groups, aryloxy groups, depending on the stability of the compound and ease of production. An arylalkyl group, an arylalkoxy group, an arylalkenyl group, or an arylalkynyl group.

Ar _{7 to} Ar ₁₂ are an alkyl group, alkoxy group, alkylthio group, substituted silyl group, substituted amino group, aryl group, aryloxy group, arylalkyl group, arylalkoxy group, arylalkenyl group, arylalkynyl group, monovalent group It may have a substituent such as a heterocyclic group.

Z of the repeating unit represented by the general formula (5) is preferably 1 or 2, and p in the general formula (6) is preferably 0 or 1. Q in the general formula (7) is preferably 1 or 2.

  In the above formulas (4), (5), (6) and (7), the arylene group is an atomic group obtained by removing two hydrogen atoms from an aromatic hydrocarbon. Here, the aromatic hydrocarbon includes those having a condensed aromatic polycycle, and those obtained by bonding two or more independent benzene rings or condensed polycycles directly or via a group such as vinylene.

  As the compound having a condensed aromatic polycycle, an aromatic compound in which the number of carbon atoms contained in the ring is usually about 6 to 60 and 2 to 5 benzene rings are condensed is preferable. Specifically, naphthalene, anthracene, phenanthrene, pyrene, perylene, naphthacene, pentacene, chrysene, coronene and the like are preferable, and naphthalene and anthracene are preferable. From the viewpoint of solubility, it preferably has at least one substituent.

  Examples of those in which two or more independent benzene rings or condensed aromatic polycycles are bonded directly or via a group such as vinylene include a stilbene group and a distilbene group. Further, one or two groups selected from the group consisting of an alkoxy group, an aryl group substituted with an alkoxy group, an aryloxy group, and an arylalkoxy group may be present on the benzene ring. The distilbene group is a group having an arylene group or a divalent heterocyclic group at the center and a vinylene group between two phenylene groups.

  Specific examples of the arylene group include a phenylene group (for example, formulas 1 to 3 in the following figure), a naphthalenediyl group (formulas 4 to 13 in the following figure), an anthracenylene group (formulas 14 to 19 in the following figure), and a biphenyl-diyl group (the following figure). And terphenyl-diyl groups (formulas 26 to 28 in the following figure), condensed ring compound groups (formulas 29 to 38 in the following figure), and the like. Of these, a phenylene group, a biphenyl-diyl group, and a fluorene-diyl group (formulas 36 to 38 in the following figure) are preferable.

  The divalent heterocyclic group is an atomic group obtained by removing two hydrogen atoms from a heterocyclic compound. Here, the heterocyclic compound includes not only carbon atoms but also hetero atoms such as oxygen, sulfur, nitrogen, phosphorus and boron in the ring as elements constituting a single ring structure such as a 5-membered ring and a 6-membered ring. Say things. Furthermore, in addition to compounds having a single ring structure, the heterocyclic compounds include those having a condensed polycycle, those having an independent single heterocyclic compound or a condensed polycycle bonded directly or via a group such as vinylene. included. Here, the condensed polycyclic heterocyclic compound is an organic compound having a cyclic structure in which two or more rings are condensed, and the elements constituting the ring are not only carbon atoms, but also oxygen, sulfur, nitrogen, phosphorus, boron. And the like containing a heteroatom in the ring. The number of carbon atoms contained in the ring is preferably about 6 to 60, and more preferably 6 to 30. Specifically, quinoline, quinoxaline, acridine, phenanthroline, benzoxazole, benzothiazole, benzoxiadiazole, benzothiadiazole, dibenzofuran, dibenzothiophene, carbazole, etc., quinoline, benzoxadiazole, benzothiadiazole, carbazole preferable. From the viewpoint of solubility, it preferably has at least one substituent.

Here, the following are illustrated as a bivalent heterocyclic group.
Divalent heterocyclic group containing nitrogen as a hetero atom; pyridine-diyl group (formula 39 to 44 in the following figure), diazaphenylene group (formula 45 to 48 in the figure below), quinoline diyl group (formula 49 to 63 in the figure below), quinoxaline Diyl groups (formulas 64 to 68 in the lower figure), acridine diyl groups (formulas 69 to 72 in the lower figure), bipyridyldiyl groups (formulas 73 to 75 in the lower figure), phenanthroline diyl groups (formulas 76 to 78 in the lower figure), and the like.
Groups having a fluorene structure containing silicon, nitrogen, sulfur, selenium and the like as a hetero atom (formulas 79 to 93 in the following figure).
5-membered heterocyclic groups containing silicon, nitrogen, sulfur, selenium and the like as a hetero atom: (formulae 94 to 98 in the following figure)
5-membered condensed heterocyclic groups containing silicon, nitrogen, sulfur, selenium and the like as a hetero atom: (Formulas 99 to 108 in the following figure).
A 5-membered heterocyclic group containing silicon, nitrogen, sulfur, selenium, etc. as a heteroatom and bonded in the α-position of the heteroatom to form two-bodies or oligomers: (Formulas 109 to 110 in the figure below) Can be mentioned.
Examples of the 5-membered heterocyclic group containing silicon, nitrogen, sulfur, selenium and the like as a heteroatom are bonded to the phenyl group at the α-position of the heteroatom (formulas 111 to 117 in the following figure).
A group in which a compound group in which a benzene ring containing nitrogen, sulfur or the like as a hetero atom and a 5-membered heterocyclic ring are condensed is bonded to another aryl group (formulas 118 to 121 in the following figure).

In the above formula (4), the divalent group having a metal complex structure refers to the remaining divalent group obtained by removing two hydrogen atoms from the organic ligand of the metal complex having an organic ligand.
Carbon number of the organic ligand of the metal complex having an organic ligand is usually about 4 to 60. Examples of the organic ligand include 8-quinolinol and derivatives thereof, benzoquinolinol and derivatives thereof, 2-phenyl-pyridine and derivatives thereof, 2-phenyl-benzothiazole and derivatives thereof, 2-phenyl-benzoxazole and derivatives thereof. Derivatives, porphyrins and derivatives thereof.
Examples of the central metal of the metal complex having an organic ligand include aluminum, zinc, beryllium, iridium, platinum, gold, europium, and terbium.
Examples of the metal complex having an organic ligand include low-molecular fluorescent materials and phosphorescent materials known as so-called triplet light-emitting complexes.

  Examples of the divalent group having a metal complex structure include the following (122 to 128).

  In the above formulas 1-128, each R is independently a hydrogen atom, alkyl group, alkoxy group, alkylthio group, substituted amino group, substituted silyl group, aryl group, aryloxy group, arylalkyl group, arylalkoxy group, arylalkenyl group. Group, arylalkynyl group, monovalent heterocyclic group, cyano group and the like.

In the above example, one structural formula has a plurality of Rs, but they may be the same or different. In order to increase the solubility in a solvent, it is preferable that at least one of a plurality of Rs in one structural formula is other than a hydrogen atom, and the shape of a repeating unit including a substituent has little symmetry. Is preferred. Moreover, it is preferable that one or more of R in one structural formula is a group containing a cyclic or branched alkyl group. A plurality of R may be connected to form a ring.
In the above formula, in the substituent in which R contains an alkyl group, the alkyl group may be linear, branched or cyclic, or a combination thereof. - ethylhexyl group, 3,7-dimethyl octyl group, a cyclohexyl group, etc. 4-C ₁ ~C ₁₂ alkyl cyclohexyl groups.
Furthermore, the methyl group or methylene group of the alkyl group of the group containing the alkyl group may be replaced with a methyl group or methylene group substituted with a hetero atom or one or more fluorine atoms. Examples of these heteroatoms include oxygen atoms, sulfur atoms, nitrogen atoms and the like.
Furthermore, when R contains an aryl group or a heterocyclic group as a part thereof, they may further have one or more substituents.

  Here, the alkyl group may be linear, branched or cyclic, and usually has about 1 to 20 carbon atoms. Specific examples thereof include a methyl group, an ethyl group, a propyl group, an i-propyl group, and butyl. Group, i-butyl group, t-butyl group, pentyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, 3,7-dimethyloctyl group, lauryl group, etc. Pentyl group, hexyl group, octyl group, 2-ethylhexyl group, decyl group, and 3,7-dimethyloctyl group are preferable.

  The alkoxy group may be linear, branched or cyclic, and usually has about 1 to 20 carbon atoms. Specific examples thereof include a methoxy group, an ethoxy group, a propyloxy group, an i-propyloxy group, and a butoxy group. I-butoxy group, t-butoxy group, pentyloxy group, hexyloxy group, cyclohexyloxy group, heptyloxy group, octyloxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, 3,7-dimethyloctyloxy A pentyloxy group, a hexyloxy group, an octyloxy group, a 2-ethylhexyloxy group, a decyloxy group, and a 3,7-dimethyloctyloxy group.

  The alkylthio group may be linear, branched or cyclic, and usually has about 1 to 20 carbon atoms. Specific examples thereof include a methylthio group, an ethylthio group, a propylthio group, an i-propylthio group, a butylthio group, an i -Butylthio group, t-butylthio group, pentylthio group, hexylthio group, cyclohexylthio group, heptylthio group, octylthio group, 2-ethylhexylthio group, nonylthio group, decylthio group, 3,7-dimethyloctylthio group, laurylthio group, etc. And a pentylthio group, a hexylthio group, an octylthio group, a 2-ethylhexylthio group, a decylthio group, and a 3,7-dimethyloctylthio group are preferable.

Examples of the substituted silyl group include an alkyl group, an aryl group, an arylalkyl group or a monovalent heterocyclic group, a silyl group substituted with 1, 2 or 3 groups selected from substituents. It is about 1-60.
Specific examples of the substituted silyl group include trimethylsilyl group, triethylsilyl group, tripropylsilyl group, tri-i-propylsilyl group, dimethyl-i-propylsilyl group, diethyl-i-propylsilyl group, t-butylsilyldimethylsilyl. Group, pentyldimethylsilyl group, hexyldimethylsilyl group, heptyldimethylsilyl group, octyldimethylsilyl group, 2-ethylhexyl-dimethylsilyl group, nonyldimethylsilyl group, decyldimethylsilyl group, 3,7-dimethyloctyl-dimethylsilyl group , Lauryldimethylsilyl group, phenyl-C ₁ -C ₁₂ alkylsilyl group (C ₁ -C ₁₂ indicates that it has 1 to 12 carbon atoms, the same applies hereinafter), C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkylsilyl group, C ₁ -C ₁₂ alkyl phenylene -C ₁ -C ₁₂ alkylsilyl group, 1-naphthyl -C ₁ -C ₁₂ alkylsilyl group, 2-naphthyl -C ₁ -C ₁₂ alkylsilyl group, a phenyl -C ₁ -C ₁₂ alkyldimethylsilyl group, triphenylsilyl Silyl group, tri-p-xylylsilyl group, tribenzylsilyl group, diphenylmethylsilyl group, t-butyldiphenylsilyl group, dimethylphenylsilyl group, trimethoxysilyl group, triethoxysilyl group, tripropyloxysilyl group, tri- Examples include i-propylsilyl group, dimethyl-i-propylsilyl group, methyldimethoxysilyl group, ethyldimethoxysilyl group, and the like.
The substituted amino group means an amino group substituted with one or two groups selected from an alkyl group, an aryl group, an arylalkyl group or a monovalent heterocyclic group, and usually has about 1 to 60 carbon atoms. . Specifically, methylamino group, dimethylamino group, ethylamino group, diethylamino group, propylamino group, dipropylamino group, i-propylamino group, diisopropylamino group, butylamino group, i-butylamino group, t -Butylamino group, pentylamino group, hexylamino group, cyclohexylamino group, heptylamino group, octylamino group, 2-ethylhexylamino group, nonylamino group, decylamino group, 3,7-dimethyloctylamino group, laurylamino group, cyclopentylamino group, dicyclopentylamino group, cyclohexylamino group, dicyclohexylamino group, pyrrolidyl group, piperidyl group, ditrifluoromethylamino group, phenylamino group, diphenylamino group, C ₁ -C ₁₂ alkoxyphenyl amino group, di (C ₁ -C ₁₂ alkoxyphenyl) amino group, di (C ₁ -C ₁₂ alkylphenyl) amino groups, 1-naphthylamino group, 2-naphthylamino group, pentafluorophenylamino group, pyridylamino group, pyridazinylamino group , pyrimidylamino group, Pirajiruamino group, triazyl amino group phenyl -C ₁ -C ₁₂ alkylamino group, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkylamino group, C ₁ -C ₁₂ alkylphenyl -C ₁ ~ C ₁₂ alkylamino groups, di (C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkyl) amino group, di (C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkyl) amino groups, 1-naphthyl - Examples thereof include a C _{1 to} C ₁₂ alkylamino group, a 2-naphthyl-C _{1 to} C ₁₂ alkylamino group, and a carbazoyl group.

Aryl group is usually about 6 to 60 carbon atoms, and specific examples thereof include a phenyl group, C ₁ -C ₁₂ alkoxyphenyl group, C ₁ -C ₁₂ alkylphenyl group, 1-naphthyl group, 2-naphthyl such groups are exemplified, C ₁ -C ₁₂ alkoxyphenyl group, is C ₁ -C ₁₂ alkylphenyl group are preferable.

Aryloxy group is usually about 6 to 60 carbon atoms, specifically, phenoxy group, C ₁ -C ₁₂ alkoxy phenoxy group, C ₁ -C ₁₂ alkylphenoxy group, 1-naphthyloxy group, 2- naphthyloxy group and the like, C ₁ -C ₁₂ alkoxy phenoxy group, a C ₁ -C ₁₂ alkylphenoxy group are preferable.

Arylalkyl group has a carbon number of usually about 7 to 60, and specific examples thereof include a phenyl -C ₁ -C ₁₂ alkyl group, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkyl group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkyl group, 1-naphthyl -C ₁ -C ₁₂ alkyl group, 2-naphthyl -C ₁ -C ₁₂ alkyl groups and the like, C ₁ -C ₁₂ alkoxyphenyl - C ₁ -C ₁₂ alkyl group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkyl group are preferable.

The arylalkoxy group usually has about 7 to 60 carbon atoms. Specific examples thereof include a phenyl-C ₁ -C ₁₂ alkoxy group, a C ₁ -C ₁₂ alkoxyphenyl-C ₁ -C ₁₂ alkoxy group, and a C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkoxy groups, 1-naphthyl -C ₁ -C ₁₂ alkoxy groups, 2-naphthyl -C ₁ -C ₁₂ alkoxy groups and the like, C ₁ -C ₁₂ alkoxyphenyl - C ₁ -C ₁₂ alkoxy group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkoxy group are preferable.

Arylamino group is usually about 6 to 60 carbon atoms, the specific examples phenylamino group, diphenylamino group, C ₁ -C ₁₂ alkoxyphenyl amino group, di (C ₁ -C ₁₂ alkoxyphenyl) amino Group, di (C ₁ -C ₁₂ alkylphenyl) amino group, 1-naphthylamino group, 2-naphthylamino group and the like are exemplified, and C ₁ -C ₁₂ alkylphenylamino group, di (C ₁ -C ₁₂ alkylphenyl) The amino group is preferred.

Arylalkenyl group has a carbon number of usually about 8 to 60, and specific examples thereof include a phenyl -C ₂ -C ₁₂ alkenyl group, C ₁ -C ₁₂ alkoxyphenyl -C ₂ -C ₁₂ alkenyl group, C ₁ -C ₁₂ alkylphenyl -C ₂ -C ₁₂ alkenyl group, 1-naphthyl -C ₂ -C ₁₂ alkenyl group, 2-naphthyl -C ₂ -C ₁₂ alkenyl groups and the like, C ₁ -C ₁₂ alkoxyphenyl - C ₂ -C ₁₂ alkenyl group, C ₁ -C ₁₂ alkylphenyl -C ₂ -C ₁₂ alkenyl groups are preferred.

The arylalkynyl group usually has about 8 to 60 carbon atoms, and specific examples thereof include phenyl-C ₂ -C ₁₂ alkynyl group, C ₁ -C ₁₂ alkoxyphenyl-C ₂ -C ₁₂ alkynyl group, C ₁ -C ₁₂ alkylphenyl -C ₂ -C ₁₂ alkynyl group, 1-naphthyl -C ₂ -C ₁₂ alkynyl group, 2-naphthyl -C ₂ -C ₁₂ alkynyl groups and the like, C ₁ -C ₁₂ alkoxyphenyl - C ₂ -C ₁₂ alkynyl group, C ₁ -C ₁₂ alkylphenyl -C ₂ -C ₁₂ alkynyl group are preferable.

The monovalent heterocyclic group usually has about 4 to 60 carbon atoms, and specific examples thereof include thienyl group, C _{1 to} C ₁₂ alkyl thienyl group, pyrrolyl group, furyl group, pyridyl group, C _{1 to} C ₁₂ is alkylpyridyl like Jill group is thienyl group, C ₁ -C ₁₂ alkyl thienyl group, a pyridyl group, a C ₁ -C ₁₂ alkyl pyridyl group are preferable. The monovalent heterocyclic group refers to the remaining atomic group obtained by removing one hydrogen atom from a heterocyclic compound.

  In order to enhance the solubility of the polymer light emitter in the solvent, it is preferable to have at least one substituent, and it is preferable that the symmetry of the shape of the repeating unit including the substituent is small.

Among the substituent examples described so far, in the substituents including an alkyl chain, they may be either linear, branched or cyclic, or a combination thereof. group, 2-ethylhexyl group, 3,7-dimethyl octyl group, a cyclohexyl group, etc. 4-C ₁ ~C ₁₂ alkyl cyclohexyl groups. In order to enhance the solubility of the polymer light emitter in the solvent, one or more of the substituents of the repeating unit represented by formula (1) or formula (2) include a cyclic or branched alkyl chain. It is preferable. Moreover, the tips of two alkyl chains may be connected to form a ring. Furthermore, some carbon atoms of the alkyl chain may be replaced with a group containing a hetero atom, and examples of the hetero atom include an oxygen atom, a sulfur atom, and a nitrogen atom.
Furthermore, among the examples of substituents, when an aryl group or a heterocyclic compound group is included in a part thereof, they may further have one or more substituents.

ここに、Ｒは、それぞれ独立に水素原子、アルキル基、アルコキシ基、アルキルチオ基、置換アミノ基、置換シリル基、アリール基、アリールオキシ基、アリールアルキル基、アリールアルコキシ基、アリールアルケニル基、アリールアルキニル基、1価の複素環基、シアノ基等を表す。 Among the repeating units represented by the general formula (5), the following are preferable.

Here, each R is independently a hydrogen atom, alkyl group, alkoxy group, alkylthio group, substituted amino group, substituted silyl group, aryl group, aryloxy group, arylalkyl group, arylalkoxy group, arylalkenyl group, arylalkynyl. Group, monovalent heterocyclic group, cyano group and the like.

  The polymer light emitter may contain a repeating unit other than the repeating unit represented by formula (4) or formula (5). The total of repeating units represented by formula (4) and / or formula (5) is usually 50 mol% or more of all repeating units.

Specific examples of polymer light emitters include, for example, WO99 / 13692 publication specification, WO99 / 48160 publication specification, GB2340304A, WO00 / 53656 publication specification, WO01 / 19834 publication specification, WO00 / 55927 publication specification, GB2348316, WO00 / 46321 published specification, WO00 / 06665 published specification, WO99 / 54943 published specification, WO99 / 54385 published specification, US5777070, WO98 / 06773 published specification, WO97 / 05184 published specification, WO00 / 35987 published Specification, WO00 / 53655 publication specification, WO01 / 34722 publication specification, WO99 / 24526 publication specification, WO00 / 22027 publication specification, WO00 / 22026 publication specification, WO98 / 27136 Open specification, US573636, WO98 / 21262 published specification, US5741921, WO97 / 09394 published specification, WO96 / 29356 published specification, WO96 / 10617 published specification, EP0707020, WO95 / 07955 published specification, JP2001-181618 JP, 2001-123156, JP 2001-3045, JP 2000-351967, JP 2000-303066, JP 2000-299189, JP 2000-252065. JP-A-2000-136379, JP-A-2000-104057, JP-A-2000-80167, JP-A-10-324870, JP-A-10-114891, JP-A-9-111233, Kaihei 9 Of polyfluorene, derivatives and copolymers thereof, polyarylene, derivatives and copolymers thereof, polyarylene vinylene, derivatives and copolymers thereof, aromatic amines and derivatives thereof disclosed in Japanese Patent No. 45478 Examples are polymers.

The light emitting layer of the organic EL device of the present invention further contains one or more materials selected from hole transport materials, electron transport materials, light emitting materials other than polymer light emitters (for example, low molecular light emitters). May be.

Next, a method for producing a polymer light-emitting body containing the repeating unit represented by the general formula (4) and / or (5) will be described.
When the polymer light emitter has a vinylene group in the main chain, for example, a method described in JP-A-5-202355 can be mentioned. That is, polymerization by a Wittig reaction of a compound having an aldehyde group and a compound having a phosphonium base or a compound having an aldehyde group and a phosphonium base, a compound having a vinyl group and a compound having a halogen atom, or a vinyl group Polymerization by Heck reaction of a compound having a halogen atom, polymerization by a Horner-Wadsworth-Emmons method of a compound having an aldehyde group and a compound having an alkylphosphonate group, or a compound having an aldehyde group and an alkylphosphonate group, halogenation Polycondensation of a compound having two or more methyl groups by dehydrohalogenation method, polycondensation of a compound having two or more sulfonium bases by sulfonium salt decomposition method, having aldehyde group A method such as polymerization by a Knoevenagel reaction of a compound having an acetonitrile group or a compound having an acetonitrile group, or a method such as polymerization by a McMurry reaction of a compound having two or more aldehyde groups. Illustrated.
When the polymer light emitter has a triple bond in the main chain, for example, the Heck reaction can be used.

Further, when the polymer light emitter does not have a vinylene group or a triple bond in the main chain, for example, a method of polymerizing from a corresponding monomer by a Suzuki coupling reaction, a method of polymerizing by a Grignard reaction, a Ni (0) catalyst Examples thereof include a polymerization method, a polymerization method using an oxidizing agent such as FeCl ₃ , an electrochemical oxidative polymerization method, and a decomposition method of an intermediate polymer having an appropriate leaving group.

  Among these, polymerization by Wittig reaction, polymerization by Heck reaction, polymerization by Horner-Wadsworth-Emmons method, polymerization by Knoevenagel reaction, polymerization method by Suzuki coupling reaction, polymerization method by Grignard reaction, Ni (0) catalyst The method of polymerizing is preferable because the structure can be easily controlled.

  Specifically, a compound that has a plurality of reactive substituents, which is a monomer, is dissolved in an organic solvent as necessary, and reacted, for example, with an alkali or a suitable catalyst at a temperature not lower than the melting point of the organic solvent and not higher than the boiling point. Can do. For example, “Organic Reactions”, Vol. 14, pp. 270-490, John Wiley & Sons, Inc., 1965, “Organic Reactions”, Vol. 27, 345-390, John Wiley & Sons, Inc., 1982, "Organic Synthesis", Collective Volume VI, 407-411, John Wiley and Sons (407-411). John Wiley & Sons, Inc.), 1988, Chem. Rev., 95, 24. 7 (1995), Journal of Organometallic Chemistry (J. Organomet. Chem.), 576, 147 (1999), Journal of Practical Chemistry (J. Prakt. Chem.), 336, 247 (1994), Macromolecular Chemistry Macromolecular Symposium (Macromol. Chem., Macromol. Symp.), Vol. 12, p. 229 (1987), etc. can be used.

  The organic solvent varies depending on the compound and reaction to be used, but it is generally preferable that the solvent to be used is sufficiently deoxygenated and the reaction proceeds in an inert atmosphere in order to suppress side reactions. Similarly, it is preferable to perform a dehydration treatment. However, this is not the case in the case of a two-phase reaction with water, such as the Suzuki coupling reaction.

  In order to make it react, an alkali and a suitable catalyst are added suitably. These may be selected according to the reaction used. The alkali or catalyst is preferably one that is sufficiently dissolved in the solvent used in the reaction. As a method of mixing the alkali or catalyst, slowly add the alkali or catalyst solution while stirring the reaction solution under an inert atmosphere such as argon or nitrogen, or conversely, slowly add the reaction solution to the alkali or catalyst solution. And the method of adding.

  When a polymer light emitter is used in an organic EL device, the purity affects the device performance such as light emission characteristics. Therefore, the monomer before polymerization is polymerized after being purified by methods such as distillation, sublimation purification, and recrystallization. It is preferable. Further, after the polymerization, it is preferable to carry out a purification treatment such as reprecipitation purification and fractionation by chromatography.

  The organic EL device of the present invention has a hole injection layer and a light emitting layer between electrodes composed of an anode and a cathode, and the hole injection layer has a conductive polymer (A) having an acid group and the following general formula: (1), (2) and (3) containing the polymer (B) having an acid group.

  The organic EL device of the present invention may have a hole transport layer or an electron transport layer in addition to the hole injection layer and the light emitting layer. Here, the hole transport layer refers to a layer having a function of transporting holes, and the electron transport layer refers to a layer having a function of transporting electrons. The electron transport layer and the hole transport layer are collectively referred to as a charge transport layer. Two or more light emitting layers, hole transport layers, and electron transport layers may be used independently. Here, the hole transport layer and / or the electron transport layer may be two or more layers.

  That is, as the organic EL element of the present invention, in addition to an element having a hole injection layer in contact with the anode and further having a light emitting layer (for example, the following a)) between electrodes composed of an anode and a cathode, for example, EL element in which a hole transport layer is provided adjacent to the light emitting layer between the hole injection layer and the light emitting layer (for example, the following b)); between the cathode and the light emitting layer, the light emitting layer EL element having an electron transport layer adjacent thereto (for example, c) below; between the cathode and the light emitting layer, an electron transport layer is provided adjacent to the light emitting layer, and the hole transport layer and the light emitting layer An EL element (for example, the following d)) in which a hole transport layer is provided adjacent to the light emitting layer is used.

a) Anode / hole injection layer / light emitting layer / cathode b) Anode / hole injection layer / hole transport layer / light emitting layer / cathode c) Anode / hole injection layer / light emitting layer / electron transport layer / cathode d) Anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / cathode (where “/” indicates that each layer is laminated adjacently, the same shall apply hereinafter).

The film thickness of the hole injection layer of the organic EL device of the present invention varies depending on the material used, and may be selected so that the drive voltage and the light emission efficiency are appropriate. At least pinholes are generated. It is necessary to have such a thickness that it does not occur. If the thickness is too large, the driving voltage of the element becomes high, which is not preferable. Therefore, the film thickness of the hole injection layer is, for example, 1 nm to 300 nm, preferably 2 nm to 150 nm, and more preferably 10 nm to 100 nm.

As a method for forming the hole injection layer, the conductive polymer (A) having an acid group described above and a method of forming a film from a solution or dispersion containing the polymer (B), or electrochemical polymerization Is performed on the anode to form a hole injection layer.
Film formation methods from solution and from emulsion-dispersed water or alcohol include spin coating, casting, micro gravure coating, gravure coating, bar coating, roll coating, and wire bar. Coating methods such as a coating method, a dip coating method, a spray coating method, a screen printing method, a flexographic printing method, an offset printing method, and an inkjet printing method can be used.

The mixing ratio (weight ratio) of the conductive polymer (A) having an acid group and the polymer (B) having an acid group is optimal depending on the material used for the hole injection material and the material used for the light emitting layer. The values are different, and the driving voltage and the light emission efficiency may be selected so as to be moderate values.The mixing ratio is, for example, 5: 1 to 1:20, preferably 3: 1 to 1:10, Preferably it is 1: 1 to 1: 5.
If the ratio of the conductive polymer (A) having an acid group is too large, the luminous efficiency tends to decrease. If the ratio of the conductive polymer (A) having an acid group is too small, the luminous efficiency is low. There is a tendency to decrease.

  The hole injection layer is preferably transparent or translucent, that is, absorbs as little light as possible in the visible region. For example, the absorbance in the visible region is 0.2 or less, preferably 0.1 or less, more preferably 0.05 or less.

  The film thickness of the light-emitting layer of the organic EL device of the present invention may be selected so that the optimum value varies depending on the material used for the light-emitting layer and the drive voltage and light emission efficiency are appropriate. It is necessary to have such a thickness that does not occur. If the thickness is too large, the driving voltage of the element increases, which is not preferable. Therefore, the thickness of the light emitting layer is, for example, 1 nm to 1 μm, preferably 10 nm to 300 nm, and more preferably 20 nm to 150 nm.

  When a low molecular light emitter is used as the light emitting material, the light emitting layer can be formed, for example, by vacuum deposition or film formation from a mixed solution with a polymer binder.

Further, when a polymer light emitter is used as the light emitting material, the film can be formed from a solution containing the light emitter. In the case of forming a film from a solution, the same film forming method as that for the hole injection layer is employed.
The solvent used when the light emitting material is formed from a solution is not particularly limited as long as it dissolves a polymer light emitter or a polymer binder. Specifically, chlorinated solvents such as chloroform, methylene chloride, dichloroethane, ether solvents such as tetrahydrofuran, and aromatics such as toluene, xylene, mesitylene, 1,2,3,4-tetramethylbenzene, n-butylbenzene, etc. A compound solvent or the like is more preferably used.

  When the organic EL device of the present invention has an electron transport layer, the film thickness of the electron transport layer varies depending on the material used, and may be selected so that the drive voltage and the light emission efficiency are appropriate. The thickness must be such that at least pinholes do not occur. If the thickness is too large, the drive voltage of the element increases, which is not preferable. Accordingly, the thickness of the electron transport layer is, for example, 1 nm to 1 μm, preferably 2 nm to 300 nm, and more preferably 5 nm to 200 nm.

As the hole transporting material and the electron transporting material used in the organic EL device of the present invention, known low molecular compounds and high molecular compounds can be used, but it is preferable to use high molecular compounds.
As specific examples of the hole transporting material and the electron transporting material, as a polymer compound, WO99 / 13692 published specification, WO99 / 48160 published specification, GB2340304A, WO00 / 53656 published specification, WO01 / 19834 published specification , WO00 / 55927 published specification, GB2348316, WO00 / 46321 published specification, WO00 / 06665 published specification, WO99 / 54943 published specification, WO99 / 54385 published specification, US5777070, WO98 / 06773 published specification, WO97 / 05184 published specification, WO00 / 35987 published specification, WO00 / 53655 published specification, WO01 / 34722 published specification, WO99 / 24526 published specification, WO00 / 22027 published specification, WO00 / 2202 Published specification, WO98 / 27136 published specification, US573636, WO98 / 21262 published specification, US5741921, WO97 / 09394 published specification, WO96 / 29356 published specification, WO96 / 10617 published specification, EP07070720, WO95 / 07955 published specification , JP 2001-181618, JP 2001-123156, JP 2001-3045, JP 2000-351967, JP 2000-303066, JP 2000-299189, JP 2000-252065, JP 2000-136379, JP 2000-104057, JP 2000-80167, JP 10-324870, JP 10-114891, JP Polyfluorene, derivatives and copolymers thereof, polyarylene, derivatives and copolymers thereof, polyarylene vinylene, derivatives and copolymers thereof, which are disclosed in JP-A-9-111233, JP-A-9-45478, and the like, Examples are (co) polymers of aromatic amines and derivatives thereof.

As the hole transporting material of the polymer compound, those described in the above-mentioned literature are more preferably used, but other polymer compounds such as polyvinyl carbazole or a derivative thereof, polysilane or a derivative thereof, side A polysiloxane derivative having an aromatic amine in the chain or main chain, polyaniline or a derivative thereof, polythiophene or a derivative thereof, polypyrrole or a derivative thereof, or poly (2,5-thienylene vinylene) or a derivative thereof can also be used.
Examples of the hole transport material of the low molecular weight compound include pyrazoline derivatives, arylamine derivatives, stilbene derivatives, and triphenyldiamine derivatives.

As the electron transporting material of the polymer compound, polyquinoline or a derivative thereof, polyquinoxaline or a derivative thereof may be used in addition to the materials described in the literatures exemplified above.
Moreover, as an electron transport material of a low molecular weight compound, oxadiazole derivatives, anthraquinodimethane or derivatives thereof, benzoquinone or derivatives thereof, naphthoquinone or derivatives thereof, anthraquinones or derivatives thereof, tetracyanoanthraquinodimethane or derivatives thereof , Fluorenone derivatives, diphenyldicyanoethylene or derivatives thereof, diphenoquinone derivatives, or metals of 8-hydroxyquinoline or derivatives thereof. JP-A-63-70257, JP-A-63-175860, JP-A-2-135359, JP-A-2-135361, JP-A-2-209998, JP-A-3-37992, JP-A-3-152184 A hole transporting material or an electron transporting material described in the publication can be suitably used.

  The hole transport layer and the electron transport layer are formed using a hole transport material and an electron transport material, respectively. In the case where the hole transporting material or the electron transporting material is a low-molecular compound, film formation from a mixed solution with vacuum deposition or a polymer binder is exemplified. In the case of a polymer compound, the film is formed from a solution or a molten state. Can be membrane.

In the case of forming a hole transporting material of a polymer compound from a solution, the solvent used in the solution is not particularly limited as long as the material is dissolved. Specifically, chlorine-based solvents such as chloroform, methylene chloride, dichloroethane, and aromatic compound-based solvents such as toluene, xylene, mesitylene, 1,2,3,4-tetramethylbenzene, and n-butylbenzene are preferable. used.
The solvent used when the hole transport layer is formed from a solution is not particularly limited as long as it can dissolve a hole transport material and a polymer binder used as necessary. Examples of the solvent include chlorine solvents such as chloroform, methylene chloride, and dichloroethane; ether solvents such as tetrahydrofuran; aromatic hydrocarbon solvents such as toluene and xylene; ketone solvents such as acetone and methyl ethyl ketone; ethyl acetate, butyl acetate, An ester solvent such as ethyl cellosolve acetate is exemplified.

  There are no particular restrictions on the method for forming the electron transport layer, but for low molecular weight electron transport materials, a vacuum deposition method from powder or a method using film formation from a solution or a molten state can be used. Then, the method by the film-forming from a solution or a molten state is illustrated, respectively. In film formation from a solution or a molten state, a polymer binder may be used in combination.

  As the polymer binder to be mixed with the hole transporting material or the electron transporting material as necessary, those not extremely disturbing charge transport are preferable, and those having no strong absorption against visible light are suitably used. As the polymer binder, poly (N-vinylcarbazole), polyaniline or a derivative thereof, polythiophene or a derivative thereof, poly (p-phenylenevinylene) or a derivative thereof, poly (2,5-thienylenevinylene) or a derivative thereof, polycarbonate , Polyacrylate, polymethyl acrylate, polymethyl methacrylate, polystyrene, polyvinyl chloride, or polysiloxane.

The organic EL device of the present invention may have layers other than the anode, the cathode, the light emitting layer, the hole injection layer, the hole transport layer, and the electron transport layer.
Examples of such a layer include an electron injection layer and an insulating layer having a thickness of 10 nm or less (a thin buffer layer provided at the interface between the charge transport layer and the light-emitting layer in order to improve adhesion at the interface or prevent mixing). It is done.
Here, the layer provided adjacent to the cathode and having the function of improving the electron injection efficiency from the cathode and having the effect of lowering the driving voltage of the element is referred to as an electron injection layer. The order and number of layers to be laminated, and the thickness of each layer can be appropriately used in consideration of light emission efficiency and element lifetime.

  Specific examples of the electron injection layer include a work function of the cathode material and an electron affinity of the light emitting material contained in the light emitting layer or an electron contained in the electron transport layer provided between the cathode and the light emitting layer or the electron transport layer. A layer containing a material having an electron affinity with a value intermediate to that of the transport material is preferably used.

When the electron injection layer is a layer containing a conductive polymer, the layer is provided adjacent to the electrode between the cathode and the light emitting layer. The electrical conductivity of the conductive polymer is preferably 10 ⁻⁷ S / cm or more and 10 ³ S / cm or less. In order to reduce the leakage current between the light emitting pixels, 10 ⁻⁵ S / cm or more. 10 ² S / cm or less is more preferable, and 10 ⁻⁵ S / cm or more and 10 ¹ S / cm or less is more preferable. Usually, in order to set the electric conductivity of the conductive polymer to 10 ⁻⁵ S / cm or more and 10 ³ S / cm or less, the conductive polymer is doped with an appropriate amount of ions. The kind of ion to dope is a cation, and examples thereof include lithium ion, sodium ion, potassium ion, and tetrabutylammonium ion.
The thickness of the electron injection layer is, for example, 1 nm to 150 nm, and preferably 2 nm to 100 nm.

  As a method for forming the electron injection layer, film formation from a solution is exemplified, and it is only necessary to remove the solvent by drying after coating the solution, which is very advantageous in production. As a film forming method from a solution, a spin coating method, a casting method, a micro gravure coating method, a gravure coating method, a bar coating method, a roll coating method, a wire bar coating method, a dip coating method, a spray coating method, a screen printing method, Application methods such as a flexographic printing method, an offset printing method, and an ink jet printing method can be used. Also, an electron injection material that is in the form of an emulsion and dispersed in water or alcohol can be formed into a film by a method similar to that for a solution.

Examples of the insulating layer of 10 nm or less provided in contact with the cathode include metal fluorides, metal oxides, and organic insulating materials, and metal fluorides and metal oxides such as alkali metals and alkaline earth metals are preferable.
A vacuum deposition method is exemplified as a method for forming the inorganic compound used for the insulating layer.

  The substrate on which the organic EL device of the present invention is formed may be any substrate that does not change when forming the electrodes and each layer of the device, and examples thereof include glass, plastic, polymer film, and silicon substrate. In the case of an opaque substrate, the opposite electrode is preferably transparent or translucent.

Next, the anode and cathode that the organic EL device of the present invention has will be described.
In the organic EL device of the present invention, it is convenient that either one of the anode and the cathode is transparent or semi-transparent, since the emitted light is transmitted, and thus the emission efficiency of the emitted light is good.

  In the present invention, the anode side is preferably transparent or translucent, but as the material of the anode, a conductive metal oxide, a translucent metal, or the like is used. Specifically, indium oxide, zinc oxide, tin oxide, and their composite materials such as indium tin oxide (ITO), indium zinc oxide, etc., conductive glass (NESA etc.), gold, platinum Silver, copper and the like are used, and ITO, indium / zinc / oxide, and tin oxide are preferable. Further, an organic transparent conductive film such as polyaniline or a derivative thereof, polythiophene or a derivative thereof may be used as the anode.

  The film thickness of the anode can be appropriately selected in consideration of light transmittance and electrical conductivity, and is, for example, 10 nm to 10 μm, preferably 20 nm to 1 μm, more preferably 50 nm to 500 nm. is there.

  Examples of a method for producing the anode include a vacuum deposition method, a sputtering method, an ion plating method, and a plating method.

  As a material for the cathode used in the organic EL device of the present invention, a material having a small work function is preferable. For example, metals such as lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, aluminum, scandium, vanadium, zinc, yttrium, indium, cerium, samarium, europium, terbium, ytterbium, and their Two or more of these alloys, or an alloy of one or more of them and one or more of gold, silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten, tin, graphite or graphite intercalation compound, etc. Is used. Examples of the alloy include magnesium-silver alloy, magnesium-indium alloy, magnesium-aluminum alloy, indium-silver alloy, lithium-aluminum alloy, lithium-magnesium alloy, lithium-indium alloy, calcium-aluminum alloy, and the like. The cathode may have a laminated structure of two or more layers.

  The thickness of the cathode can be appropriately selected in consideration of electric conductivity and durability, but is, for example, 10 nm to 10 μm, preferably 20 nm to 1 μm, and more preferably 50 nm to 500 nm.

  As a method for producing the cathode, a vacuum deposition method, a sputtering method, a laminating method in which a metal thin film is thermocompression bonded, or the like is used.

  A protective layer for protecting the organic EL element may be attached after the cathode is produced. In order to use the organic EL element stably for a long period of time, it is preferable to attach a protective layer and / or a protective cover in order to protect the element from the outside.

  As the protective layer, a polymer compound, metal oxide, metal nitride, metal nitride oxide, metal fluoride, metal boride and the like can be used. Further, as the protective cover, a glass plate, a plastic plate having a low water permeability treatment on the surface, or the like can be used, and a method of sealing the cover by bonding it to the element substrate with a thermosetting resin or a photocurable resin is preferable. Used for. If the space is maintained by using the spacer, it is easy to prevent the element from being damaged. If an inert gas such as nitrogen or argon is enclosed in the space, the cathode can be prevented from being oxidized. Further, a desiccant such as barium oxide or calcium oxide can be installed in the space in the manufacturing process. It becomes easy to prevent the adsorbed moisture from deteriorating the performance of the device. Among these, it is preferable to take any one or more measures.

  The organic EL element of the present invention can be used as a planar light source, a segment display device, a dot matrix display device, a backlight of a liquid crystal display device, and the like.

In order to obtain planar light emission using the organic EL element of the present invention, the planar anode and cathode may be arranged so as to overlap each other. In addition, in order to obtain pattern-like light emission, a method of installing a mask provided with a pattern-like window on the surface of the planar light-emitting element, an organic material layer of a non-light-emitting portion is formed extremely thick and substantially non- There are a method of emitting light and a method of forming either one of the anode or the cathode or both electrodes in a pattern. By forming a pattern by any of these methods and arranging some electrodes so that they can be turned on / off independently, a segment type display element capable of displaying numbers, letters, simple symbols and the like can be obtained. Further, in order to obtain a dot matrix element, both the anode and the cathode may be formed in a stripe shape and arranged so as to be orthogonal to each other. Partial color display and multi-color display are possible by a method of separately coating a plurality of types of polymers having different emission colors or a method using a color filter or a fluorescence conversion filter. The dot matrix element may be either passive drive or active drive combined with a thin film transistor using amorphous silicon or low-temperature polysilicon. These display elements can be used as display devices for computers, televisions, mobile terminals, mobile phones, car navigation systems, video camera viewfinders, and the like.
Furthermore, the planar light-emitting element is a self-luminous thin type, and can be suitably used as a planar light source for a backlight of a liquid crystal display device or a planar illumination light source. If a flexible substrate is used, it can be used as a curved light source or display device.

The composition of the present invention contains a conductive polymer (A) having an acid group and a polymer (B) having an acid group selected from the above general formulas (1), (2) and (3). .

The composition of the present invention is useful as a material for thin films such as a conductive thin film, an antistatic thin film, an organic semiconductor thin film, a solar cell, and a charge injection thin film (hole injection layer).

  The preferred mixing ratio of the conductive polymer (A) to the polymer (B) of this composition varies depending on the application, but for example, when used as a material for a charge injection thin film (hole injection layer), the conductivity is high. The weight ratio of molecule (A) to polymer (B) is in the range of 5: 1 to 1:20.

Although the thickness of a thin film changes with the uses, it is 0.01-5 micrometers normally.
When a thin film is used as, for example, a hole injection layer, the film thickness is usually 1 nm to 300 nm. In addition, when used in applications such as antistatic purposes, the film thickness is about 0.01 μm to 5 μm (for example, JP 2003-039618 A).

  When used as a thin film for various purposes, it is useful that there is little absorption in the visible region. For example, when an organic EL device is produced using a thin film made of these compositions as a hole injection material, light is usually extracted from ITO. Therefore, if the thin film has absorption in the visible region (wavelength 400 to 800 nm), the luminous efficiency is small. Become. Accordingly, the absorbance of these thin films is preferably 0.2 or less, more preferably 0.1 or less.

When the thin film is a conductive thin film, its electric conductivity is 1 × 10 ⁻⁶ S / cm or more.

  When these compositions are used in various applications, a characteristic of this composition is that it has a conductivity indicating a semiconductor to a conductor.

  These compositions have sufficient conductivity to achieve an antistatic layer and can provide a solution suitable for substrate coating.

  The thin film has a certain degree of electrical conductivity and can be used as an organic semiconductor thin film. In recent years, organic semiconductor thin films have been used in various fields, not limited to organic LEDs and solar cells, but also to secondary batteries, fuel cells, capacitors, sensors, electronic components, organic TFTs, biofunctional devices, organic semiconductor lasers, etc. Has been deployed.

  In solar cells, materials that receive light energy, such as the sun and light bulbs, generate electrical energy. This solar cell mainly uses inorganic compound semiconductors, but studies using organic compounds are actively conducted due to low cost and environmental problems. The composition of the present invention can be used as a material for a cathode electrode or a charge transport layer.

  The composition of the present invention can be used as a charge injection thin film for light emitting devices.

The solution composition of the present invention is obtained by further adding a polar solvent to the composition of the present invention.

The proportion of the composition in the solution composition of the present invention is usually about 0.1 wt% to 50 wt% with respect to the total weight of the solution composition.

As the polar solvent, those having a dipole moment of 1.4 or more and 3.0 or less are preferable, and examples thereof include water, alcohol solvents, ether solvents, ketone solvents, ester solvents, amine solvents, sulfoxide solvents, amides. System solvents and the like.
Examples of alcohol solvents include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, t-butanol, pentanol, hexanol, and cyclohexanol. An alcohol solvent having 3 or less carbon atoms is preferred.
Examples of ether solvents include tetrahydrofuran and tetrahydropyran. Preferably, it is an ether solvent having 6 or less carbon atoms.
Examples of the ketone solvent include acetone, diethyl ketone, dibutyl ketone, 5-methyl-3-heptanone, cyclohexanone, and cyclopentanone. Preferably, it is a ketone solvent having 10 or less carbon atoms.
Examples of the ester solvent include methyl formate, ethyl formate, ethyl acetate, butyl acetate and the like. Preferably, it is an ester solvent having 10 or less carbon atoms.
Examples of amine solvents include pyridine. Preferably, it is an amine solvent having 10 or less carbon atoms.
Examples of the sulfoxide solvent include dimethyl sulfoxide. Preferably, it is a sulfoxide solvent having 10 or less carbon atoms.
Examples of the amide solvent include dimethylacetamide and N-methylpyrrolidone. An amide solvent having 10 or less carbon atoms is preferred.
Here, the polar solvent is preferably water, an alcohol solvent having 3 or less carbon atoms, an ether solvent having 4 or less carbon atoms, a ketone solvent having 5 or less carbon atoms, or a sulfoxide solvent having 4 or less carbon atoms. Furthermore, water is preferable.

  Since both compositions of the present invention have polar groups, they are soluble in a solvent having a high dipole moment. By obtaining a solution in which this composition is dissolved, processing for each application is facilitated.

Examples will be shown below for illustrating the present invention in more detail, but the present invention is not limited to these examples.
Here, with respect to the weight average molecular weight and the number average molecular weight, an average molecular weight in terms of polystyrene was determined by gel permeation chromatography (GPC) using chloroform as a solvent.

化合物Ａ
不活性雰囲気下１ｌの四つ口フラスコに２，８−ジブロモジベンゾチオフェン ７ｇとＴＨＦ ２８０ｍｌを入れ、室温で撹拌、溶かした後、−７８℃まで冷却した。ｎ−ブチルリチウム ２９ｍｌ（１．６モルヘキサン溶液）を滴下した。滴下終了後、温度を保持したまま２時間撹拌し、トリメトキシボロン酸 １３ｇを滴下した。滴下終了後、ゆっくり室温まで戻した。３時間室温で撹拌後、ＴＬＣで原料の消失を確認した。５％硫酸 １００ｍｌを加えて反応を終了させ、室温で１２時間撹拌した。水を加えて洗浄し、有機層を抽出した。溶媒を酢酸エチルに置換した後、３０％過酸化水素水 ５ｍｌを加え、４０℃で５時間撹拌した。その後有機層を抽出し、１０％硫酸アンモニウム鉄（II）水溶液で洗浄後乾燥、溶媒を除去することにより、茶色の固体 ４．４３ｇを得た。ＬＣ−ＭＳ測定からは二量体などの副生成物も生成しており、化合物Ａの純度は７７％であった（ＬＣ面百）。
ＭＳ（ＡＰＣＩ（−））：（Ｍ−Ｈ）^- ２１５ Synthesis Example 1 (Synthesis of Compound A)

Compound A
Under an inert atmosphere, 7 g of 2,8-dibromodibenzothiophene and 280 ml of THF were placed in a 1 l four-necked flask, stirred and dissolved at room temperature, and then cooled to -78 ° C. 29 ml of n-butyllithium (1.6 molar hexane solution) was added dropwise. After completion of dropping, the mixture was stirred for 2 hours while maintaining the temperature, and 13 g of trimethoxyboronic acid was added dropwise. After completion of dropping, the temperature was slowly returned to room temperature. After stirring at room temperature for 3 hours, disappearance of the raw material was confirmed by TLC. The reaction was terminated by adding 100 ml of 5% sulfuric acid and stirred at room temperature for 12 hours. Water was added for washing, and the organic layer was extracted. After replacing the solvent with ethyl acetate, 5 ml of 30% aqueous hydrogen peroxide was added and stirred at 40 ° C. for 5 hours. Thereafter, the organic layer was extracted, washed with a 10% aqueous solution of ammonium iron (II) sulfate, dried and the solvent was removed to obtain 4.43 g of a brown solid. By-products such as dimers were also produced from LC-MS measurement, and the purity of Compound A was 77% (LC area percentage).
MS (APCI (-)) :( M-H) - 215

化合物Ｂ
不活性雰囲気下で２００ｍｌの三つ口フラスコに化合物Ａ ４．４３ｇと臭化ｎ−オクチル ２５．１ｇ、および炭酸カリウム １２．５ｇ（２３．５ｍｍｏｌ）を入れ、溶媒としてメチルイソブチルケトン ５０ｍｌを加えて１２５℃で６時間加熱還流した。反応終了後、溶媒を除き、クロロホルムと水で分離、有機層を抽出し、さらに水で２回洗浄した。無水硫酸ナトリウムで乾燥後、シリカゲルカラム（展開溶媒：トルエン／シクロヘキサン＝１／１０）で精製することにより、８．４９ｇ（ＬＣ面百９７％、収率９４％）の化合物Ｂを得た。
¹Ｈ−ＮＭＲ（３００ＭＨｚ／ＣＤＣｌ₃）：
δ０．９１（ｔ、６Ｈ）、１．３１〜１．９０（ｍ、２４Ｈ）、４．０８（ｔ、４Ｈ）、７．０７（ｄｄ、２Ｈ）、７．５５（ｄ、２Ｈ）、７．６８（ｄ、２Ｈ） Synthesis Example 2 (Synthesis of Compound B)

Compound B
Under an inert atmosphere, 4.43 g of compound A, 25.1 g of n-octyl bromide, and 12.5 g (23.5 mmol) of potassium carbonate were placed in a 200 ml three-necked flask, and 50 ml of methyl isobutyl ketone was added as a solvent. The mixture was heated to reflux at 125 ° C. for 6 hours. After completion of the reaction, the solvent was removed, the organic layer was extracted with chloroform and water, and further washed twice with water. After drying over anhydrous sodium sulfate, purification was performed with a silica gel column (developing solvent: toluene / cyclohexane = 1/10) to obtain 8.49 g (LC area percentage 97%, yield 94%) of Compound B.
¹ H-NMR (300 MHz / CDCl ₃ ):
δ 0.91 (t, 6H), 1.31-1.90 (m, 24H), 4.08 (t, 4H), 7.07 (dd, 2H), 7.55 (d, 2H), 7 .68 (d, 2H)

化合物Ｃ Synthesis Example 3 (Synthesis of Compound C)

Compound C

In a 100 ml three-necked flask, 6.67 g of compound B and 40 ml of acetic acid were added, and the temperature was raised to 140 ° C. in an oil bath. Subsequently, 13 ml of 30% aqueous hydrogen peroxide was added from the condenser, and after vigorously stirring for 1 hour, the reaction was terminated by pouring into 180 ml of cold water. After extraction with chloroform and drying, the solvent was removed to obtain 6.96 g (LC area percentage 90%, yield 97%) of Compound C.
¹ H-NMR (300 MHz / CDCl ₃ ):
δ 0.90 (t, 6H), 1.26 to 1.87 (m, 24H), 4.06 (t, 4H), 7.19 (dd, 2H), 7.69 (d, 2H), 7 .84 (d, 2H)
MS (APCI (+)): (M + H) ^<+> 473

化合物Ｄ
不活性雰囲気下２００ｍｌ四つ口フラスコに化合物Ｃ ３．９６ｇと酢酸／クロロホルム＝１：１混合液 １５ｍｌを加え、７０℃で撹拌し、溶解させた。続いて、臭素 ６．０２ｇを上記の溶媒 ３ｍｌに溶かして加え、３時間撹拌した。チオ硫酸ナトリウム水溶液を加えて未反応の臭素を除き、クロロホルムと水で分離、有機層を抽出、乾燥した。溶媒を除去し、シリカゲルカラム（展開溶媒：クロロホルム／ヘキサン＝１／４）で精製することにより、４．４６ｇ（ＬＣ面百９８％、収率８４％）の化合物Ｄを得た。
¹Ｈ−ＮＭＲ（３００ＭＨｚ／ＣＤＣｌ₃）：
δ０．９５（ｔ、６Ｈ）、１．３０〜１．９９（ｍ、２４Ｈ）、４．１９（ｔ、４Ｈ）、７．０４（ｓ、２Ｈ）、７．８９（ｓ、２Ｈ）
ＭＳ（ＦＤ⁺）Ｍ⁺ ６３０ Synthesis Example 4 (Synthesis of Compound D)

Compound D
Under an inert atmosphere, 3.96 g of Compound C and 15 ml of a 1: 1 mixture of acetic acid / chloroform were added to a 200 ml four-necked flask, and the mixture was stirred at 70 ° C. to dissolve. Subsequently, 6.02 g of bromine was dissolved in 3 ml of the above solvent, and the mixture was stirred for 3 hours. An aqueous sodium thiosulfate solution was added to remove unreacted bromine, and the mixture was separated with chloroform and water, and the organic layer was extracted and dried. The solvent was removed and the residue was purified by a silica gel column (developing solvent: chloroform / hexane = 1/4) to obtain 4.46 g (LC area percentage 98%, yield 84%) of Compound D.
¹ H-NMR (300 MHz / CDCl ₃ ):
δ 0.95 (t, 6H), 1.30 to 1.99 (m, 24H), 4.19 (t, 4H), 7.04 (s, 2H), 7.89 (s, 2H)
MS (FD ⁺ ) M ⁺ 630

化合物Ｅ
不活性雰囲気下２００ｍｌ三つ口フラスコに化合物Ｄ ３．９ｇとジエチルエーテル ５０ｍｌを入れ、４０℃まで昇温、撹拌した。水素化アルミニウムリチウム １．１７ｇを少量ずつ加え、５時間反応させた。水を少量ずつ加えることによって過剰な水素化アルミニウムリチウムを分解し、３６％塩酸 ５．７ｍｌで洗浄した。クロロホルム、水で分離、有機層を抽出後乾燥した。シリカゲルカラム（展開溶媒：クロロホルム／ヘキサン＝１／５）で精製することにより、１．８ｇ（ＬＣ面百９９％、収率４９％）の化合物Ｅを得た。
¹Ｈ−ＮＭＲ（３００ＭＨｚ／ＣＤＣｌ₃）：
δ０．９０（ｔ、６Ｈ）、１．２６〜１．９７（ｍ、２４Ｈ）、４．１５（ｔ、４Ｈ）、７．４５（ｓ、２Ｈ）、７．９４（ｓ、２Ｈ）
ＭＳ（ＦＤ⁺）Ｍ⁺ ５９８ Synthesis Example 5 (Synthesis of Compound E)

Compound E
Under an inert atmosphere, 3.9 g of Compound D and 50 ml of diethyl ether were placed in a 200 ml three-necked flask, heated to 40 ° C. and stirred. Lithium aluminum hydride 1.17 g was added little by little and allowed to react for 5 hours. Excess lithium aluminum hydride was decomposed by adding water little by little and washed with 5.7 ml of 36% hydrochloric acid. Separated with chloroform and water, the organic layer was extracted and dried. Purification by a silica gel column (developing solvent: chloroform / hexane = 1/5) gave 1.8 g (LC area percentage 99%, yield 49%) of Compound E.
¹ H-NMR (300 MHz / CDCl ₃ ):
δ 0.90 (t, 6H), 1.26 to 1.97 (m, 24H), 4.15 (t, 4H), 7.45 (s, 2H), 7.94 (s, 2H)
MS (FD ⁺ ) M ⁺ 598

According to the MS (APCI (+)) method, peaks were detected at 615 and 598.

Synthesis Example 6
<Synthesis of Polymer Compound 1>
2,7-dibromo-9,9-dioctylfluorene (26 g, 0.047 mol), 2,7-dibromo-9,9-diisopentylfluorene (5.6 g, 0.012 mol) and 2,2′-bipyridyl (22 g, 0.141 mol) was dissolved in 1600 mL of dehydrated tetrahydrofuran, and the system was purged with nitrogen by bubbling with nitrogen. Under a nitrogen atmosphere, bis (1,5-cyclooctadiene) nickel (0) {Ni (COD) ₂ } (40 g, 0.15 mol) was added to this solution, and the temperature was raised to 60 ° C. and allowed to react for 8 hours. It was. After the reaction, this reaction solution was cooled to room temperature (about 25 ° C.), dropped into a mixed solution of 25% ammonia water 200 mL / methanol 1200 mL / ion-exchanged water 1200 mL and stirred for 30 minutes, and then the deposited precipitate was filtered. Air dried. Then, it melt | dissolved in 1100 mL of toluene, it filtered, and the filtrate was dripped at 3300 mL of methanol, and was stirred for 30 minutes. The deposited precipitate was filtered, washed with 1000 mL of methanol, and dried under reduced pressure for 5 hours. The yield of the obtained copolymer was 20 g (hereinafter referred to as polymer compound 1). The average molecular weight and weight average molecular weight in terms of polystyrene of the polymer compound 1 were Mn = 4.6 × 10 ⁴ and Mw = 1.1 × 10 ⁵ , respectively.

Synthesis example 7
<Synthesis of Polymer Compound 2>
2,7-dibromo-9,9-dioctylfluorene (5.8 g, 0.0105 mol), the above N, N′-bis (4-bromophenyl) -N, N′-bis (4-n-butylphenyl) -1,4-Phenylenediamine (3.1 g, 0.0045 mmol) and 2,2′-bipyridyl (6.6 g) were dissolved in 20 mL of dehydrated tetrahydrofuran, and the inside of the system was purged with nitrogen by bubbling with nitrogen. Under a nitrogen atmosphere, bis (1,5-cyclooctadiene) nickel (0) {Ni (COD) ₂ } (12.0 g) was added to this solution, the temperature was raised to 60 ° C., and the reaction was continued for 3 hours with stirring. I let you. After the reaction, this reaction solution is cooled to room temperature (about 25 ° C.), dropped into a mixed solution of 25% aqueous ammonia 50 mL / methanol about 200 mL / ion exchanged water about 300 mL, and stirred for 1 hour, and then the deposited precipitate is filtered. And dried under reduced pressure for 2 hours, and dissolved in about 350 mL of toluene. Thereafter, about 200 mL of 1N hydrochloric acid was added and stirred for 1 hour. The aqueous layer was removed, and about 200 mL of 4% aqueous ammonia was added to the organic layer. After stirring for 1 hour, the aqueous layer was removed. About 200 mL of ion exchange water was added to the organic layer and stirred, and then the aqueous layer was removed. The organic layer was dropped into about 700 mL of methanol and stirred for 1 hour, the deposited precipitate was filtered, dried under reduced pressure for 2 hours, and dissolved in about 350 mL of toluene. Thereafter, purification was performed through an alumina column, the recovered toluene solution was added dropwise to about 700 ml of methanol and stirred for 1 hour, and the deposited precipitate was filtered and dried under reduced pressure for 2 hours. The yield of the obtained copolymer (hereinafter referred to as polymer compound 2) was 3.5 g. The number average molecular weight and weight average molecular weight in terms of polystyrene were Mn = 3.4 × 10 ⁴ and Mw = 5.4 × 10 ⁴ , respectively.

Reference synthesis example 8
<Synthesis of polymer compound 3 aqueous solution> (Synthesis of sulfonated polyaniline aqueous solution)
The sulfonated polyaniline aqueous solution was synthesized according to a method described in known literature (Macromoleclues 1996, 29, p3950; JACS 1990, 112, p2800).
While 80 ml of fuming sulfuric acid was placed in a flask and cooled in an ice bath, 1.0 g of emeraldine base polyaniline (manufactured by Aldrich) was divided and charged as a solid. After completion of the preparation, the ice bath was removed and the mixture was stirred overnight.
After completion of the reaction, 400 ml of methanol was placed in a 1 liter beaker, and the reaction solution was added little by little over 30 minutes so that the internal temperature was around 15 to 20 ° C. while cooling in an ice bath. Furthermore, 200 ml of acetone was added and stirred, and then the precipitate was filtered with a glass filter. The operation of washing and filtering while repulping with 100 ml of methanol was repeated four times. About 1.1 g of a green solid was obtained.
Further, it was dissolved in 50 ml of a 0.1 mol / liter sodium hydroxide aqueous solution. It became a deep blue liquid. Excess sodium hydroxide was removed by dialysis using a dialysis cellulose tube (size 36/32) manufactured by Sanko Junyaku Co., Ltd., and about 50 g of a green aqueous solution was obtained through an ion exchange resin (manufactured by Aldrich). The solid content was about 1.7%.
The composition of the resulting sulfonated polyaniline was confirmed by elemental analysis. The obtained results agreed well with the calculated values when the sulfonation rate was 54% and the water content was 10 mol%.

※１：含水１０モル％で補正した分析値
※２：含水１０モル％、スルフォン化率５４％の場合の計算値

* 1: Analytical value corrected with water content of 10 mol% * 2: Calculated value when water content is 10 mol% and sulfonation rate is 54%

Reference synthesis example 9
<Synthesis of Polymer Compound 4>
1.50 g of SUMIKAEXCEL PES5200P (manufactured by Sumitomo Chemical Co., Ltd.) was dissolved in 20 g of 10% fuming sulfuric acid and sulfonated at room temperature for 3 days. The polymer sulfuric acid solution was then poured into ice water for dilution, and the polymer dilute sulfuric acid solution was dialyzed with a dialysis membrane (UC36-32-100, purchased from Sanko Junyaku Co., Ltd.) for 2 days in pure water to remove the sulfuric acid. The aqueous solution after dialysis was concentrated and dried to obtain sulfonated PES.

Example 1
After adding an aqueous solution of polymer compound 3 and an aqueous solution of polymer compound 4 in a weight ratio of 1: 2 to a glass substrate on which an ITO film having a thickness of 150 nm is formed by a sputtering method and mixing well, The mixed solution was formed into a film at 1000 rpm by spin coating. Then, it dried for 10 minutes at 110 degreeC on the hotplate in nitrogen atmosphere. Next, the polymer compound 1 and the polymer compound 2 obtained above were mixed at a ratio of 3: 7 and dissolved in toluene. At this time, it prepared so that the density | concentration of solid content might be about 1.5 wt%. A film was formed at 1400 rpm by spin coating using this toluene solution. Further, this was dried at 80 ° C. under reduced pressure for 1 hour, and then, as a cathode, lithium fluoride was deposited at about 4 nm, calcium was deposited at about 5 nm, and aluminum was then deposited at about 70 nm to produce an organic EL device. After the degree of vacuum reached 1 × 10 ⁻⁴ Pa or less, metal deposition was started.
When voltage was applied to the obtained device, blue light emission having a peak wavelength of 468 nm was exhibited, and the light emission starting voltage at 1 cd / cm ² was 3.1V.
When voltage was applied to the obtained device and the current density was set to 25 mA / cm ² , the initial luminance was 240 cd / m ² and the time until the luminance was attenuated to 60% was 70 hours.

Comparative Example 1
A device was prepared in the same manner as in Example 1 except that polyacrylic acid was used instead of the polymer compound 4 in Example 1. This device emitted blue light with an emission peak of 464 nm. The emission start voltage at 1 cd / cm ² was 4.6V. The highest efficiency was 0.2 cd / A. When voltage was applied to the obtained device and the current density was set to 25 mA / cm ² , the initial luminance was 71 cd / m ² and the time until the luminance was attenuated to 60% was 0.4 hours.

Comparative Example 2
A device was prepared in the same manner as in Example 1 except that polyvinyl alcohol was used instead of the polymer compound 4 in Example 1. This device emitted blue light with an emission peak of 464 nm. The light emission starting voltage at 1 cd / cm ² was 2.9V. The highest efficiency was 2.1 cd / A. When voltage was applied to the obtained device and the current density was set to 25 mA / cm ² , the initial luminance was 308 cd / m ² and the time until the luminance was attenuated to 60% was 7.2 hours.

Comparative Example 3
A device was prepared in the same manner as in Example 1 except that polystyrenesulfonic acid was used instead of the polymer compound 4 in Example 1. This device emitted blue light with an emission peak of 464 nm. The light emission starting voltage at 1 cd / cm ² was 3.2V. When voltage was applied to the obtained device and the current density was set to 25 mA / cm ² , the initial luminance was 305 cd / m ² and the time until the luminance was attenuated to 60% was 35 hours.

Claims (19)

A hole injection layer and a light-emitting layer are provided between electrodes composed of an anode and a cathode, and the hole injection layer includes an electroconductive polymer (A) having an acid group and the following general formulas (1), (2) and An organic electroluminescent device comprising a polymer (B) having a sulfo group selected from (3).

-(-Ar ₁ -X _1- ) _m- (1)
[Wherein, m represents an integer of 10 or more, Ar ₁ represents a divalent aromatic group, and the divalent aromatic group includes an alkyl group having 1 to 10 carbon atoms and an alkoxy group having 1 to 10 carbon atoms. group, may be substituted with an aryl group or an aryloxy group having 6 to 10 carbon atoms of 6 to 10 carbon atoms, more Ar ₁ may be the same or different and at least one of Ar ₁ A sulfo group is bonded directly or via a linking group. X ₁ represents —O—, —S—, —SO—, —SO ₂ —, —CO—, —CR ′ ″ R ″ ″ — or a direct bond, and R ′ ″ and R ″. '' are each independently an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryloxy group an aryl group or a C 6-10 having 6 to 10 carbon atoms, more X ₁ is , May be the same or different. ]

_{- (- Ar 2 -X 2 -Ar} 3 -X 3 -) m - (2)
[Wherein, m represents an integer of 10 or more, Ar ₂ and Ar ₃ each independently represent a divalent aromatic group, and the divalent aromatic group includes an alkyl group having 1 to 10 carbon atoms, carbon It may be substituted with an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms or an aryloxy group having 6 to 10 carbon atoms, and a plurality of Ar ₂ and Ar ₃ may be the same or different. And a sulfo group is bonded to at least one of Ar ₂ and Ar ₃ directly or via a linking group. X ₂ and X ₃ each independently represent —O—, —S—, —SO—, —SO ₂ —, —CO—, —CR ′ ″ R ″ ″ — or a direct bond; '''AndR''''each independently represent an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aryloxy group having 6 to 10 carbon atoms. And a plurality of X ₂ and X ₃ may be the same or different. ]

— (— Ar ₄ —X ₄ —Ar ₅ —X ₅ —Ar ₆ —X ₆ —) _m — (3)
[Wherein, m represents an integer of 10 or more, Ar ₄ , Ar ₅ and Ar ₆ each independently represents a divalent aromatic group, and the divalent aromatic group represents an alkyl group having 1 to 10 carbon atoms. Group, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms or an aryloxy group having 6 to 10 carbon atoms, and a plurality of Ar ₄ , Ar ₅ and Ar ₆ are each They may be the same or different, and a sulfo group is bonded to at least one of Ar ₄ , Ar ₅ and Ar ₆ directly or via a linking group. X _4, X ₅ and X ₆ are each independently —O—, —S—, —SO—, —SO ₂ —, —CO—, —CR ′ ″ R ″ ″ — or a direct bond. R ′ ″ and R ″ ″ each independently represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aryl having 6 to 10 carbon atoms Represents an oxy group, and a plurality of X _4, X ₅ and X ₆ may be the same or different from each other; ]   The conductive polymer (A) having an acid group is polyacetylene having an acid group, polyphenylene having an acid group, polyphenylene vinylene, polyphenylene sulfide having an acid group, polyphenylene oxide having an acid group, polypyrrole having an acid group, an acid group The organic electroluminescence device according to claim 1, which is polythiophene having an acid group, polyfuran having an acid group, polyselenophene having an acid group, polytellurophene having an acid group, polyaniline having an acid group, or polyaminopyrene having an acid group. Acid group is a carboxyl group of the conductive polymer having an acid group (A), phospho group, a sulfo group, sulfonylimide, perfluoroalkylene sulfo group, according to claim 1 or perfluorophenylene sulfo group or perfluoroalkylene imide 2. The organic electroluminescence device according to 2. The light emitting layer contains a polymer light emitter containing at least one type of repeating unit represented by the following general formula (4) and having a polystyrene-equivalent number average molecular weight of 1 × 10 ³ to 1 × 10 ^7. The organic electroluminescent element according to claim 1.

_{-Ar 7 - (Y 1) k} - (4)
[Wherein Ar ₇ represents an arylene group, a divalent heterocyclic group or a divalent group having a metal complex structure, Y ₁ represents —CR ₁ ═CR ₂ — or —C≡C—, R ₁ and R ₂ each independently represent a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group or a cyano group. k is an integer of 0-2. When a plurality of Y ₁ are present, they may be the same or different. ]   The organic light-emitting device according to claim 4, wherein the light-emitting layer further contains one or more materials selected from a hole transport material, an electron transport material, and a light-emitting material.   A planar light source using the organic electroluminescence element according to claim 1.   A segment display device using the organic electroluminescence element according to claim 1. A dot matrix display device using the organic electroluminescence element according to claim 1.   A liquid crystal display device comprising the organic electroluminescence element according to claim 1 as a backlight. A conductive polymer having an acid group (A), under following general formula (1), (2) and (3) a composition containing a polymer (B) having a sulfo group selected from.
-(-Ar ₁ -X _1- ) _m- (1)
[Wherein, m represents an integer of 10 or more, Ar ₁ represents a divalent aromatic group, and the divalent aromatic group includes an alkyl group having 1 to 10 carbon atoms and an alkoxy group having 1 to 10 carbon atoms. group, may be substituted with an aryl group or an aryloxy group having 6 to 10 carbon atoms of 6 to 10 carbon atoms, more Ar ₁ may be the same or different and at least one of Ar ₁ A sulfo group is bonded directly or via a linking group. X ₁ represents —O—, —S—, —SO—, —SO ₂ —, —CO—, —CR ′ ″ R ″ ″ — or a direct bond, and R ′ ″ and R ″. '' are each independently an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryloxy group an aryl group or a C 6-10 having 6 to 10 carbon atoms, more X ₁ is , May be the same or different. ]

_{- (- Ar 2 -X 2 -Ar} 3 -X 3 -) m - (2)
[Wherein, m represents an integer of 10 or more, Ar ₂ and Ar ₃ each independently represent a divalent aromatic group, and the divalent aromatic group includes an alkyl group having 1 to 10 carbon atoms, carbon It may be substituted with an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms or an aryloxy group having 6 to 10 carbon atoms, and a plurality of Ar ₂ and Ar ₃ may be the same or different. And a sulfo group is bonded to at least one of Ar ₂ and Ar ₃ directly or via a linking group. X ₂ and X ₃ each independently represent —O—, —S—, —SO—, —SO ₂ —, —CO—, —CR ′ ″ R ″ ″ — or a direct bond; '''AndR''''each independently represent an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aryloxy group having 6 to 10 carbon atoms. And a plurality of X ₂ and X ₃ may be the same or different. ]

— (— Ar ₄ —X ₄ —Ar ₅ —X ₅ —Ar ₆ —X ₆ —) _m — (3)
[Wherein, m represents an integer of 10 or more, Ar ₄ , Ar ₅ and Ar ₆ each independently represents a divalent aromatic group, and the divalent aromatic group represents an alkyl group having 1 to 10 carbon atoms. Group, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms or an aryloxy group having 6 to 10 carbon atoms, and a plurality of Ar ₄ , Ar ₅ and Ar ₆ are each They may be the same or different, and a sulfo group is bonded to at least one of Ar ₄ , Ar ₅ and Ar ₆ directly or via a linking group. X _4, X ₅ and X ₆ are each independently —O—, —S—, —SO—, —SO ₂ —, —CO—, —CR ′ ″ R ″ ″ — or a direct bond. R ′ ″ and R ″ ″ each independently represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aryl having 6 to 10 carbon atoms Represents an oxy group, and a plurality of X _4, X ₅ and X ₆ may be the same or different from each other; ] The composition according to claim 10, wherein the weight ratio of the conductive polymer (A) having an acid group to the polymer (B) having a sulfo group is 5: 1 to 1:20.   The composition according to claim 10 or 11, further comprising a polar solvent.   A thin film comprising the composition according to claim 10 or 11 and having a thickness of 0.01 to 5 µm.   14. The thin film according to claim 13, wherein the absorbance at a wavelength of 400 to 800 nm is 0.2 or less. A conductive thin film comprising the composition according to claim 10 or 11 and having an electric conductivity of 1 × 10 ⁻⁶ S / cm or more.   The antistatic thin film containing the composition of Claim 10 or 11.   The organic-semiconductor thin film containing the composition of Claim 10 or 11.   The solar cell containing the composition of Claim 10 or 11.   A charge injectable thin film of a light emitting device containing the composition according to claim 10.